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Crystal and molecular structures of some cyclic phosphonitriles Marsh, Wayne Clifford 1970

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THE CRYSTAL AND MOLECULAR STRUCTURES OF SOME CYCLIC PHOSPHONITRILSS by WAYNE CLIFFORD MARSH B.A.(Hon.), U n i v e r s i t y o f Saskatchewan, M.A., U n i v e r s i t y o f Saskatchewan,  196$, 1967,  A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY  i n t h e Department of Chemistry  We a c c e p t t h i s t h e s i s a s c o n f o r m i n g t o t h e required  standard  THE UNIVERSITY OF BRITISH COLUMBIA June,  1970  \  ii  ABSTRACT Supervisor:  Professor  James T r o t t e r  S i n g l e c r y s t a l X-ray d i f f r a c t i o n methods have been usee to determine the s t r u c t u r e s o f f o u r c y c l i c  phosphoni-  1,1,5,5-tetrafluoro-3 ,3,7,7-tetramethylcyclotetra-  triles:  phosphenitriie,  ; 1,1,3,3,5,5-hexafluoro-7,7-dimethyl-  N^P^F^Me  cyclotetraphosphonitrile,  N,P,F_-Me ; hexaphenoxycyclotriphos0  4 4 °  phonitrile,  ^ N P C d P h ^ j y,  and dodeca(dimethylamino )-  cyclchexaphosphonitrilechlorocopper (I),  NgP^(KKeg )_2^ ^^J CuCJJ2~« u  +  (II)  dichlorocuprate  I n t e n s i t y measurements  were made on a Datex automated General E l e c t r i c  diffractometer  u s i n g a s c i n t i l l a t i o n counter; Cu-K ^. r a d i a t i o n being used for  the f i r s t three  s t r u c t u r e d e t e r m i n a t i o n s and Mo-K  r a d i a t i o n f o r the f o u r t h . The Patterson  s t r u c t u r e of N^P^F^Me^ has been determined by  and F o u r i e r methods ana r e f i n e d by f u l l - m a t r i x  least-squares.  The molecule i s s i t u a t e d on a  a x i s , and  the p h o s p h o n i t r i l i c r i n g has t h e 'saddle' conformation. D i f f e r e n t e l e c t r o n e g a t i v i t i e s o f the s u b s t i t u e n t i n two d i s t i n c t P-N bond l e n g t h s , i n terms o f  1.53  f f -bonding t h e o r i e s .  and 1.59  groups r e s u l t \ explicable  In  presenting  this  an a d v a n c e d  degree  the  shall  I  Library  f u r t h e r agree  for  scholarly  by h i s of  thesis at  the U n i v e r s i t y  make  that  it  thesis  purposes  written  for  may  financial  is  of  August 1 0 , 1970  British  by  for  gain  Columbia  shall  the  that  not  requirements  Columbia,  I  agree  r e f e r e n c e and copying  t h e Head o f  understood  Chemistry  The U n i v e r s i t y o f B r i t i s h V a n c o u v e r 8 , Canada  of  for extensive  be g r a n t e d  It  fulfilment of  available  permission.  Department  Date  freely  permission  representatives.  this  in p a r t i a l  of  or  that  study.  this  thesis  my D e p a r t m e n t  copying  for  or  publication  be a l l o w e d w i t h o u t  my  iii  P a t t e r s o n , F o u r i e r , and f u l l - m a t r i x l e a s t - s q u a r e s methods have been used t o determine t h e s t r u c t u r e o f N^P^F^Me^.  This* m o l e c u l e i s a l s o s i t u a t e d on a CL, a x i s and  has t h e 'saddle' planarity.  c o n f o r m a t i o n , but t e n d s s t r o n g l y towards  The most i n t e r e s t i n g f e a t u r e s o f t h e r i n g a r e  f o u r d i s t i n c t P-N bond l e n g t h s 1.437 2 ) , and l a r g e v a l e n c y  a n g l e s (145°) a t n i t r o g e n , w h i c h  are e x p l i c a b l e i n terms o f The  structure of  (1.534, 1.470, 1.532, and  f f -bonding t h e o r i e s . [ N P ( G P h ) l o was d e t e r m i n e d from 9  P a t t e r s o n and F o u r i e r s y n t h e s e s , and r e f i n e m e n t o f p o s i t i o n a l and  t h e r m a l parameters o f t h e atoms by b l o c k - d i a g o n a l  squares.  The p h o s p h o n i t r i l i c r i n g i s s l i g h t l y o  least-  non-planar,  w i t h two n i t r o g e n atoms d i s p l a c e d by 0.15 A i n o p p o s i t e e c t i o n s from t h e p l a n e o f t h e o t h e r f o u r The  dir-  (3P and I N ) atoms.  c o n f o r m a t i o n s o f t h e phenoxy groups a r e d i f f e r e n t a t t h e  t h r e e phosphorus atoms, and t h e r e a r e s m a l l d e v i a t i o n s among chemically-equivalent  angles;  these d i f f e r e n c e s a r e probably  a r e s u l t o f i n t r a - and i n t e r m o l e c u i a r are no d i f f e r e n c e s among c h e m i c a l l y  steric effects.  equivalent  bond  There  lengths,  the mean o d i s t a n c e s b e i n g P-N 1.575(2), P-0 1.532(2), 0-C 1.406(3) A .  The  structure of  determined by P a t t e r s o n , squares methods.  F o u r i e r , and f u l l - m a t r i x l e a s t -  The s t r u c t u r e i s i o n i c w i t h t h e c a t i o n and  iv  a n i o n each s i t u a t e d on a  axis.  The c a t i o n c o n s i s t s o f a  C u ( I I ) bonded t o f o u r n i t r o g e n s o f t h e p h o s p h o n i t r i i i c (N-Cu 2.07  A) and a c h l o r i n e  square pyramid. bond l e n g t h  The Cu( 1)0^2  o f 2.11  A*.  fY  -bonding t h e o r y .  2) i n a distorted  a n i o n i s l i n e a r w i t h a Cu-C£  There a r e two d i s t i n c t P-N bond l e n g t h s  i n the p h o s p h o n i t r i i i c r i n g , by  (Cfl-Cu 2.28  ring  1.62  and 1 . 5 5  A,  explicable  The o v e r a l l shape o f the  structure  i s d e t e r m i n e d p r i m a r i l y by s t e r i c e f f e c t s and the d i s t o r t i o n o f the p h o s p h o n i t r i i i c r i n g caused by t h e bonding t o copper.  V  TABLE OF CONTENTS PAGE TITLE PAGE .  i  ABSTRACT  i i  TABLE OF CONTENTS  v  LIST OF TABLES  v i i  LIST OF FIGURES  x  ACKNOWLEDGEMENTS  .  x i i 1  GENERAL INTRODUCTION PART I .  THE CRYSTAL AND MOLECULAR STRUCTURES OF 1,1,5,5-TETRAFLUORO-3,3,7,7-TETRAMETHYLCYCLOTETRAPHOSPHONITRILE AND 1 , 1 , 3 , 3 , 5 , 5 HEXAFLUORO-7,7-DIMETHYLCYCLOTETRAPHOSPHONITRILE  . . . . .  1.1  INTRODUCTION  1.2  THE CRYSTAL AND MOLECULAR STRUCTURE OF  , . . . .  4 5  1,1,5,5-TETRAFLUORO-3,3,7,7-TETRAMETHYLCYCLO-  1.3  TETRAPHOSPHONITRILE  15  1.2.1  Experimental  15  1.2.2  Structure Analysis  16  1.2.3  Discussion  22  THE CRYSTAL AND MOLECULAR STRUCTURE OF 1,1,3,3,5,5-HEXAFLUORO-7,7-DIMETHYLCYCLOTETRAPHOSPHONITRILE  32  vi  PART I I .  1.3.1  Experimental  32  1.3.2  Structure Analysis  34  1.3.3  Discussion  44  THE STRUCTURE DETERMINATION OF HEXAPHENOXYCYCLOTRIPHOSPHONITRILE  49  2.1  INTRODUCTION  50  2.2  EXPERIMENTAL  52  2.3  STRUCTURE ANALYSIS  53  2.4  DISCUSSION  64  PART I I I .  THE CRYSTAL AND MOLECULAR STRUCTURE OF D ODECA(DIMETHYLAMINO)CYCLOHEXPH OSPH ONITRILECHLOROCOPPER(II) DICHLOROCUPRATE  (I). . .  75  3.1  INTRODUCTION.  76  3.2  EXPERIMENTAL  77  3.3  STRUCTURE ANALYSIS  79  3.4  DISCUSSION  88  REFERENCES  100  vii  LIST OF TABLES TABLE I  PAGE S t r u c t u r a l parameters f o r t e t r a m e r i c 10  phosphonitriles 1»1»5 > 5 - t e t r a f l u o r o - 3 . 3 . 7 , 7 - t e t r a f l u o r o cyclotetraphosphonitrile II  E - s t a t i s t i c s f o r N. P, F.Me. 4 4 4 4  III  Observed and f i n a l c a l c u l a t e d  18 structure 20  factors IV  F i n a l p o s i t i o n a l parameters w i t h standard d e v i a t i o n s and a n i s o t r o p i c thermal  para21  meters V  Bond l e n g t h s and v a l e n c y angles w i t h  stan-  dard d e v i a t i o n s VI  .  Bond l e n g t h s and valency angles i n N.P. F, Me 4 4 4 4 and r e l a t e d molecules 1.1.3  .3 .5  >  24  28*  5-hexafluoro-7,7-dimethylcyclo-  tetraphosphonitrile VII  35  E - s t a t i s t i c s f o r N P F Me, 4 4 6 calculated 4  VIII  Observed and f i n a l  structure 36  factors IX  F i n a l p o s i t i o n a l parameters w i t h  standard  d e v i a t i o n s and a n i s o t r o p i c thermal parameters  3#  viii  X  Bond l e n g t h s and valency a n g l e s w i t h 40  standard d e v i a t i o n s Hexaphenoxycyclotriphosphonitrile XI  S t r u c t u r a l parameters  f o r t r i m e r i c phospho51  nitriles XII  Observed and f i n a l c a l c u l a t e d factors  XIII  55  . . .  F i n a l p o s i t i o n a l and a n i s o t r o p i c parameters  6l  and C atoms  F i n a l p o s i t i o n a l and i s o t r o p i c parameters  thermal  w i t h standard d e v i a t i o n s f o r  the P, N, 0, XIV  structure  thermal  w i t h standard d e v i a t i o n s f o r 65  the H atoms XV  Bond l e n g t h s and v a l e n c y angles w i t h s t a n 66  dard d e v i a t i o n s XVI  Bond l e n g t h s and a n g l e s i n  [NP(0Ph) ] 2  ^ 72  and r e l a t e d molecules Dodeca(dimethylamino)cyclohexaphosphonitrilechlorocopper(II) dichlorocuprate(I) XVII  Comparison of elemental a n a l y s e s f o r the p o s t u l a t e d and a c t u a l formula  XVIII  Measured and f i n a l c a l c u l a t e d  SO structure 82  factors XIX  F i n a l p o s i t i o n a l and thermal w i t h standard d e v i a t i o n s  parameters 86  Bond l e n g t h s and v a l e n c y a n g l e s w i t h standard d e v i a t i o n s  X  LIST OF.FIGURES FIGURE 1  PAGE Endo- and e x o c y c l i c  rf -bonding i n  phosphonitriles  7  1.1.5,5-tetrafluoro-3,3.7.7-tetrafluorocyclotetraphosphonitrile 2  Bond l e n g t h s (A*) and valency a n g l e s  (degrees)  i n the p h o s p h o n i t r i l i c r i n g o f N P.F Me . . .  4 4 4 3  The N P F Me  4  P r o j e c t i o n o f the N P . F. Me.  4 4 4 The N P F Me  4 4 4  25  ~ 4 4 4  5  4  molecule, viewed a l o n g c * . . .  4  23  s t r u c t u r e down b.  4  26  ~  molecule viewed a l o n g c *  4  i l l u s t r a t i n g the thermal e l l i p s o i d s o f 0.5 probability  27  1.1.3.3.5.5-hexafluoro-7,7-dimethylcyclotetra6  phosphonitrile Bond l e n g t h s {%) and v a l e n c y a n g l e s (degrees) i n the p h o s p h o n i t r i l i c r i n g o f N.P.F.Me  4 4 6 7  The N P F Me  8  P r o j e c t i o n o f t h e N,P F^Me  4 4 6  39  2  molecule, viewed a l o n g c * . . .  41  2 4 4 6  9  . . .  s t r u c t u r e down b.  2  42  -  General view o f the N P F Me  4 4 6  molecule  2  i l l u s t r a t i n g the thermal e l l i p s o i d s o f 0.5 probability  (  43  xi  10  ( i ) D e v i a t i o n o f i n d i v i d u a l bond from the mean, and  lengths  ( i i ) bond-atom p o l a r -  i z a b i l i t i e s f o r t h e N P F,.Me  4>6  molecule . . .  47  2  Hexaphenoxycyclotriphosphonitrile 11  The  fNP(OPh) "1  molecule viewed down b. .  2 12  60  3  Views a l o n g t h e normals t o the l o c a l 0P0 planes showing arrangement o f t h e phenoxy groups  63  Dodeca(dimethylamino)cyclohexaphosphonitrilechlorocopper(II) dichlorocuprate(I) 13  The  [ N J P . (NMe ) 1 6  6 .  2  Cud  } CuCP ~ s t r u c t u r e +  J  1 2  <•  viewed a l o n g b . . . 14  General  85  view o f t h e N^P.(NMe_) „CuCA  +  60  1$  91  2 12  Bond l e n g t h s and angles i n t h e phosphonitriiic  r i n g o f the N,P,(NMe ) 00  16  ion. .  The s t r u c t u r e o f  [NP^NMe L  viewed a l o n g b  6 6  CuC£  +  ion .  94  2 12 )  CuC* 1  2 12  J  CuCJl"  * 98  xii  ACKNOWLEDGEMENTS I would l i k e t o express my a p p r e c i a t i o n t o P r o f e s s o r T r o t t e r f o r h i s guidance and a s s i s t a n c e  through-  out my r e s e a r c h . I would a l s o l i k e t o thank P r o f e s s o r N. Paddock f o r the c r y s t a l samples o f the p h o s p h o n i t r i l e s and f o r a great d e a l o f very h e l p f u l d i s c u s s i o n . The award o f a Studentship  by the N a t i o n a l  Research C o u n c i l o f Canada i s a l s o g r a t e f u l l y acknowledged.  G E N E R A L  I N T R O D U C T I O N  2  X - r a y s w e r e  f i r s t  1913."''  i n  s i n c e  h a s  b u ti  s p e e d  i  s q u a r e s d i r e c t  d i s c o v e r e d s t r u c t u r e f X - r a y  i  m e t h o d s ,  f e wy e a r s  a n aa u t o m a t e d  d i f f r a c t i o n ,  a r ew e l l  H . B r a g g i n c r e a s e d  t h e a v a i l a b i l i t y o  o  c o l l e c t i o n  f m u c h  n u m b e r s .  a n dm o r e  k n o w n  a n d  b y v7.  a c c u r a c y  T h e b a s i c  p r i n c i p l e s  F o u r i e r ,  r e c e n t l y  a n d h a v e  f  e q u i p m e n t  g r e a t e r  a s t h eP a t t e r s o n ,  m e t h o d s ,  n 1895  h a s s t e a d i l y  d a t a  s t r u c t u r e s  s u c h  i  d e t e r m i n a t i o n  n u n p r e c e d e n t e d  r e f i n e m e n t  b y R o e n t g e n  d i f f r a c t i o n  nt h e l a s t  n c r y s t a l  r e p o r t e d  X - r a y  na  c o m p u t e r s  r e s u l t e d  b e i n g  i  T h eu s eo  t h e n  h i g h  o f  u s e d  w e r e  b e e n  l e a s t -  t h e s o - c a l l e d r e v i e w e d  i  n a  2-8 l a r g e  n u m b e r  h e r e .  A n y  t h e  t h e s i s  o  f r e f e r e n c e  t e x t s ,  c r y s t a l l o g r a p h i c  ~  a n dw i l l  n o m e n c l a t u r e  h a st h e c o n v e n t i o n a l  n o tb e  o r s y m b o l  m e a n i n g  a s g i v e n  d i s c u s s e d  u s e d  i  i  n  n t h e  9 " I n t e r n a t i o n a l  T a b l e s  f o rX - R a y  T h i s  t h e s i s  i s d i v i d e d  c o n s i s t s f o u r o f  c y c l i c  t h e i r  P a r t  o  f a n a c c o u n t  s t r u c t u r a l  I c o n s i s t s  w e l l  m e r i c  o  f e a t u r e s  f a a  b r i e f  r e v i e w  a s t h es t r u c t u r e p h o s p h o n i t r i l e s ;  i n t o  t h r e e  f t h es t r u c t u r e  p h o s p h o n i t r i l e s ,  p h o s p h o n i t r i l e s , a s  o  C r y s t a l l o g r a p h y . "  b y m e a n s o  f k n o w n  s e c t i o n s  d e t e r m i n a t i o n s  a n d a n a t t e m p t  r e v i e w o  m a i n  o  f  f t h i s  o  f  t o i n t e r p r e t  TT  - b o n d i n g  b o n d i n g  t e t r a m e r i c  d e t e r m i n a t i o n s  o  a n d  s o m e  t h e o r y .  t h e o r y  f o r  p h o s p h o n i t r i l e s ,  f t w o r e l a t e d  t e t r a -  1 , 1 , 5 , 5 - t e t r a f l u o r o - 3 , 3 , 7 , 7 - t e t r a m e t h y l -  c y c i o t e t r a o h o s p h o n i t r i l e ,  N , P . F . M e . , 4  4  a n d 1,1,3,3,5,5-hexafluoro-  4  7 , 7 - d i m e t h y l c y c l o t e t r a p h o s p h o n i t r i l e ,  Ni ?i+F£N 2e  ¥  ^  n  P  a  r  t  H  3  t h e  s t r u c t u r e  d e t e r m i n a t i o n  o f  a  t r i m e r i c  h e x a p h e n o x y c y c l o t r i p h o s p h o n i t r i l e , a n d  i n  p l e x , ( I I )  p a r t  I I I  t h e  s t r u c t u r e  d o d e c a ( d i m e t h y l a m i n o d i c h l o r o c u p r a t e  d e s c r i b e d c o m p l e x e s .  a n d  c o m p a r e d  ( I ) , w i t h  o f  a  p h o s p h o n i t r i l e ,  |^ N P ( O P h )  2  "|  -3 >  ^  d e s c r i b e d ;  s  m e t a l - p h o s p h o n i t r i l e  c o m -  j c y c l o h e x a p h o s p h o n i t r i l e c h l o r o c o p p e r | T N P ( N M e 6  6  o t h e r  2  )  1  2  C u C f i  J CuCJc. ~, +  2  m e t a l - p h o s p h o n i t r i l e  i s  T H E  C R Y S T A L  A N D M O L E C U L A R  S T R U C T U R E S  O F  1 , 1 , 5 , 5 - T E T R A F L U O R O - 3 , 3 , 7 , 7 - T E T R A M E T K Y L C Y C L O T E T R A P H O S P H O N I T R I L E  A N D  1 , 1 , 3 , 3 , 5 , 5 - H S X A F L U O R O - 7 , 7 - D I M E T H Y L C Y C L O T E T R A P H O S P H C N I T R I L E  5  1.1  I N T R O D U C T I O N 1834  I n r e p o r t e d :  t h e  J^NPCl^^  f o r m a t i o n  t h e  w a s  a n d  p h o n i t r i l e m e r i c  u n i t ,  A n o t h e r b e i n g  X  n a m e  2  b y  12  S t o k e s ,  a n a l o g y  -  N ,  t o  ~~"  a n a l o g y e t c .  t o A  s u m m a r i z i n g  i n f o r m a t i o n  o r g a n i c  u s e d  i s  l a r g e  w h i c h  s t r u c t u r e  g r e a t  T h e  13  n a m e  o f  d e a l  R  -  t h i s  p h o s m o n o -  C  _ =  n a m e  c o m p o u n d s :  t r i h a v e  s t r u c t u r a l  o b t a i n e d  N . a l s o  r e v i e w s  o f  c o m o f  h y p o t h e t i c a l  o r g a n i c  b e e n  t h e s e  s t u d i e s  n i t r i l e s ,  n u m b e r  h a s  X - r a y  t h e  p h o s p h o r u s  f o r  p h o s p h a z e n e ,  s i m i l a r  a  b e t w e e n  c o n f i r m e d . o f  s i m u l t a n e o u s l y -  p h o s p h o n i t r i l e s ,  w h i c h  b y  W o h l e r " ^  r e a c t i o n  c y c l i c  A  d e r i v e d P  a n d o f  t h e  l a t e r  t e t r a z e n e ,  c h e m i c a l  s e r i e s  ^ N P C l ^ j ^ ,  b y  p u b l i s h e d  a  L i e b i g  f r o m  f r e q u e n t l y  d e r i v e d  a z e n e , b e e n  w a s  o f  a m m o n i a .  p r o p o s e d  t e t r a m e r ,  a n d  3-7,  =  y\*  y  p e n t a c h l o r i d e p o u n d s  R o s e ^  s i n c e  a n d  t h e  i n i t i a l  13 X - r a y  d i f f r a c t i o n I n  o f  t h e  g i v e n b y  t o  t h e  h e r e .  C r a i g  c e n t  o r d e r  c o m p o u n d s  d u c t i o n  c l a t u r e w i l l b e  t o  b o n d i n g  F o r  i n t e r p r e t l a t e r  t h e o r y  b o n d i n g  P a d d o c k ,  p a  h e l p  d e s c r i b e d  T h i s  a n d  r e v i e w .  s t u d i e s .  i n  f o r  t h e o r y a n d  t h e  s t r u c t u r a l t h e s i s  a  h a s  t h e  b e e n  b e e n  s u m m a r i z e d  C r a i g a t o m s  a n d m a y  i n t r o -  w i l l  d e v e l o p e d  c o n v e n t i o n s  a n d o r b i t a l l a b e l l i n g g i v e n b y f o l l o w e d h e r e . T h e p h o s p h o r u s  f e a t u r e s  b r i e f  p h o s p h o n i t r i l e s  h a s  c o n v e n i e n c e  t h e  b e  p r i m a r i l y i n  f o r  a  r e -  n o m e n -  24—28  P a d d o c k b e c o n s i d e r e d  28  o  a s  p e n t a v a l e n t  w i t h  a  v a l e n c e  c o n f i g u r a t i o n  (3s)(3p_)  (3d).  6  T h e  s i g m a  s p ^  h y b r i d  p h o r u s  b o n d s  i  n p h o s p h o n i t r i l e s  o r b i t a l s  w h i c h  a r ea p p r o x i m a t e l y  a r e  f o u r - c o o r d i n a t e ,  a r e  a p p r o x i m a t e l y  a r e  l e s s  t h a n  TT  - s y s t e m  •IT  - b o n d i n g  a  w e l l  3p_  o r b i t a l s  s i n g l e  m u s t  a l s o  s y s t e m  h a v e  p h o s p h o n i t r i l e s 2.L.  P a d d o c k . l o c a l t h e  '  t +  -~'  b e i n v o l v e d  i  i n v o l v e  i  o r b i t a l s  o n  i n d i c a t e s  b o n d ,  a  n t h es i g m a  t h e  TT  t h ec o n v e n t i o n s  s e c o n d a r y  o n  n i t r o g e n ,  t h e 3s_  a n d  b o n d i n g .  - b o n d i n g o  l e n g t h s  T h i s  o r b i t a l s s i n c e  t h e y  b o n d  n t h eb o n d i n g .  t h e2p_  a t o m s  t h a t  t h eo b s e r v e d  f  p h o s -  t h ep h o s p h o r u s  o n p h o s p h o r u s ,  i l l u s t r a t e s  T h e  c o  N P N p l a n e ,  t h eo t h e r  S i n c e  b y o v e r l a p o  f C r a i g  s y s t e m  i  n  a n d  2& z - a x i s  t h ey _ - a x i s  N - P - N a n g l e ,  t o  a n a l y s i s  u t i l i z e d  u s i n g  s i n c e  p h o s p h o r u s - n i t r o g e n  o r b i t a l s  1  h y b r i d  s p ^ ,  X - r a y  m u s t  b e e n  F i g u r e  21  a n d  v / i t h  t e t r a h e d r a l .  a s t h e 3d  a s  o n n i t r o g e n  a r ef o r m e d  a n d  t w o .  i  s c h o s e n s i  t h ex - a x i s  T h e r e  a r et w o  i  p l a n e  s o r t h o g o n a l t y p e s  o  b i s e c t s  v / i t h TT  r e s p e c t  - b o n d i n g .  o r b i t a l v / i t h a l i n e a r c o m b i n a t i o n o 3d,._ o r b i t a l s c o n t a i n i n g t h es i n g l e — y z  f t h ep h o s p h o r u s 3_xz 3d e l e c t r o n . S i n c e —  o r b i t a l s  w i t h  f l e c t i o n  i  n a t e d  TT a , a n d  a d d i t i o n  t h e r e  b e t w e e n  t h e  n the  N P N  i  i s a  f t h es i n g l y  f  a n d  2p_ a n d  i n v o l v e d  o  n t h eN P N  t o t h e  f i r s t  t h e  o v e r l a p  p e r p e n d i c u l a r  The z  i n v o l v e s  i  a r ea n t i s y m m e t r i c  p l a n e  t h i s  TT  s i l l u s t r a t e d s e c o n d  p h o s p h o r u s  3d o —x*"— y  fT  i  - s y s t e m n F i g u r e  - s y s t e m  o a n d  o c c u p i e d  3dv„ — x y  r e s p e c t h a s  l  n i t r o g e n  b e e n  a a n d  i n v o l v i n g o r b i t a l s  l b .  t o  r e -  d e s i g I n  o v e r l a p a n d t h e  8  n i t r o g e n t h e i n  sp_  h y b r i d  o r b i t a l s t h e  t y p e  o f  o n  i n v o l v e d  t y p e  t h e  3d  v  l o n e  a r e  w i t h IT  l a b e l l e d  o f  b o n d i n g .  m a y  a s  t h e  t h e r e  p r i n c i p a l  a  i n  H e r e  r e f l e c t i o n  l c  i s  a n d  a  t o  I d  t h i r d  e x o c y c l i c  p h o s p h o r u s  F i g u r e  l e s s e r  t o  F i g u r e  - b o n d i n g  i l l u s t r a t e d t o  s.  TV  e l e c t r o n s .  r e s p e c t  F i n a l l y  p e r m i t  H e r e  p a i r  l e ,  o r b i t a l  w i t h  t h e  e x t e n t .  —"vCZ IT  T h e d o  2>  t h e  s y m m e t r i c  p a r t i c i p a t i n g  3d _  y ci  w h i c h  a r e  p h o s p h o r u s .  i s  a n d  a n d  t h i s  o v e r l a p  l i g a n d s  3d  i n v o l v e d  K P N p l a n e  i l l u s t r a t e  c o n t a i n i n g  t h e  d - o r b i t a l s  a n d  1T  i n v o l v e d  i n  a  s  s y s t e m s  t h e m  a r e  n o t  i n t e r a c t  e q u i v a l e n t  w i t h  t h e  n o r  n i t r o g e n  26 £ - o r b i t a l s  e q u a l l y .  C r a i g  o f  i n t e g r a l s  t h a t  o v e r l a p  b i t a l t h e  i s  3d  s y s t e m  t h e  p r e d o m i n a n t  o  o  i s  a s  a  w h o l e  p l a n a r i t y  t h e  t h e  a n d i n  t h e  o n e  m o r e  P a d d o c k  w h e r e a s  i m p o r t a n t .  p r e d o m i n a t e s ,  i m p o r t a n c e  o f  a  TT  i n  h a v e  s h o w n  s y s t e m  t h e tr  t h e  t h e  a s (I  t h e  s  o r -  s y s t e m  t h e  r i n g s  s y s t e m  m e a n s  3d  s  F u r t h e r m o r e  b u t  b y  a  TT  d e p a r t  f r o m  i n c r e a s e s ,  t h e  26 r e l a t i v e c u l a r  c o n t r i b u t i o n  o r b i t a l - o r b i t a l  TT  d e p e n d i n g  c a l c u l a t i o n s i s  a l w a y s  f o r  f o r  p h o s p h o n i t r i l e s  4n  o r  z a t i o n b o n s ,  4n  + m u s t  2  h y d r o c a r b o n s .  TT d i f f e r  h o w e v e r ,  s h o w  d u e  t o  t h a t  A s i s  c o n f o r m a t i o n .  t h e  t h a t  t h e  a  r e s u l t  T h e f o u n d  b o n d  u p p e r m o s t  w h e r e a s  p r e d i c t e d  - e l e c t r o n s . f r o m  t h e  n o n - d e g e n e r a t e  d e g e n e r a t e c y c l i c  o n  i n  a n  t h e  p o l a r i t y  o c c u p i e d i s  d o u b l y  a r o m a t i c  w h e t h e r  n a t u r e  i t  M o l e -  o f  t h e y  n a t u r e h a v e  t h e  d e l o c a l i -  a r o m a t i c  h y d r o c a r -  c a u s e d  b y  t h e  d i f f e r e n t  9  e l e c t r o n e g a t i v i t i e s o f  t h e  c h a r a c t e r A n  o  o  fp h o s p h o r u s  ft h e  a l t e r n a t e  a n d n i t r o g e n ,  p h o s p h o r u s a p p r o a c h  a n d  b e c a u s e  3 d - o r b i t a l s .  h a s  b e e n  p r o p o s e d  b  y D e w a r  29 e t  a l .  U n l i k e  b o n d i n g p h o r u s  s y s t e m  i s  x  o f  i n v o l v e s  z  t h r e e  l a n d s  o  TT  fe l e c t r o n  a  r e s u l t ,  d on o t  a s  a  w h o l e .  A s w i l l  h o w e v e r ,  c e r t a i n  i n  o  e n t i r e  fa  o n  t h e  t h e  s t r u c t u r e s  m e r i c  o  s e v e r a l f o u n d  d i f f e r e n t o n l y  i  fl i n e a r  p h o s -  c o m b i n a t i o n s  w i l l  i  e n c o m p a s s  l a t e r  TT  f  i n t e r a c t t o f o r m  s a  s e r i e s  a  o  a r o u n d  t h e  ( s e c t i o n  s y s t e m  f  P N P s e g m e n t s  o b s e r v a t i o n s o  s o m e  c o m m e n t  ' i s a n d ,  r i n g  1.3.3),  c a n o n l y  - e l e c t r o n s  o  a n d  fX - r a y  a r e  a  w h i c h  X I a n d s e c t i o n c o n f o r m a t i o n s  o  b a s i s  b e e x p l a i n e d  a r o u n d  t h e  p e r h a p s  ft h e  b e  m a d e  t e t r a m e r i c  f o r t h e  p h o s -  d i s c u s s i o n o  N ^ P ^ F ^ M e ^ s t r u c t u r e  c o m p i l e d  f l u o r i d e .  s h o u l d  f e a t u r e s  p r o v i d e  fN ^ P ^ F ^ M e ^  nt h e  w h i c h  d e l o c a l i z a t i o n  s t r u c t u r a l  r e s u l t s  ( T a b l e  ft h e  -  r i n g .  p h o s p h o n i t r i l e s ,  p l a n a r i t y  o  o r b i t a l s  2^  b e d i s c u s s e d  p h o s p h o n i t r i l e s  t r i m e r i c  i s  p e r m i t  p o i n t  w h i c h  T h e  w h i c h  d e l o c a l i z a t i o n  t h i s  o  T h e r e s u l t  e x p e r i m e n t a l  s i g n i f i c a n t  p h o n i t r i l e s  n i t r o g e n  - b o n d s .  p h o s p h o n i t r i l i c A t  A p a i r  TT  t h i s  p a r t i c i p a t i o n  t w o 3 d - o r b i t a l s  d e n s i t y '  a s  t e r m s  t h e s e  a d j a c e n t  c e n t e r  n e q u a l  a p p r o a c h  z  f r o m  w i t h  a  a n d P a d d o c k  o r b i t a l s .  y  c o n s t r u c t e d  s e p a r a t e l y  C r a i g  a n d 3d  3d„„  r  t h e  i  a n a l y s e s  nT a b l e  d e v i a t e  o n l y  2.4), t h e a n a a  I .  o  f  U n l i k e  s l i g h t l y t e t r a m e r s  p l a n a r  T h e p a r t i c u l a r  t e t r a t h e f r o m a d o p t  c o n f i g u r a t i o n c o n f o r m a t i o n  f  T A B L E  I  S t r u c t u r a l parameters o f t e t r a m e r i c p h o s p h o n i t r i l e s with standard d e v i a t i o n s o f bond l e n g t h s a n d v a l e n c e a n g l e s i n p a r e n t h e s e s . Compound [NPMe ] 2  [  N P G 1 2  4  (K)  ]4  [NP(CKe) ] 2  [  K  P  C  1  2 ]  4  (T)  H  4 N, P, Ph, (NHMe ), 4 4 4 4  P-N-P(degrees)  N-P-N(degrees) R i n g Conformation  Reference  1.596(3)  131.9(3)  119.8(2)  tub,  4  30  1.578(10)  133.0(6)  120.1(5)  tub,  4  31  1.57(1)  131.3(6)  121.2(5)  tub,  4  32  1.57  132  122  saddle, 4  33  1.56(1)  133.6(8) 137.6  120.5(7)  chair,  1  34  1.57(1)  132.4(6) 138.6(6)  120.4(5)  chair,  1  35  1.507(17)  147.2(10)  122.7(10)  planar  1.59(1)  124.6(6) 131.2(6)  119.6(5)  chair,  t  N P Ph C I 4 4 4 4 [ PF_]  P-N(A)  36  T  35  i— o  1 1  a d o p t e d m e n t s  i s  a n a  a t h e  b e n d i n g  i n  I  a r e  t h e r e  r e s u l t  o f  a  r e l a t i v e  t h e  i m p o r t a n c e  p h o s p h o n i t r i i i c  t h r e e  m a i n  i n  t e t r a m e r i c  w h e r e  t h e  r i n g  a t o m s  o c c u r  b e l o w  t h e  m e a n  p l a n e  t h r o u g h  i n  s y m m e t r y .  T h i s  b e c a u s e  i t  b e  s t a g g e r e d  i n  a  a l l o w s  c o n f o r m a t i o n  t h e i r  t h e  s a m e  s i d e  o f  a r e  n o t .  i n v o l v e d  i n  t h e  t h e  z - a x i s ,  t h e  o n  s u c c e s s i v e  t h e  n i t r o g e n  p h o s p h o r u s . o n  t h e t h e  t w o a  r i n g  s y s t e m  n e i g h b o r i n g  r i n g  „  v  w i t h  w o r d s  a t o m s  a  t h e  a r e  t h e a b o v e  o n  t h e  d o f  a l t e r -  a r e  w h e n  w h i c h  l o c a l  z - a x e s  t h e  d fp o r b i t a l s — a  a l i g n e d  w h i c h  g i v e s  a n  o v e r l a p  t h e  a r e i n  o f  t o  t h e  o n  t h e y  m e a s u r e  d e g r e e  t h i s  i n t e r s e c t  t h e  tv/o  t o  i n  a t o m s  a t o m s  )  i d e a l l y  a t o m s  p h o s p h o r u s  a n d  a n d  f a v o r a b l e  a n g l e s  t h e  T a b l e  '.tub',  r e s u l t i n g  m i s m a t c h e d  o r i e n t a t i o n s g i v e s  i s  p h o s p h o r u s  w h e n  i n  c o m m o n l y  O n e  a s  s  TT  s e e n  s t e r i c a l l y  r i n g  o r  ( d  b e  d i h e d r a l  t h e  r e q u i r e -  a n d  a r e  a t o m s  t h e  o r b i t a l s  o r b i t a l s o t h e r  m a y  w h i c h  i s  T h e  p l a n e ,  3d  a t o m s  ^ i r  A s  r i n g  o n  a  1T  a l t e r n a t e l y  a l i g n e d ,  m e a n  r e l a t i v e  I n  t h e  a r o u n d  z - a x e s  TT  n  p a i r s  c o n f o r m a t i o n  v a r y  h a v e  S i n c e  i n  s t e r i c  t h e  p h o s p h o n i t r i l e s .  a r r a n g e m e n t .  n a t i v e l y  o f  r i n g .  s u b s t i t u e n t s  w o u l d  b e t w e e n  c o n f o r m a t i o n s  f o u n d  S^  t h e  c o m p r o m i s e  o f o n  z - a x e s  e s t i m a t e  o f  2 1 t h e  i m p o r t a n c e  c o n f o r m a t i o n a r e  i n  o p p o s i t e  a  p l a n e  o f i s  t h e  a l s o w i t h  d i r e c t i o n s  TT  a  c o m m o n  b o n d i n g a n d  s u c c e s s i v e f r o m  t h e  s y s t e m .  h e r e  t h e  n i t r o g e n  p l a n e  T h e  p h o s p h o r u s a t o m s  r e s u l t i n g  ' s a d d l e ' a t o m s  d e v i a t i n g i n  D 2 d  i n  s y m m e t r y  1 2  i n  t h e  i d e a l  c a s e .  a n g l e s  t o  a p p r o x i m a t e l y  i n  z - a x e s  t h e  b e  e q u a l i s i n g A  f o r m a t i o n T h e r e  i s  d i h e d r a l i n  t h e  a r r a n g e m e n t  o n t h e r i n g  t h e  s t e r i c a l l y  T h i s  e q u a l a t o m s  i n t e r a c t i o n s  u n f a v o r a b l e  i s  t h a t  a l s o  a  a n g l e s ' s a d d l e '  r e q u i r e s  a r o u n d b e i n g  b e t w e e n  t h e  ' c h a i r '  f o r m  b e t w e e n  a d j a c e n t  c o n f o r m a t i o n .  r e s u l t i n g  m i s m a t c h e d ,  s u c c e s s i v e  ' s a d d l e ' a r e n o w  s y m m e t r y  1  r i n g  a t o m s  I n t h i s  t h u s  T T - o r b i t a l s .  o f t h e  s u b s t i t u e n t s  h a v i n g  d i h e d r a l  r i n g  e q u a l l y  c h a r a c t e r i s t i c  t h e p h o s p h o r u s  t h e  c o n e c l i p s e d .  i n w h i c h  t h e  a r e l a r g e r  c o n f o r m a t i o n  t h a n  t h e i m -  21 p o r t a n c e p o i n t e d  o f t h e  s  e a c h  a - s y s t e m  t h a t  o t h e r  p e r p e n d i c u l a r .  TT"  s y s t e m  o u t , h o w e v e r ,  c o m p l e m e n t a r e  fT  i n c r e a s e d .  I t  t h e t w o s y s t e m s  s i n c e  A s a  i s  t h e i r  r e s u l t  r e s u l t s  i n a n  r e s u l t s  o f a  p l a n e s  T T - b o n d i n g  o f m a x i m u m  d e c r e a s e d  i n c r e a s e  o f  s h o u l d . b e  o v e r l a p  o v e r l a p  o f  t h e  i n t h e p a r t i c i p a t i o n  o f  s - b o n d i n g . T h e w o u l d a n d o f  s e e m  t o  i n d i c a t e  r e c e n t  t h a t  ' t u b ' c o n f o r m a t i o n s  s t r u c t u r e  d e t e r m i n a t i o n  t h e d i s t i n c t i o n  c a n n o t b e  v e r y  b e t w e e n  g r e a t .  b i s - ( o c t a m e t h y l c y c l o t e t r a p h o ' s p h o n i t r i l i u m )  t h e  T h e  ' s a d d l e  s t r u c t u r e  t e t r a c h l o r o -  - -3 7 c o b a l t a t e  ( I i)  c o n t a i n s  t w o e i g h t - m e m b e r  r i n g s ,  o n e o f w h i c h  a p p r o x i m a t e s  a d o p t s  t h e  . c o n f o r m a t i o n .  o f  ' s a d d l e '  a n o v e r a l l  i n a n t l y  fT  a  p r e f e r e n c e o r  t o w a r d s  TV s - b o n d i n g  a  a  p h o s p h o n i t r i i i c  ' t u b ' w h i l e T h e r e  i s  s h a p e  w h i c h  w i t h i n  t h e  n o  r i n g ,  t h e  o t h e r  i n d i c a t i o n f a v o r s t h e  p r e d o m d i f f e r e n c e  13  i n  c o n f o r m a t i o n  o f  m o s t  A s  w a s  e x o c y c l i c  fT  e n t s .  T h i s  h a s  p r o b a b l y  m e n t i o n e d  e a r l i e r  - b o n d i n g b e e n  b e i n g  b e t w e e n  f o u n d  i n  d u e  t o  t h e r e  c r y s t a l  e x i s t s  p h o s p h o r u s  s e v e r a l  p a c k i n g .  t h e  a n d  p o s s i b i l i t y  i t s  31  s t r u c t u r e s ,  s u b s t i t u -  33  '  36*  '  39  '  31 b u t  t h e  b e c a u s e t h a n  a  t e t r a m e r i c n o t p u r e  o c c u r r i n g t h e  o n l y  d i m e t h y l a m i d e ^ a r e  s i n g l e  b e t w e e n  t h e  d i m e t h y l a m i n o  g r o u p s ,  i s  o r i e n t e d  n h o s n h o r u s  3d  0  w i t h  s o  o r b i t a l  t h e  b u t  t o  w h i l e  i n  p h o s p h o n i t r i l e s  e n t s  o n  e f f e c t  f a c t o r i s  p h o s p h o r u s . o f  a  c h a n g e  i n t h e  p a i r  e l e c t r o n s  o n  n i t r o g e n  t h u s  s t r e n g t h e n i n g  S i m i l a r l y  t h e  p h o s p h o r u s  3d  fT  a  s y s t e m .  t e t r a m e r i c m a d e  o v e r l a p o r b i t a l s  o f  i s  o n  w i t h  e a c h t h e  o r i e n t e d  t o  o r b i t a l s . — y z  e l e c t r o n e g a t i v i t y  o f  t h e  s u b s t i t u -  t h a t  t h e  b e e n  p o i n t e d  o u t  e l e c t r o n e g a t i v i t y  a r e  c o m p o n e n t n i t r o g e n  f a c i l i t a t e d h a v e b u t  b e e n  t h e s e  s u b s t i t u t e d  i s  o n  i n c r e a s e s  d e l o c a l i z e d  s_  C o m p a r i s o n s  h o m o g e n e o u s l y  g r o u p  o f  b o n d i n g  t h e  i s  n i t r o g e n s  t h e  fT  p h o s p h o n i t r i l e s  b e t w e e n  g r o u p  e l e c t r o n e g a t i v i t y  t h e  t h e  i s  i n  l i g a n d  A s  i s  - b o n d i n g  o v e r l a p  3d  s h o r t e r  i m p o r t a n t  h a s  - s y s t e m .  fT  g o o d  o t h e r o r  w h i c h  t h e I t  t h e  l e n g t h s fT  a n d  i n t e r e s t i n g  d i m e t h y l a m i n o  — x z  r  A n o t h e r  t h a t  h a v e  3d  p h o s p h o r u s ^  b o n d  a t o m s  o n e  a s  e s p e c i a l l y  P - N  i n d i c a t i n g  p h o s p h o r u s  p h o s p h o r u s  o v e r l a o  e x o c y c l i c  b o n d , t h e  i s  o f 2p_z  t o  a  t h e  t h e  t h e  l o n e  g r e a t e r  e x t e n t  b o n d i n g .  o r b i t a l  r e s u l t i n g m a d e  m a i n  w i t h  i n  b e t w e e n  c o m p a r i s o n s c o m p o u n d s .  a  t h e s t r o n g e r  v a r i o u s  h a v e I t  b e e n w o u l d  14  be  i n t e r e s t i n g  l i g a n d s s a m e  o  f d i f f e r e n t  r i n g .  l e n g t h s  i  t o e x a m i n e  i n e q u a l i t i e s  a s e x p e c t e d o  l a r g e r b o n d b y  a n d N  f s u c h s i z e  J  P ~ F . J> 4  f r o m  o c c u r  i  TT - e l e c t r o n  b e e n  c a u s e d  r i n g  b o n d  v a r i a t i o n s N o  s t r u c -  g e m i n a l l y  s u b s t i t u t e d  r i n g s  a l t h o u g h  a l t e r n a t i o n  o  r e p o r t e d  o f a  n t h e  40  t h e o r y .  b y t h ep e r t u r b a t i o n  t h ep r o t o n a t i o n  i  n t h e P - N  r i n g s o f N ^ P ^ C A ^ P h g , i p P h ~ , a n dt h e s e o b s e r v e d  i n h o m o g e n e o u s l y  h a v e  l e n g t h s  0  w h e n  a r ep r e s e n t  n t h e s i x - m e m b e r e d I "1  t u r e s  o n t h eb o n d i n g  e l e c t r o n e g a t i v i t i e s  S y s t e m a t i c  N . P _ C j { _ P h , , ; j ^ V a r e  t h e e f f e c t s  n i t r o g e n  o c t a m e t h y l c y c l o t e t r a p h c s p h o n i t r i l i u m  o  f t h e  TT  f  o  f  r i n g  - s y s t e m  h a sb e e n f o u n d 37 4 3 i o n s , a n d  i  n t w o  i  n  i N ^ P ^ C A ^ ( N H P r ~ )  •H C J Z . A  t e t r a p h o s p h o n i t r i l e s l i t h i u m o f  v / i t h  t h e s e  s e r i e s  o  w a sp r e p a r e d  f g e m i n a l  f l u o r o m e t h y l c y c l o -  b y t h e r e a c t i o n  o c t a f l u o r c c y c l o t e t r a p h o s p h o n i t r i l e ^ ^  o  f  m e t h y l -  a n d t w o  1 , 1 , 5 , 5 - t e t r a f l u o r o - 3 , 3 , 7 , 7 - t e t r a m e t h y l -  c o m p o u n d s ,  c y c l o t e t r a p h o s p h o n i t r i l e ,  N ^ P ^ F ^ M e ^ ,  7 , 7 - d i m e t h y l c y c l o t e t r a p h o s p h o n i t r i l e ,  a n d  1,1,3,3,5,5-hexafluoro-  N^P^F^Me2>  w e r e  i s o l a t e d  f o r c r y s t a l s t r u c t u r e N , P , Me a n d N . P , F 4 4 o 4 4 o  a n a l y s i s . S i n c e t h e s t r u c t u r e s o f a r ek n o w n , t h ea v a i l a b i l i t y o f t h e s e  m i x e d  m e t h y l - f l u o r i d e  t e t r a m e r s  s t u d y  t h e e f f e c t s  r  a s  t  w e l l  r  t  o n t h eb o n d i n g  a s o n t h e r i n g  g r a d u a l l y  c h a n g e d  a f f o r d e d  f r o m  i  n t h ep h o s p h o n i t r i l i c  c o n f o r m a t i o n s , m e t h y l s  t o  a n o p p o r t u n i t y  a s t h el i g a n d s  f l u o r i n e s .  t o r i n g s ,  w e r e  1 5  1.2  THE CRYSTAL AND MOLECULAR STRUCTURE OF 1,1,5,5TETRAFLUORO-3,3,7,7-TETRAMETHYLCYCLOTETRAPHOSPHOWITRILE  1.2.1  Experimental Crystals of  1,1,5,5-tetrafluoro-3,3,7,7-tetra-  m e t h y l c y c l o t e t r a p h o s p h o n i t r i l e are c o l o u r l e s s prisms gated  a l o n g £, w i t h  Unit-cell  {lio} w e l l d e v e l o p e d  a n d s m a l l e r (00lJ .  a n d s p a c e g r o u p d a t a were o b t a i n e d f r o m  various  r o t a t i o n , Weissenberg, and p r e c e s s i o n photographs; unit-cell cedure^  elon-  accurate  p a r a m e t e r s were o b t a i n e d by a l e a s t - s q u a r e s p r o applied to 20  measured on a  v a l u e s f o r twenty  general  reflexions  spectrogoniometer.  C r y s t a l Data. — c l i n i c , a = 12.910(5),  C  4 12 4W H  F  316.1.  =  Mono-  b - 9 . 2 3 6 ( 4 ) , £ = 1 2 . 3 2 9 ( 5 ) A,  =  117.13(3)° ( s t a n d a r d d e v i a t i o n s i n p a r e n t h e s e s ) , U = 1308.3 A ^ , D = 1.59 ( f l o t a t i o n i n CHBr / C . H j , 2 = 4, _ , = 1.604, -m 3 o 6 ~— F (. 0 0 0 ) = 6 4 0 . A (Cu-K _ ) = 1.5418 A, M ( C u - K• _ ) = 56 cm" . — —- C\ S p a c ? ( r o u p _2/£(Cp^) o r C c ( C ^ ) , f r o m  systematic  hk_ when (h + k ) i s o d d , h O i when A i s o d d . structure  C2/£ f r o m  analysis. The  (Cu-K^ )  absences:  ^  intensities  of a l l reflexions with 2 0  120° (minimum i n t e r p l a n a r s p a c i n g , 0.89 A )  were m e a s u r e d o n a D a t e x - a u t o m a t e d G e n e r a l Spectrogoniometer,  with a scintillation  m o n o c h r o m a t i c Cu-K _  radiation  Electric  counter,  XRD 6  approximately  ( N i f i l t e r and pulse  height  1 6  a n a l y z e r ) , 2 O  .  a n d  6-2©  B a c k g r o u n d  b e g i n n i n g s e c t i o n  a n d  o f  w h i c h  m m .  a n d  w h e r e  a  n e t  <S~ ( I )  i s  w e r e  S  a n d  t a k e n  s i g n e d  a s  2  f r o m  2©  a r e  g r o u p s ,  t h e  3  u s e d  h a d  0.5  m m .  o f  c o m p o u n d s e a l e d  a s  <s~  a t  i s  i n  a  c r o s s N o  L i n d e m a n n  f a c t o r s  a b o v e  t h e  s l i g h t l y  a  u s u a l .  i n  w e r e  a p p l i e d ,  R e f l e x i o n s  b a c k g r o u n d ,  b y  +  s c a n  f a c t o r s  B  +  a n d  e q u a l  r e f i n e m e n t .  (0.05  S )  2  b a c k g r o u n d T h e s e  c o u n t s  r e s p e c t i v e l y ,  r e f l e x i o n s  t o  t h e  m e a s u r e d  O f  t h e  930  w e r e  444  w e r e  v a l u e s  p o s s i b l e  c l a s s i f i e d  a s  a s b u t  w e r e  b e t w e e n  p l a c e d  o n  a n  t h e  t w o  a b s o l u t e  p o s s i b l e s c a l e  o b s e r v e d .  s p a c e u s i n g  4 7 W i l s o n ' s [ E  |  ,  d e f i n e d  m e t h o d ,  w e r e b y ^  a n d  d e r i v e d .  n o r m a l i z e d T h i s  s t r u c t u r e  n o r m a l i z e d  a m p l i t u d e s ,  s t r u c t u r e  w e r e  r e f l e x i o n s  A n a l y s i s  d i f f e r e n t i a t e d a t a  w a s  d e r i v e d  u n o b s e r v e d .  120°,  l e n g t h  m i n u t e  m a d e  c r y s t a l  T h e  t h a n  p e r  w e r e  p o l a r i z a t i o n  l e s s  3  =  t h e  t h e  ^  T o  w e r e  b e i n g  S t r u c t u r e  1.2.2  f a c t o r s  (I)  a  u s e d  a n d  o f  T h e  a n d  L o r e n t z  d e g r e e s  s e c o n d s  m a d e .  c r y s t a l  d e f i n e d  s t r u c t u r e  e x c l u d e d w i t h  B  m m .  w e r e  t w o  20  s c a n .  0.3  c o u n t  r  w h e r e  b y  o f  f o r  e a c h  t h e  s t r u c t u r e  h a d  c o u n t s o f  c a p i l l a r y .  t h e  s c a n  c o r r e c t i o n s  h y g r o s c o p i c , g l a s s  e n d  0.2  a b s o r p t i o n  a n d  a  f a c t o r  i s  17  E  ,2  -hk£  I  14k* n  _  — *  where  F, , . i s the  '  2  j-i  structure  f a c t o r f o r the plane hki, th~  f .(hk£) i s the atomic s c a t t e r i n g f a c t o r f o r the f o r the  s c a t t e r i n g angle a s s o c i a t e d  j  atom  w i t h the plane hk2,  i s the t o t a l number of atoms i n the u n i t c e l l , and i s r e l a t e d to the m u l t i p l i c i t y of the E - s t a t i s t i c s are  N  £,  r e f l e x i o n hkfi.  ^ The  compared with the t h e o r e t i c a l r e s u l t s f o r 49  c e n t r i c and  non-centric d i s t r i b u t i o n s  choice of C2/£ prove  i s i n d i c a t e d , and  i n Table I I .  t h i s c h o i c e was  The  later to  correct. The  i n t e n s i t i e s of a l l r e f l e x i o n s w i t h A odd  extremely weak, so t h a t  i t was  expected t h a t the  were  crystal  contained molecules r e l a t e d approximately by t r a n s l a t i o n The  t h r e e - d i m e n s i o n a l sharpened P a t t e r s o n f u n c t i o n  phosphorus p o s i t i o n s a s :  (0, +0.21, z),  (+0.16, 0,  (-0.16, 0,  or  z + 0.16), and  the two  gave  c/2, the  (0, -0.21, :z),  z - 0.16), w i t h z =  s o l u t i o n s g i v i n g i d e n t i c a l P-P  vectors.  0  A  three-dimensional e l e c t r o n - d e n s i t y  map,  computed w i t h phases  based on the phosphorus atoms, had  a f a l s e m i r r o r plane a t  y_ = 0, but  e l o n g a t i o n s of the l i g h t - a t o m peaks  deviations  from 2/m  m o l e c u l a r symmetry.  of approximate t e t r a h e d r a l  By the  indicated assumption  geometry a t the phosphorus atoms  1 8  TABLE I I E - 3 t a t i s t i c s f o r N P,F Me 4 4 4  4  Theoretical Observed  Centro.  Ifon-Centro.  Mean i E 1  0.740  0.798  0.886  Mean |  0.985  1.000  1.000  1.094  0.968  0.736  0.54  0.30  0.01  > 2 (percent)  7.10  5.00  1.80  S > 1 (percent)  25.27  32.00  37.00  Mean | 2 E -11 E > 3 (percent) E  19  two  p o s s i b l e s t r u c t u r e s c o u l d be d e r i v e d , w i t h m o l e c u l e s o f  symmetry 1 and  2 r e s p e c t i v e l y , l y i n g on the a p p r o p r i a t e  metry element i n space group C2/c_.  These two  sym-  s t r u c t u r e s gave  e q u a l l y r e a s o n a b l e s t r u c t u r e f a c t o r agreement f o r ^ the 4 even r e f l e x i o n s , but the X - s t r u c t u r e gave v e r y poor agreement f o r the £ odd  r e f l e x i o n s , w h i l e the 2 - s t r u c t u r e  gave much  more e n c o u r a g i n g agreement f o r these r e f l e x i o n s , and appeared t o be  thus  correct.  T h i s s t r u c t u r e was  r e f i n e d by f u l l - m a t r i x l e a s t -  squares methods, w i t h the s c a t t e r i n g f a c t o r s from the 9 n a t i o n a l T a b l e s , and  f i n a l w e i g h t s , w = 0 f o r the  r e f l e x i o n s and w = 1/(7.0 - 0.3  | F\ Q  Inter-  unobserved 2  + 0.004 | F.J  ) for  the observed r e f l e x i o n s , the c o e f f i c i e n t s b e i n g d e r i v e d f r o m 2 an a n a l y s i s of w(F - F ) o v e r ranges o f | F I . The maximum o ~c -o r a t i o o f s h i f t to e s t i m a t e d s t a n d a r d d e v i a t i o n on the c y c l e was  0.$,  and  r e f l e x i o n s , and  the f i n a l R was  0.153  f o r a l l 930  0.081  final  f o r the 444  reflexions.  observed  Measured  c a l c u l a t e d s t r u c t u r e f a c t o r s a r e l i s t e d i n Table I I I . f i n a l d i f f e r e n c e map,  computed w i t h  (F - F ) as —o —c  and A  Fourier °-3  c o e f f i c i e n t s , showed maximum f l u c t u a t i o n s o f + 0.5  e.A  .  Although t h e r e were r e g i o n s o f p o s i t i v e e l e c t r o n d e n s i t y around the carbon atoms, a c o n s i s t e n t not be  s e t o f hydrogen atoms c o u l d  located. F i n a l p o s i t i o n a l and  i n Table IV.  Atoms P ( l ) and  t h e r m a l parameters are  given  P(3) are i n p o s i t i o n s 4(e)  of  2 0  T A B L E O b s e r v e d  a n d  U n o b s e r v e d  f i n a l  I I I  c a l c u l a t e d  r e f l e x i o n s  h a v e  a n  s t r u c t u r e a s t e r i s k  f a c t o r s . f o l l o w i n g  F,  21  TABLE IV F r a c t i o n a l p o s i t i o n a l parameters w i t h estimated d e v i a t i o n s i n parentheses, and a n i s o t r o p i c °2  (A Atom  0 0.1590(2) 0 0.1176(8) 0.0758(11) 0.1801(13)  P(3) N(l) N(2)  C(l)  0.3011(10)  C(2)  F(l) F(2)  P(l) P(2) P(3)  N(l) N(2) G(l) C(2) F(l) F(2)  thermal  parameters  2 x 1CT).  x  P(D P(2)  Atom  standard  0.0216(8) 0.0708(9)  U  U  0.2134(7) 0.0015(7) -0.2132(7) 0.1375(10) -0.1379(13) 0.0461(14) -0.0422(16) 0.3219(13) -0.3240(11)  -11  -22  ^33  4.18 4.35 5-94 4.60 8.08 9.51 5.13 7.53 12.63  4.00 5-54  8.06 5.02 4.71 7.64 4.34 5.42 10.52 20.30 9.74  3.91 4.73 6.25 9.49 10.66  13.67 8.69  %2 0 •0.35 0 •0.56 -0.99 -3.18 3.72 •0.95 5.22  1/4 0.4104(3) 1/4 0.3237(9) 0.3712(10) 0.5632(12) 0.4234(14) 0.1706(12) 0.2134(9)  *13 1.10 0.70 0.37 0.96 0.79 3.01 3.67 2.31 2.05  U  2 3  0 0.11 0 1.01 0.50 - 3.40 3.40 10.54 - 1.34  2 2  o,  C_2/c_, and the other atoms a r e i n 8 ( f ) .  The thermal v i b r a t i o n s  of the s u b s t i t u e n t atoms, p a r t i c u l a r l y the f l u o r i n e atoms, are f a i r l y l a r g e , w i t h root mean square o high as 0.4 A.  displacements as  Bond l e n g t h s and angles p e r t a i n i n g t o the r i n g  are shown i n Figure 2, while the complete i n t r a m o l e c u l a r bond l e n g t h s ana a n g l e s , w i t h t h e i r standard d e v i a t i o n s , are g i v e n i n Table V.  A view o f the molecule  along c * i s  shown i n Figure 3 and the molecular packing arrangement viewed along b i n Figure 4-  F i g u r e 5 i s a view o f the molecule  along c * shov/ing the thermal 1.2.3  e l l i p s o i d s o f 0.5 p r o b a b i l i t y .  Discussion  In the N,P F Me molecule, t h e r e i s a marked v a r 4 4 4 4 i a t i o n i n P-N bond l e n g t h s around the r i n g ( F i g u r e 2 ) ; the mean P-N bond d i s t a n c e i n v o l v i n g the m e t h y l - s u b s t i t u t e d phoso  phorus atoms i s 1.59(1) A, and the corresponding l e n g t h f o r o  the f l u o r i n e - s u b s t i t u t e d phosphorus atoms i s 1.53(1) A. These bond l e n g t h s are not s i g n i f i c a n t l y d i f f e r e n t from the P-N d i s t a n c e s o f 1.596(3) and 1.51(2) A* found 30  individually  36  i n t h e parent octamethyl and o c t a f l u o r o compounds (Table V I ) . The d i f f e r e n c e i n P-N bond l e n g t h s may be i n t e r 24—28 preted i n terms o f TT* -bonding theory.  The s t r o n g l y  e l e c t r o n e g a t i v e f l u o r i n e atoms withdraw e l e c t r o n s from the r i n g , r e s u l t i n g i n a subsequent t r a n s f e r o f e l e c t r o n s from the adjacent n i t r o g e n atoms i n t o . a  tr -bonding system o f  23  the  phosphonitriiic  ring  of  N.P.F 4  4  M e 4  . 4  2 4  TABLE V o  Bond l e n g t h s (A) and valency a n g l e s  (degrees) with  standard  d e v i a t i o n s i n parentheses. P(1)-K(D P(3)-N(2) P(2)-N(l) P(2)-N(2)  1.54(1) 1.53(1) 1.58(1) 1.60(1)  N(l' )-P(I)-N(l) N(2» )-P(3)-K(2) N(l)-P(2)-N(2)  125.8(9) 125-9(10) 117.5(5)  P(l)-N(l)-P(2) P(2)-K(2)-P(3)  134.6(7) 134.6(8)  F(l» ) - P ( l ) - F ( l ) F(2' )-P(3)-F(2) C ( l )-P(2)-C(2)  97.0(13) 96.4(10) 106.9(7)  P(l)-F(l) P(3)-F(2) P(2)-C(l) P(2)-C(2)  1.5KD 1.54(1) 1.82(1) 1.81(1)  F ( I )- P ( l ) - N ( l ) F(l')-P(l)-N(l) F ( 2 ) - P(3 )-N(2) F ( 2 M -P(3)-N(2) C ( D - P(2)-N(l) C(2)- P(2)-N(l) C ( D - P(2)-N(2) C ( 2 ) - P(2)-W(2)  105.1(6) 110.1(5) 111.2(6) 104.2(6) 111.4(7) 104.7(7) 104.9(7) 111.1(7)  2 7  28  TKBLE  VI  o Bond l e n g t h s ( A ) a n d v a l e n c y a n g l e s and r e l a t e d  ( d e g r e e s ) i n N P F Me 4 4 4 4 molecules.  30 \  P  4  K  e  8  1.51(2)  P - F  1.51(2)  F-P-N 1.596(3)  Me-P-N  104.0(2)  Me-P-Me 2  N-P(Me  j-N  119.8(2) 131.9(3)  96.7(12) 106.9(7)  123.0(10)  N-F(F )-N  1.53(1) 1.59(1)  100.0(10)  F - P - F  P - N - P  1.81(1)  1.805(4)  P - C  1.52(1)  125.9(9) 117.5(5)'  147.0(10)  134.6(7)  29  the  FgP-N b o n d s , c a u s i n g t h e s e bonds t o be s t r o n g e r and  s h o r t e r t h a n t h e Me P-N b o n d s .  The P-F (1.52 A) and P-CH  2  (1.81  3  A ) bond l e n g t h s a r e s i m i l a r  compounds  to those  i n the parent  (Table V I ) . With  t h e e x c e p t i o n o f t h e P-N-P a n g l e s a l l t h e  endocyclic  and e x o c y c l i c  antly  those  from  bond a n g l e s do n o t d i f f e r  i n the parent  compounds  signific-  (Table V I ) .  The  P-N-P a n g l e o f 1 3 4 . 6 ° i s v e r y much s m a l l e r t h a n t h e a n g l e o f 147°  found  i n the tetrameric f l u o r i d e .  In t h e p r e s e n t  compound t h e r e a r e o n l y h a l f a s many f l u o r i n e s , tive  e f f e c t s a r e presumably  a result  t h e P-N-P a n g l e  and t h e i n d u e  not as l a r g e a s i n (NPF^)^.  As  i s c l o s e r t o t h e v a l u e s found i n 21  most o f t h e o t h e r t e t r a m e r i c p h o s p h o n i t r i l e s The  phosphonitrilic  has t h e s o - c a l l e d  ring  (Table i ) .  i n the present  'saddle' conformation, w i t h t h e phosphorus  atoms on a p l a n e v / i t h t h e n i t r o g e n s a l t e r n a t i n g below.  structure  The e q u a t i o n o f t h e p l a n e t h r o u g h  above and  the four  phosphorus  atoms i s -0.8370 X + 0.5473 = 2.6776, v/here X', Z' a r e o c o o r d i n a t e s i n A r e f e r r e d t o o r t h o g o n a l a x e s a , b, and c * , and t h e d i s p l a c e m e n t s o f t h e n i t r o g e n atoms f r o m t h i s p l a n e ?  a r e N ( l ) - O.48, N(2) + O.48, N ( 2 ) - O.48, and N ( I ' ) +. O.48 f  T h i s c o n t r a s t s v/ith t h e t e t r a m e r i c f l u o r i d e  i n which the r i n g  36 is planar, the  and t h e t e t r a m e r i c m e t h y l compound w h i c h h a s 30 'tub' conformation. C o n s i d e r a b l e a t t e n t i o n has been  30  g i v e n  t o  i n  e f f o r t  a n  t h e  s h a p e s t o  o f  d e d u c e  t h e  t e t r a m e r i c  p h o s p h o n i t r i i i c  t h e  i m p o r t a n c e  o f  r i n g s  T T - b o n d i n g  i n  t h e s e  21 c o m p o u n d s . f o u n d a n d  I t  i n  a t  t h e  i s  p o i n t e d  o c t a m e t h y l  t h e  s a m e  t i m e  i s  o u t  t h a t  t h e  ' t u b '  d e r i v a t i v e  a l l o w s  s t e r i c a l l y  f a v o u r a b l e  c o n f o r m a t i o n  s t r o n g  TT  a s  - b o n d i n g ,  i t  a l l o w s  21 t h e  m e t h y l  g r o u p s  o c t a f l u o r o  t o  b e  c o m p o u n d  s t a g g e r e d .  i s  i n d u c t i v e  i n f l u e n c e  o f  e x t e n s i v e  d e l o c a l i z a t i o n  T h e  p r o b a b l y  t h e o f  p l a n a r i t y  a  r e s u l t  o f  f l u o r i n e  a t o m s ,  w h i c h  t h e  n i t r o g e n  o f  t h e  l o n e  s t r o n g p r o d u c e s  p a i r s ,  a n d  21,36  o r e s u l t s  i n  a n I n  t h e  c o n f o r m a t i o n  a t o m s  t w e e n  i n  p r o b a b l y  a n d t h e  a d j a c e n t  i n t o  e c l i p s e d  b r i n g i n g  r a d i u s " ^  o f  a  g r o u p  a c t i o n s . C ( l )  a n d  g r e a t e r  T h e  (2.00 c l o s e s t  F ( l ' ) t h a n  b e t w e e n  t h e  t h e  s u m  s h o r t e r m e t h y l  t h e  r e s u l t  a l l o w s  o f  a n d  H o v / e v e r  o n  .  a d o p t i o n a  o f  t h e  c o m p r o m i s e T h e  n i t r o g e n  147  t o  TT  a t o m s , t h e  s i n c e  ' s a d d l e '  b e t w e e n  a r r a n g e m e n t  e f f i c i e n t  s u b s t i t u e n t s  o f  - b o n d i n g b u t  a t  b e -  t h e  p h o s p h o r u s t h e  v a n  d e r  a t o m s i v a a l s  (1.35 A ] i s m u c h s m a l l e r t h a n t h a t o f o A ) t h i s c a u s e s n o s e r i o u s s t e r i c i n t e r o c r o s s - r i n g  [ r e l a t e d  t h e  a n g l e s  r e q u i r e m e n t s .  p o s i t i o n .  f l u o r i n e  T h e t a c t s  s t e r i c  P - N - P  s t r u c t u r e  p h o s p h o r u s  o f  m e t h y l  t h e  ' s a d d l e '  e x p e n s e a n  o f  p r e s e n t  i s  - b o n d i n g  1T t h e  i n c r e a s e  t h e  o f  t o t h e  F ( l ) v a n  b y d e r  i n t e r m o l e c u l a r g r o u p s  a n d  (3.84  c o n t a c t t h e  C_  W a a l s  2  a x i s ]  i s a n d  b e t w e e n i s  r a d i i .  d i s t a n c e s  f l u o r i n e s  A )  a n d  i n v o l v e  c o n -  c o r r e s p o n d  31  t o  v a n  cier  V / a a l s  i n t e r a c t i o n s .  T h e  s h o r t e s t  d i s t a n c e  i s  a  o C . . . F a n d  c o n t a c t  C ( 2 )  o f  o f  t h e  3 . 2 5  A  m o l e c u l e  b e t w e e n a t  ( i  F ( l ) -  x ,  o f ~  +  t h e y_,  s t a n d a r d i  -  z).  m o l e c u l e  32  1.3  THE  CRYSTAL AND  MOLECULAR STRUCTURE OF 1,1,3,3,5,5-  KEXAFLUORO-7,7-DIMETHYLCYCLOTSTRAPHOSPHONITRILE 1.3.1  Experimental 1,1,3,3,5,5-Hexafluoro-7,7-dimethylcyclotetraphos-  p h o n i t r i l e c r y s t a l l i z e d as c o l o u r l e s s fragments, g e n e r a l l y elongated  along c_.  U n i t - c e l l and  space group data were d e t e r -  mined from v a r i o u s r o t a t i o n , Vfeissenberg, and graphs, and  on a spectrogoniometer.  No  p r e c e s s i o n photo-  suitable liquid  could  be found f o r d e n s i t y measurement. C r y s t a l Data  —  C„H  F,N 6 t> 4  P , M=  321.0.  Monoclinic,  4  a = 9.355 (5 ), b = 1 2 . 4 0 0 ( 5 ) , c = 11.132(5) A,  (2  =113.75(3)° o 3  (standard d e v i a t i o n s i n p a r e n t h e s e s ) , U = 1182.0 A p_ = 1.820. F ( 0 0 0 ) - 640. A ( C u - K ^ ) = 1.5418 A ,  , Z = 4,  c  u  s  (Cu-K  _  K  w  ) = 65 cm.  ^.  Space group I2/a  _  from systematic absences: when h i s odd.  ) or Ia _ (C^, —2h  (C^) ~s_  hkJL when (h + k_ + __) i s odd;  h0__!  I2/a from s t r u c t u r e a n a l y s i s  A great deal of d i f f i c u l t y was taining a suitable crystal f o r analysis.  encountered i n obNo  well-formed  c r y s t a l s were a v a i l a b l e , only fragments which were very hygroscopic. d i f f i c u l t , and  T h i s made p r e l i m i n a r y o p t i c a l examination very a c r y s t a l which gave s u i t a b l e photographs  found only a f t e r a l a r g e number had been examined. that the c r y s t a l s had  no r e c o g n i z a b l e f a c e s , and  The  was fact  the n e c e s s i t y  33  o f  s e a l i n g  t h e m  i n  m a d e  t h e  i n i t i a l  u s e d  f o r  d a t a  s e c t i o n No  w e r e  l i n e - u p  a p p r o x i m a t e l y  K ^  )  1 2 0 ° o n  m o n o c h r o m a t i c  i n  2  t h e  a n d  9 •  i o n s  b y  w a s  0 . 2  a  -  a l l  0  -  2 Q  ( N i  w h e r e  w h e r e w e r e  S  a n d  t a k e n  s t r u c t u r e c l u d e d  3 a s  a r e  f a c t o r s  f r o m  t h e  0 . 5  m m .  s e c o n d s  2)  X R D  6  p u l s e  h e i g h t  p e r  w e r e  m i n u t e  m a d e  a t  s c a n .  i n  o f  f a c t o r s  t h e  l e s s  d e f i n e d  u s u a l  t h a n  3  w e r e  a p p l i e d  m a n n e r . s i g m a  a n d  R e f l e x -  a b o v e  b a c k -  b y  2  ( I )  t h e  b e i n g  0 . 8 9  d e g r e e s  2  <r  o f  a p p r o x i m a t e l y  a n d  2 0  e a c h  i s  f i l t e r  f o r  c o u n t s  c o u n t  c r o s s -  0  E l e c t r i c  t w o  d e r i v e d  ( I )  c"  2  s p a c i n g  o f  p o l a r i z a t i o n  n e t  f i n a l l y  w i t h  l e n g t h  w i t h  s c a n  a n d  a  a  s c i n t i l l a t i o n c o u n t e r ,  L o r e n t z  h a d  a n d  G e n e r a l  o f  w h i c h  m m .  i n t e r p l a n a r  e n d  f a c t o r s  c r y s t a l  f r a g m e n t ,  r e f l e x i o n s  r a d i a t i o n  a  T h e  h y d r o l y s i s ,  m a d e .  a n d  s t r u c t u r e  g r o u n d ,  w i t h  p r e v e n t  i r r e g u l a r  D a t e x - a u t o m a t e d  B a c k g r o u n d  b e g i n n i n g  t h e  C u  a n  m m .  o f  t o  d i f f i c u l t .  ( m i n i m u m  a  S p e c t r o g o n i o m e t e r  a n a l y z e r ) ,  0 . 2  i n t e n s i t i e s  ^  m e a s u r e d  v e r y  c o r r e c t i o n  T h e -  c a p i l l a r i e s  c o l l e c t i o n w a s  a b s o r p t i o n  ( G u  g l a s s  =  s c a n  S + B +  a n d  u n o b s e r v e d .  e q u a l  t o  r e f i n e m e n t .  t h e  (.05s)  b a c k g r o u n d T h e s e m e a s u r e d  O f  t h e  8 5 0  c o u n t s  r e f l e x i o n s v a l u e s  r e s p e c t i v e l y , w e r e  b u t  i n d e p e n d e n t  w e r e  a s s i g n e d e x -  r e f l e x i o n s  34  2 0  w i t h  1 2 0 ° ,  ^  S t r u c t u r e  1.3.2  T h e  {73%)  6 2 1  w e r e  c l a s s i f i e d  g e s t e d u s e d (3  i  d a t a  w e r e  p l a c e d  o n a n a b s o l u t e  b y  E  -s t a t i s t i c s  n p r e f e r e n c e  t o t h ec o n v e n t i o n a l  b y  g r o u p ,  ( T a b l e T h i s  I2/a.  V I I )  s u g -  o r i e n t a t i o n  C2/c_,  w h i c h  w a s  h a d  a  l a r g e  (131°). i  nt h e  N P  r e f l e x i o n s  w i t h  R o d d  w a s  N , P. F . M e  4 4 6  a x i s  t h e  s p a c e  s t r u c t u r e t h e  a n a  t h ec e n t r i c  A s a l l  s c a l e  49  m e t h o d ,  a n g l e  o b s e r v e d .  A n a l y s i s  47 W i l s o n ' s  a s  b e i n g  d e r i v e d  i  m o l e c u l e  2  p o s s i b l e  f u l l - m a t r i x  F . M e ,  4 4 4  i  s t r u c t u r e ,  4  w e r e  na  e x t r e m e l y  s i m i l a r  s i t u a t e d nt h i s  w e a k ,  f a s h i o n ,  o n a  c a s e .  l e a s t - s q u a r e s  t h ei n t e n s i t i e s a n d  o n l y  a  a  m e t h o d s ,  s t r u c t u r e  w i t h  f  t r i a l  m o d e l  c r y s t a l l o g r a p h i c  T h i s  o  w i t h  C  —2  w a s  r e f i n e d  t h e s c a t t e r i n g  9 f a c t o r s  f r o m  t h e  I n t e r n a t i o n a l  m e n t  c o n v e r g e d  a t R =  e n c e  s y n t h e s i s  i n d i c a t e d  v i b r a t i o n , o f  w ( F  o  p a r t i c u l a r l y  -  F ) ~~c  a p p r o p r i a t e f l e x i o n s ,  2  i  n r a n g e s  f o r o  w =  0  a n i s o t r o p i c  f u l l - m a t r i x  r e f i n e m e n t ,  t h ef i n a l  r e f l e x i o n s  a n d  f ( F  c a l c u l a t e d  s t r u c t u r e  —o  w a s  l e a s t  a l l  f a c t o r s  r e f i n e -  t h r e e - d i m e n s i o n a l a m o u n t  o  \  w =  s q u a r e s  d i f f e r -  f a n i s o t r o p i c a t o m s .  i n d i c a t e d 1 f o r  t h e u n o b s e r v e d  R b e i n g  0.084 f o r  I s o t r o p i c  t h ef l u o r i n e  s c h e m e  f o r  a  l a r g e  *  w e i g h t i n g  a n d  a n d  0.28, a  T a b l e s .  A n  t h a t  t h e  a n a l y s i s  t h e  0.067 f o r  t h e  350  r e f l e x i o n s .  a r e  l i s t e d  i  m o s t  o b s e r v e d r e -  r e f l e x i o n s . c y c l e s  t h e r m a l  T h r e e  c o m p l e t e d 621  o b s e r v e d  M e a s u r e d  n T a b l e  t h e  V I I I .  a n d A  35  TABLE V I I E - 3 t a t i s t i c s f o r N P.F,Me_  4 4 o  <L  Theoretical Observed  Centro.  Non-centro.  0.726  0.798  0.886  1.043  1.000  1.000  Mean |, s - i |  1.195  0.968  0.736  E > 3 (percent)  1.53  0.30  0.01  E > 2 (percent)  7.06  5.00  1.80  E > 1 (percent)  24.71  32.00  37.00  Mean 1 E l Mean \ E |  2  2  36 VIII  T A B L E  Observed and N^P  F^Me^.  final  calculated  structure  factors  for  U n o b s e r v e d r e f l e x i o n s have a n a s t e r i s k  follow-  ing  7S  2  }S  ? s  7  21  7  21  1  21  27 22  2 * >  2b  ? 7 2  21 20 21  20 2b  2 f>  2 7  ^l  2  si  I  l-  2k  il  2a  72 ID ?J  77. 7t.  37  f i n a l d i f f e r e n c e map showed maximum f l u c t u a t i o n s o f + 0.3  e.A  w i t h no c l e a r i n d i c a t i o n o f hydrogen atom p o s i t i o n s . F i n a l p o s i t i o n a l and t h e r m a l parameters  a r e i n p o s i t i o n s 4(e_) o f  i n Table IX. Atoms P ( l ) and P(3) I2/a: (GOO;  (000; ^ ^ ^) +  t  n  e  rj- —) + ( x , y_, z_; x,  are given  o t h e r atoms a r e i n 8 ( f ) : + z).  Bond l e n g t h s and  v a l e n c y a n g l e s p e r t a i n i n g t o the p h o s p h o n i t r i i i c r i n g a r e shown s c h e m a t i c a l l y i n F i g u r e 6 and a complete g i v e n i n Table X.  listing i s  A view o f t h e m o l e c u l e down c * i s shown  i n F i g u r e 7 and t h e m o l e c u l a r p a c k i n g i n t h e u n i t c e l l down b i n F i g u r e 8.  A g e n e r a l view o f t h e m o l e c u l e  viewed  illus-  t r a t i n g t h e t h e r m a l e l l i p s o i d s o f 0.5 p r o b a b i l i t y i s shown i n F i g u r e 9. The t h e r m a l parameters  (Table V) c o r r e s p o n d t o a  l a r g e amount o f a n i s o t r o p i c t h e r m a l m o t i o n , p a r t i c u l a r l y f o r the f l u o r i n e atoms, where t h e r o o t mean square a m p l i t u d e s o f o v i b r a t i o n a r e a s h i g h as 0.6 A. ( F i g u r e 9 ) . Since the data were c o l l e c t e d a t room temperature o $1 m e l t s a t 50 ,  ( c a . 20°) and t h e compound  t h e h i g h t h e r m a l v i b r a t i o n i s not s u r p r i s i n g ;  n e v e r t h e l e s s i t d i d seem n e c e s s a r y t o examine whether t h e observed parameters  c o u l d i n f a c t be a r e s u l t o f d i s o r d e r  i n space group I 2 / a , o r o f a t r u e symmetry l a . E i t h e r o f these p o s s i b i l i t i e s would however r e s u l t i n t h e o b s e r v a t i o n of an apparent m o l e c u l a r symmetry h i g h e r t h a n t h a t t o be expected f o r t h e m o l e c u l e , whereas t h e observed bond l e n g t h s  33  TABLE IX F i n a l p o s i t i o n a l parameters, w i t h standard d e v i a t i o n s i n o2 ^ p a r e n t h e s e s , and a n i s o t r o p i c t h e r m a l parameters (A x 10 ) Atom P(D  F(2) P(3) N(l) N(2) F(l) F(2) F(3) C(l) Atom P(D  P(2) P(3) N(l)  W(2)  F(l) F(2) F(3) C(l)  0 0.2060(2) 0 0.1261(8) 0.1463(8) 0.0690(7) 0.2455(12) 0.3701(6) 0.0657(10) U  -11 6.98 6.99 6.31 11.52 8.32 16.70 31.64 7.28 12.14  U  -22 4.94 6.07 4.68 6.68 6.28 10.94 14.89 12.91 8.18  0.1734(2) 0.0084(2) -0.1635(2) 0.1177(5) -0.0967(5 ) 0.2548(5) 0.0031(6) 0.0173(5) -0.2508(7)  -33 10.55 11.03 18.65 25.88 20.81 15.39 38.54 39.21 9.07  U  -12 0 0.07 0 1.51 -0.37 -4.32 7.60 -0.74 0.33  1/4 0.2340(3 ) 1/4 0.2250(9) 0.2543(9) 0.3549(6) 0.1167(11 0.3259(10 0.3904(8)  -13 3.79 7.47 3.94 12.02 7.51 6.25 29.20 5.34 3.37  u  2 3  0 1.63 0 2.61 -0.12 -4«46 7.42 1.50 0.80  39  F i g u r e 6.  Bond l e n g t h s  (A) and valency angles  in t h e phosphonitrilic  (degrees)  r i n g of N. P. F/Me  ,  40  T A B L E B o n d  l e n g t h s  (A*)  s t a n d a r d  a n d  v a l e n c y  d e v i a t i o n s  X a n g l e s i n  ( d e g r e e s ) ,  v / i t h  p a r e n t h e s e s .  P ( l ) - N ( l )  1 . 4 8 7 ( 6 )  P ( D - F ( 1 )  1 . 4 8 1 ( 5 )  P ( 2 ) - N ( l )  1 . 5 3 2 ( 6 )  P ( 2 ) - F ( 2 )  1 . 4 9 5 ( 8 )  P ( 2 ) - N ( 2 )  1 . 4 7 0 ( 6 )  P ( 2 ) - F ( 3 )  1 . 4 6 6 ( 6 )  P ( 3  1 . 5 8 4 ( 6 )  P ( 3 ) - C ( l )  1 . 7 9 4 ( 8 )  1 2 4 . 6 ( 5 )  F ( l ) - P ( l ) - N ( l )  109.7(4)  N ( l ) - P ( 2 ) - N ( 2 )  1 2 6 . 1  F ( l »  1 0 7 . 2 ( 4 )  N ( 2 '  1 1 6 . 9 ( 5 )  N ( l »  ) - N ( 2 )  ) - P ( l ) - N ( l )  ) - P ( 3 ) - N ( 2 )  ( 3 ).  ) - P ( l ) - N ( l )  F ( 2 ) - P ( 2 ) - N ( l )  1 0 5 . 5 ( 4 )  F ( 3 ) - P ( 2 ) - N ( D  1 0 9 . 0 ( 4 )  P ( l ) - N ( l ) - P ( 2 )  1 4 3 . 3 ( 5 )  F ( 2 ) - P ( 2 ) - N ( 2 )  1 0 9 . 8 ( 5 )  P ( 2 ) - N ( 2 ) - P ( 3 )  1 4 6 . 7 ( 5 )  F ( 3 ) - P ( 2 ) - N ( 2 )  1 0 8 . 4 ( 4 )  C ( l ) - P ( 3 ) - N ( 2 )  1 0 7 . 5 ( 4 )  C ( I '  1 0 9 . 3 ( 4 )  F ( l '  ) - P ( l ) - F ( l )  F ( 2 ) - P ( 2 ) - F ( 3 ) G ( l ' ) - P ( 3 ) - C ( l )  9 4 . 1 ( 5 ) 9 3 . 2 ( 5 ) 1 0 5 . 7 ( 6 )  ) - P ( 3 ) - K ( 2 )  43  Figure 9.  General view of the N,P.F„Ke„ molecule i l l u s 4 4 o 2 t r a t i n g the thermal e l l i p s o i d s of 0.$ probability.  44  a n d  v a l e n c y  a n g l e s  c o n f o r m a t i o n C . .  I t  a r e  a  i s  1 . 3 . 3  ( F i g u r e  l i k e l y  t r u e  7 )  t h e n  t h e r m a l  6  a n d  T a b l e  c o r r e s p o n d t h a t  t h e  t o  h i g h  X )  a n d  m o l e c u l a r  m o l e c u l a r  s y m m e t r y  t e m p e r a t u r e  p a r a m e t e r s  e f f e c t .  D i s c u s s i o n T h e  b o n d o A  ( F i g u r e  N , P F , H e m o l e c u l e 4 4 6 2  l e n g t h s :  . ( F i g u r e  c a u s e d  I.584,  . . 6 ) .  b y  T h i s  t h e  1 , 4 7 0 ,  1 , 5 3 2 ,  v a r i a t i o n  d i f f e r i n g  e x h i b i t s a n d  r e s u l t s  f o u r 1 . 4 8 7  d i s t i n c t (  f r o m  t h e  e l e c t r o n e g a t i v i t i e s  o f  P - N  =-  6~  0 . 0 0 6 )  p e r t u r b a t i o n t h e  s u b s t i t u 2 4  e n t s , T h e  a n d  m a y  g r e a t e r  b e  e x p l a i n e d  t o  t h e  t r o n s  b e  d r a w n  P ( 3 )  m e t h y l  f r o m  b o s h  o c t a f l u o r o  c o m p o u n d ,  f o u n d  p h o s p h o n i t r i i i c  a b i l i t y  a o f  t T  ( N P F ^ 2  - e l e c t r o n s  i n t o  - b o n d i n g  f l u o r i n e ( F i g u r e  a t o m s  6 ) ,  f r o m  N ( 2 )  B e c a u s e  ( 1 . 5 3 4  o A )  P ( 2 ) , e l e c -  t h e  i s  n d e s t p a r e n t r  o f  t h i s  a v a i l -  d o n a t i o n  f r o m  N ( l )  t h e  r e s u l t i s a n i n c r e a s e i n o 1 . 5 3 2 A . T h i s i n t u r n e n h a n c e s l e n g t h T h e  0  b o n d  a t  c a u s e s  d o n a t i o n f r o m N ( l ) t o P ( l ) r e s u l t i n g i n a b o n d o o 1 . 4 3 7 A w h i c h i s 0 . 0 2 A s h o r t e r t h a n i n ( K P F ) . .  P ( 3 ) - N ( 2 )  t h e o r y .  t h e  m o l e c u l e .  P ( 2 ) i s l e s s f a v o u r e d a n d . . . . t h e P ( 2 ) - N ( l ) b o n d l e n g t h t o  o f  t h e  fT  o f  P ( 2 ) - N ( 2 ) TT - b o o n d ( 1 . 4 7 0 A ) b e i n g t h e s h o r t o r t e r t h a n t h e b o n d s i n t h e 3 6 ) , a n d t h e s h o r t e s t so f a 4  t o  t h e  o f  g r o u p s  N ( 2 )  a n d r e s u l t s i n t h i s P - N i n t h e m o l e c u l e , 0 . 0 4 2  i n  t e r m s  e l e c t r o n e g a t i v i t y  c o m p a r e d t o  i n  t h e  l o n g e s t  P - N  b o n d  i n  t h e  m o l e o  c u l e ,  b u t  i s  a p p a r e n t l y  s l i g h t l y  s h o r t e r  t h a n  t h e  1 . 5 9 6  A  45  bond i n t h e  p a r e n t o c t a m e t h y l compound.  pected t h a t the  P(3 )-N(2) bond s h o u l d  o c t a m e t h y l compound, b e c a u s e o f t h e N(2)  e l e c t r o n s t o P ( 2 ) , but  i s the  greater  of a i l the  be  longer  of  this  tendency  d e l o c a l i z a t i o n of the lone  pair  electrons  fluorine substituents.  t a n c e i n N, P F^M'e . 4 4 6 2 I t m i g h t be  large  not  be  inductive  I t appears that P(3)-N(2) bond  n o t e d t h a t t h e bond l e n g t h  o b s e r v e d i n N P, F,Ke can 4 4 6 2  explained ^  i n bond l e n g t h a r o u n d t h e  ring;  ring.  Thus t h e  dis-  i n terms of  1T - b o n d i n g must be  f u r t h e r m o r e must be d e l o c a l i z e d o v e r t h e  the  alternations  bond i n a u c t i v e e f f e c t s , w h i c h w o u l d p r o d u c e a g r a d u a l  phonitrilic  the  counteracting  e f f e c t i s a s l i g h t decrease i n the  and  ex-  than i n  favoured donation  n i t r o g e n atoms, because of the  e f f e c t s of the net  I t m i g h t be  6 ^ change  involved,  e n t i r e phos-  TT - b o n d i n g s y s t e m  postulated  29 by  Dewar  w h i c h was  o u t l i n e d i n s e c t i o n 1.1  does not  seem  probable. The  magnitude of the  bond l e n g t h  v a r i a t i o n i s sim-  ilar  t o t h a t o b s e r v e d i n r i n g s w h i c h a r e p e r t u r b e d by p r o t o 37,43,44 J . _ _ , nation at nitrogen, and i s a t t r i b u t a b l e t o t h e p o l a r i z a b i l i t y of the the  TT - b o n d i n g s y s t e m i n p h o s p h o n i t r i l e s ,  range of v a r i a t i o n o f bond l e n g t h s  being  much  greater  t h a n i n o r g a n i c compounds f o r s i m i l a r c h a n g e s i n s u b s t i t u e n t . The e f f e c t o f a ft* - i n d u c t i v e p e r t u r b a t i o n a t p h o s p h o r u s  4 6  has been e s t i m a t e d t h r o u g h t h e c a l c u l a t i o n o f bond-atom 52 — 5/j. polarizabilities from s i m p l e H i i c k e l t h e o r y f o r a de55 localized Tt -system based on an eight-membered r i n g . They a r e shown i n F i g u r e 1 0 ,  i n comparison v/ith t h e observed  d e v i a t i o n s o f i n d i v i d u a l bond l e n g t h s from t h e mean, f o r t h e f o u r s u c c e s s i v e d i s t i n c t bonds i n N P F,Me 4 4 6  correspondence  .  The c l o s e  2  i n p a t t e r n seems a d d i t i o n a l evidence f o r  1T - e l e c t r o n d e l o c a l i z a t i o n i n p h o s p h o n i t r i l e s . The mean P-F d i s t a n c e (1.48 (1.79  A ) and the P-C d i s t a n c e  o A) a r e q u i t e s i m i l a r t o t h e l e n g t h s i n N,P F Me 36  30  ^ 4 4 4  , and  i n the o c t a f l u o r o and o c t a m e t h y l compounds. The most n o t a b l e f e a t u r e s o f t h e v a l e n c y a n g l e s a r e the l a r g e v a l u e s a t the n i t r o g e n s ( F i g u r e 6 ) , t h e average o o . . v a l u e o f 145 a p p r o a c h i n g t h e v a l u e o f 147 found i n (NPF„J . c  4  In the o c t a f l u o r o compound t h i s has been a t t r i b u t e d t o t h e 36  large i n d u c t i v e e f f e c t s of the f l u o r i n e s ,  and t h i s i s most  l i k e l y t h e case i n t h e p r e s e n t s t r u c t u r e as w e l l . c y c l i c a n g l e s a t P ( l ) and P(2) ponding a n g l e a t P(3)  The endo-  a r e l a r g e r than t h e c o r r e s o  by an average o f 8 , t h i s b e i n g r e -  l a t e d t o the e x o c y c l i c F-P-F a n g l e s a t P ( l ) and P(2) 12°  being  s m a l l e r than the C-P-C a n g l e a t P ( 3 ) . The eight-membered p h o s p h o n i t r i l i c r i n g has t h e  'saddle' c o n f o r m a t i o n  (Figure 7),  w i t h the f o u r n i t r o g e n  atoms a l t e r n a t i n g above and below the p l a n e c o n t a i n i n g t h e  47  -0.05  J  I  I  1  1  a  b  c  d  Bond  Figure  10.  (i)  Deviation  t h e mean, and for  of individual ( i i ) bond-atom  the N , P . F , M e 4 4 6 2  molecule.  bond l e n g t h s  from  polarizabilities  4 8  f o u r  p h o s p h o r u s  0 . 0 3 1 1  X '  r e f e r r e d o f  t h e  t o N  4  t o  4  M e  4  a d o p t s T h e  t h e ,  V  =  f  a t o m s  N ( 2 ' )  -  r i n g  ' t u b '  a x e s  0 . 1 5 ,  b ,  I n  t h e  a r e  i n  A ,  d i s p l a c e m e n t s -  A .  0 . 1 $ ,  I t  e  u s e f u l 3 0 N . P, M e a , '  s e r i e s  i s  4  c o m p o u n d a n  i s  M ( l )  t h e  p r i m a r i l y  b e i n g  Z '  T h e  0 . 1 5  T h e  r  n i t r o g e n s p l a n e .  +  36  a n d  a r e :  f o r  N , P , F , . 4 4 8  p l a n e  c * .  p l a n e N ( l ' )  t h e  X '  a n d  c o n f o r m a t i o n s  c o n f o r m a t i o n  t h e  p h o s p h o r u s  a ,  a n d  a n d  o f  w h e r e  t h i s  t e t r a m e t h y l t e t r a f l u o r o w i t h  e q u a t i o n  2 . 4 4 3 0 ,  f r o m  I-T P M e F , , 4 4 2 6'  t h e  m a t i o n t h e  F  Z  T h e  o r t h o g o n a l  0 . 1 5 ,  c o m p a r e P  0 . 9 9 6 7  n i t r o g e n +  N(2)  +  a t o m s .  h a s  o c t a m e t h y l ' f o r  s t e r i c  t h e  ' s a d d l e  a v e r a g e  p r e s e n t  o f  0 . 4 8  c o m p o u n d  4  8  c o m p o u n d r e a s o n s .  .  c o n f o r -  1  A  t h i s  o  o f f d i s p l a c e -  o m e n t  i s  r e d u c e d  p l a n a r . b e r  o f  a g a i n t h e  T h u s  b e i n g  t h e a t  c o r r e l a t i o n  t e n d e n c y t o  t h e  o c t a f l u o r o  t o w a r d s l a r g e  i n t e r m o l e c u l a r  f l u o r i n e s  T h e  x ,  t h e  d i r e c t  t h e  s h o r t e s t  b e t w e e n  +  a n d  a  a n d  c o m p o u n d  b e t w e e n  t h e  p l a n a r i t y ,  i n d u c t i v e  i s n u m -  t h i s  e f f e c t s  o f  s u b s t i t u e n t s .  s t a n d a r d ( - £  i s  a t t r i b u t a b l e  T h e  a c t i o n s .  A,  0 . 1 5  t h e r e  f l u o r i n e s  f l u o r i n e  t a c t s  t o  s h o r t e s t m o l e c u l e  2  -  il>  a n d  2j.  c o r r e s p o n d  d i s t a n c e ( a t  x ,  d i s t a n c e s  y_,  t o o  i s  3-33  A  z)  a n d  F(3)  v a n  i n v o l v e d e r  b e t w e e n o f  t h e  c o n -  W a a l s  F ( l )  i n t e r -  o f  m o l e c u l e  P A R T  T H E  S T R U C T U R E  I I  D E T E R M I N A T I O N  OF  H E X A P H S N O X Y C Y C L O T R I P H O S P H O N I T R I L E  5 0  2 . 1  I n t r o d u c t i o n T h e  s t r u c t u r e s  h a v e  b e e n  r e p o r t e d  s e e n  o n l y  t h e  s l i g h t  c h a i r  p l a n a r i t y  i n  t h e  h a v i n g  s e v e r a l  e x t e n t  b e e n  T h e  l i s t e d  56  i s  e f f e c t s .  t h e  p a r t i c u l a r  r i n g s  t o  a n d i n -  t h e  1 . 1 , T a b l e  c o n f o r m a t i o n s  c o n f o r m a t i o n  f r o m  i n t r a -  r e s e m b l e s  i s  h a v e  s i t u a t i o n I )  w h e r e ,  h a v e  b e e n  i n f l u e n c e d  f o u n d , t o  f o r c e s .  c r y s t a l  g e o m e t r y  a s c r i b e d  w h i c h  m a y b e  t h e d e v i a t i o n s  T h i s  r i n g  X I , a n d a s  T h e o t h e r  ( s e c t i o n  d i f f e r e n t  a n d m o l e c u l a r  x y c y c l o t r i p h o s p h o n i t r i l e , c o m p a r e  i n T a b l e  v a r i o u s l y  s t e r i c  p h o s p h o n i t r i l e s  p l a n a r .  c o m p o u n d s  o f a b y  t r i m e r i c  c o n f o r m a t i o n s ,  s t e r i c  a d o p t i o n  s o m e  b o a t  t e t r a m e r i c  a l t h o u g h t h e  f l u o r i d e o r  t e r m o l e c u l a r  a r e  o f  s t r u c t u r e  jJ'JPfOPh),^  w i t h  t h e  o t h e r  ,  o f  h e x a p h e n o -  w a s u n d e r t a k e n  h o m o g e n e o u s l y  t o  s u b s t i t u t e d  c y c l o t r i p h o s p h o n i t r i l e s , t o  o b t a i n  e x a m i n e p o s s i b l e o x y g e n  a c c u r a t e  t h e  i n t r a -  b y  o f t h e m o l e c u l a r  a n d i n t e r m o l e c u l a r  e x o c y c l i c  - b o n d i n g  TT  s t e r i c  b e t w e e n  d i m e n s i o n s , e f f e c t s  p h o s p h o r u s  t o o f  a n d  a t o m s . T h e  p l a c e m e n t  v a l u e s  o f  r e a c t i o n  t r i m e r i c c h l o r i n e  w i t h  p h e n o x y a t o m s  s o d i u m  c o m p o u n d  o n t h e  p h e n o x i d e .  N a O P h b e n z e n e  i s  p r e p a r e d  c o r r e s p o n d i n g  60  b y  r e -  c h l o r i d e  T A B L E X  I  S t r u c t u r a l parameters o f t r i m e r i c p h o s p h o n i t r i l e s deviations Compound  with standard  o f bond l e n g t h s and valence angles i n parentheses.  P-N(2)  P-N-P(degrees)  N-P-N(degrees)  Conformation  Reference  N  3 3 6  1.56(1)  121(1)  119(1)  planar  56  N  3 3  6  1.59(2)  120(1)  120(1)  chair  57  N  3 3 6  1.58(4)  121(3)  117(2)  slight  chair  53  N  3 3 6  1.597(6)  122.1(4)  117.8(3)  slight  chair  59  N  3 3°V 2  1.615(5) 1.555(5)  122.0(3) 119.2(3)  115-2(2) 119.7(3)  slight  chair  40  \  1.556(8) 1.609(8) 1.578(8)  121.0(5) 124.9(5)  120.7(4) 115.5(4)  s l i g h t boat  41  N P F Ph 3 3 4 2  1.618(5) 1.558(4) 1.539(5)  120.5(2)  115.5(3) 120.6(3)  s l i g h t boat  42  1.670(5) 1.56*0(5) 1.560(5)  132.0(4) 125.5(4)  120.0(4) 107.5(4)  distorted boat  44  P  F  P  P  CJl  B r  P  P h  P  h  1.578(5)  y  c 3  *  p 2  N P CJl (NHPr ). •HCA 3 3 2 4 i  X  52  2 . 2  E x p e r i m e n t a l C r y s t a l s  c o l o u r l e s s  n e e d l e s  g r o u p  w e r e  a n d  d a t a  f o r  b y  a  h e x a p h e n o x y c y c l o t r i p h o s p h o n i t r i l e  e l o n g a t e d  o b t a i n e d  p r e c e s s i o n  m i n e d  o f  f i l m s ;  f r o m  g e n e r a l  a .  U n i t  v a r i o u s  a c c u r a t e  l e a s t - s q u a r e s  t w e n t y - f i v e  a l o n g  c e l l  a n d  r o t a t i o n ,  l a t t i c e  a p p l i e d  t o  r e f l e x i o n s  m e a s u r e d  s p a c e  W e i s s e n b e r g ,  p a r a m e t e r s  p r o c e d u r e  a r e  w e r e  2 &  o n  d e t e r -  v a l u e s  a  s p e c t r o -  g o n i o m e t e r .  C r y s t a l  d a t a .  — M o n o c l i n i c , A,  (3  U  =  '2 =  a  D  P, =  ~ ( C u - K  1.323  ,  ft  s y s t e m a t i c k  i s  =  =  19.6  N  30  3  0,P  6 3  =  .  M  d e v i a t i o n s i n  1440.  =  ~ c  19.270(3),  ( f l o t a t i o n  F ( 0 0 0 )  a b s e n c e s :  6 9 3 - 5 8 . =  1 6 . 1 7 1 ( 4 )  i n  p a r e n t h e s e s ) ,  C H B r  / C  ( C u - K *  A  )  ) ,  6  =  1.5418  5  - 1 c m .  H  6  .  hOj?  S p a c e w h e n  g r o u p  (h+jL)  i s  P 2  / n ( C  o d d ,  ),  O k O  f r o m  w h e n  o d d .  T h e 2 0  1.32  " )  b  H  A  3D  ( s t a n d a r d  =  £  M.  C _  1 1 . 1 7 6 ( 4 ) ,  9 2 . 0 7 ( 2 ) °  =  3 4 8 0 . 2 4 ,  =  —  ( O u - K ^  0.97  A )  t r i c  Z R D  )  w e r e 6  p u l s e  p e r  m i n u t e  4-  105°  m e a s u r e d  o f  o n  a  m o n o c h r o m a t i c  h e i g h t i n  2 0.  a l l  ( m i n i m u m  d i f f r a c t o m e t e r ,  a p p r o x i m a t e l y a n d  i n t e n s i t i e s  r e f l e x i o n s  i n t e r p l a n a r  D a t e x - a u t o m a t e d w i t h  a  C u - K  x  d  G e n e r a l  E l e c -  r a d i a t i o n 0-20  B a c k g r o u n d  c o u n t s  a n d  s p a c i n g ,  s c i n t i l l a t i o n  a  a n a l y s e r ) ,  w i t h  o f  =  c o u n t e r ,  ( N i  f i l t e r  s c a n  a t  2 0  2 °  s e c o n d s  A ,  53  w e r e  m a d e  a t t h eb e g i n n i n g  3  <5~ ( I )  a b o v e  e n d  o  2899 (75£>)  i n d e p e n d e n t ' r e f l e x i o n s , t h a n  a n d  b a c k g r o u n d ,  f e a c h  h a d  O f 3883  s c a n .  i n t e n s i t i e s  w h e r e  6~ ( I )  i  s  g r e a t e r d e f i n e d  b y  <r (i)  = s + B +  2  a n d  3 =  s c a n  r e f l e x i o n s i o n  w a s  c o u n t ,  w e r e  B =  e v e r y  t e n s i t y  v a r y i n g  o f  c o l l e c t i o n .  d a t a  w e r e T h e x  a p p l i e d ,  t h e  m a x i m u m  o  L o r e n t z  a n d  m m . ,  a n d  n o a b s o r p t i o n  S t r u c t u r e  a  0.52  p h o s p h o r u s  f u n c t i o n o  t r i a n g l e  i n c l u d i n g  d u r i n g  i  t h e  p o l a r i z a t i o n  a n d  r e f l e x t  s i n h o u r s  c o r r e c t i o n s  w ere  d e r i v e d .  r  w a s  984  168  c r o s s - s e c t i o n  c o r r e c t i o n  a t o m  p o s i t i o n s  s h a r p e n e d u s e d  w a s  ft h eP a t t e r s o n  t h ei n t r a m o l e c u l a r  l a t e r a l  A c h e c k  a m p l i t u d e s  m m .  o t h e r  m m .  0.21  m a d e .  A n a l y s i s  t h r e e - d i m e n s i o n a l  s h a r p e n i n g  T h e  r e f l e x i o n s ,  f + 1.5/b  t h es t r u c t u r e  l e n g t h  I n t e r p r e t a t i o n t h a t  a n d  c o u n t .  s e v e n t y - f i v e  h a d  T h e f r o m  b ya  2  a s u n o b s e r v e d .  c r y s t a l  0.19  2.3  b a c k g r o u n d  c l a s s i f i e d  m o n i t o r e d  (0.05s)  o  t h et h r e e  f s i d e  P - P  P a t t e r s o n  (2 s i n w a s  v e c t o r s  2.85  p h o s p h o r u s  2.  w e r e  s i m p l i f i e d  T h e  a t o m s  a  + b  n e a r l y  i n i t i a l o n l y  f u n c t i o n ;  ) / ( I  2Q  f o r m  d e t e r m i n e d  w a s  c o s  2Q  y a s s u m i n g e q u i -  d i s c r e p a n c y O.56. T h e  ).  54  r e m a i n i n g t h r e e a t  f o r t y - f i v e  s u c c e s s i v e  t h i s  s t a g e  a t o m s  e l e c t r o n - d e n s i t y  m a p s .  w a s  T h e a n d  n o n - h y d r o g e n  l e a s t - s q u a r e s  s c a l e m e t h o d s ,  2  i  n F,  f r o m  T h e d i s c r e p a n c y  a n d i s o t r o p i c  f a c t o r  ^^^(FQ-F^) , w i t h v a r i a n c e  l o c a t e d  0.40.  p o s i t i o n a l  a n o v e r a l l  w e r e  w e r e  r e f i n e d  t h e f u n c t i o n w  t a k e n  t h e r m a l b y  p a r a m e t e r s  b l o c k - d i a g o n a l  m i n i m i z e d  b e i n g  a s t h e r e c i p r o c a l  a s d e t e r m i n e d  f r o m  o ft h e  t h e c o u n t i n g  s t a t i s t i c s . 9  T h e  s c a t t e r i n g  w e r e  u s e d .  r e f l e x i o n s . p a r a m e t e r s  t h r e e - d i m e n s i o n a l a l l  t h i r t y  d e n s i t y i n  m a x i m a  v / i t h  t h e i n t e r n a t i o n a l  w a sr e a c h e d S i x  f u r t h e r  r e d u c e d  b e i n g  a t o m s  a t  R =  c y c l e s  R t o 0 . 0 5 8 .  d i f f e r e n c e  h y d r o g e n  t h e m a p .  m e n t ,  f r o m  C o n v e r g e n c e  o b s e r v e d t h e r m a l  f a c t o r s  i  a m o n g  T a b l e s  0.095 f o r t h e  v / i t h  a n i s o t r o p i c  A t t h i s  s y n t h e s i s  s t a g e  c l e a r l y  n t h e m o l e c u l e ,  T h eh y d r o g e n  a t o m s  w e r e  t h e s c a t t e r i n g  c u r v e  o f S t e w a r t ,  r e v e a l e d  t h e i r  t h e t h i r t y - s e v e n  e l e c t r o n -  h i g h e s t  i n c l u d e d  a  i  p e a k s  n t h e  r e f i n e -  D a v i d s o n , a n d  6l S i m p s o n , w a s  a n d i s o t r o p i c  c o n t i n u e d  o b s e r v e d f a c t o r s F i n a l  u n t i l  r e f l e x i o n s .  t h e r m a l  c o n v e r g e n c e M e a s u r e d  a t  p h o s p h o r u s ,  a n d t h e r m a l  n i t r o g e n ,  o x y g e n ,  R =  R e f i n e m e n t  0.037 f o r t h e  a n d c a l c u l a t e d  A v i e w o f t h e m o l e c u l e a r e l i s t e d i n T a b l e I I I . p o s i t i o n a l  p a r a m e t e r s .  i s s h o w n  p a r a m e t e r s a n d c a r b o n  2 8 9 9  s t r u c t u r e  i n F i g u r e 1 1 .  a r e g i v e n a t o m s  f o r t h e  i n T a b l e  XIII,  T.-iBLE X X I O b s e r v e d  a n a  [NP(0Ph) ] 2  h k I R R  f i n a l .  c a l c u l a t e d  U n o b s e r v e d  20 8. .0 4 2 -3 9. .9 7 10 .6 15.6I .4 14 3. .1 01.012.3 6 1 1 . 1 2 3 2. .9 8.0 4 1 1 4 . 7 _ 10. 8_  55  s t r u c t u r e  r e f l e x i o n s  f a c t o r s  h a v e  a  f o r  n e g a t i v e  8 637. 138.5 1 B 7 -I2. . 970 .2 7 61 ii 8 109 7 12 9. 1 12 9. . 1 1 . 7 il a8 1 3 7 . 3 1 7 . 4 5 . 8 4 6 .0 2 lft 2 0 . 2 1 9 . f t 4914 37 0. .0 0 6.S 4 . 22 . 0 1 9 --11?2 10 4. .0 0 16 4. .4 9 1 9 3 1 9 1 0 2 9 . 6 2 8 . 6 1 1. .9 0 22 0. .3 5 I1 199 ---8T9 2 2 4 . 2 4. .9 8 12.7 99 --54 2 12 1 4 . 3 32 6. .9 3 1 7.4 5 -1 119.7 19.6 1 1 9 3 2 2 . 5 99 -2-14 9. .6 5 48.3 27.7 2 14 8. ,9 42 14 8. 5" 1 7 .7 4 1 1«r -5 5 95 3 2 6 1 6 5 . 9 1 3 . 01 3 9 9e4 0' .4.9 7 19 10.3 I1 55 78 19 2 2. . 2 " 1 28 7. .9 99 20 6. .5 -5 1 9 1 7 . 8 1 8 . 0 1 9 3 3 6 . 6 3 5 . 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T .. 22-<U 32.0 1  6 1 .96 7 6 . 70 7. .1 4 284 .. 95 2 8 . 2 6 0 6 5 . 4 6 2 . T 6 6 , 5 1 2 B . 1 1 3 6 . 105.710779..32P . 9B. 1  *  2206..81 H.7 " 4.7  34.6 50.0 54.0 39.2  5 9. 6 5 2 338.. 3  5 B 2 2. .0 4 33 9 . 3 4 . 1 2 9 . 1 55 4. .6 2 4.0 2 1 17.47.6  3 1 1 5. .5 0 7 4 . 5 31 47 .. 96 3 4 3. .6 7 4 1 . 4 1 7 . 6 11 0. .3 2 4 7. 2 2 0 .0 5 7 2 19 3. .0 2 . 7 1139..58 -1 0.2  5 7  T A B L E  continued hk F F c  0  .-20.1..I a. 3.  41.4 . 16.00.6 _3 24 5. .1 3_? 6.1• 3 _ 3 3 2 5 . 3 2 5 . 3 5 3 . 3 5 1 . 9 20.5 18.9  9.40 "26 2.1 .8 ih.i  25 . 4 2 4. . 2 0 4 9 90 46 8. . 4 -5 .9 3 5 . 4 16 6 . 6 3 . 5 12 2. .9 0 23 .9 5 25 5. . 2 5 10 5. .1 3  6 0 . 6 2 5 . 2 2 3 . 0 20.8  3 . 8 3 7 . 6 -6 . 1 3 8. 4 2 11 3. .8 1 4 1 . 7 16 2. -6 0 11 5. . 2 4 1 8 . 8 1 9 . 0 2O 1 . 2 . 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B 3 6 . 9 3 0 . 8 2 8 . 7 . 1 5. 7 -4 4 . 7 30 4. .6 6 15 0. .3 9 5 4. .3 8 3 93 3 1 . 32 .1 4 1 . 2 2 36 6. .9 3. 7 . 9 37 8. .3 7 12 0 1 . 5 1 0 . 4 0 .0 4 34 9. .0 2 4 . 0 2 0 3 8 . 1 34.9 54. 4 2 . 1 78 9 . 4 3 5. .8 7 68 6 . 2 4 8. .5 7 -5 1 5. .8 19.T 15 7 5. 3 3 .9 8 30 . 7 2 1 . 8 1 9 . 4 1 5 . 0 2 5 . 5 4 0 . 2 2 2 . 2 4 8. . 4 T 7 3 3 9 . 6 5 0 . 9 1 0. .8 15 7 3 .1 5  12. .5 2 -6 3.3 9 1. .9 3 2 1 .92 2 0 2 0 . 3 I B . 9 5 . 3 0 . 7 1 6 . 2 3 8 . 5 37 . 8 3 7 . 9 7. .3 0 2 3 . 23 2 4 3 2 . 8 3 3 . 5 4 7 . 0 4 5 . C 10 6. .3 34 14. .7 5 5 89 7.6  2 8 . 3 15 9. .1 3 2 I7 T. .0 7 2 2 4 . 9  10 4. .0 0 13 . 7 1 . 9 -5 . 6 4 . 7 0 . 0 3.3 7 , 1 _2 5 2 4i_. 4_ 33 9, . 1 9 .7 8 40 5. 1 5 . 0 9 7 . 3 1 5. .6 9 1 5 . 9 1 2 . 9 1 2 . 4 2 . 6 10 0. .1 3.0 2 IT9 .2.6 4 8 0 -10 .1. 0_  3 9 18 5. . 3 18 5. 3 8 . 7 . 3 1 . 2 9 . 8 3 4 . 0 _4 3. 55 .85 1 9 . 1 2 0 1 3 . 2 1 3 . 1 9.1 0 52 8. 852 2 14. .6 15. .6 72 2—  60 .. 3 4 . 2_4 10 2. . 1 17 0. .8 2 5 8 2 0 16 1. .5 74 1 3 . 2 4 7 . 1 _5 . 8 _ 5 . p . 4 7 . 4 4 9 . 4 9 13 2. .5 9 13 1. . 14 9. .6 1 2 2 . 3 12 3 .1 8 1 8 . 7 . 1 5. .5 7_1 1 8 . 2. _1 4 . 0 8 . 5 2 2 . 5 2 1 4 7. . 24 8. . 2.9 2 0 7 26 1 5 -67 ..5_ T .3 __1 5, 3. 14.7 . 1 15 0 . 0 1 . 3  -9.7 ,_I3 T. .0 6.  .9 .8 2<r.t_ 9.  10 5. 1 3 5 12 2. . 9 4 . 2 2 6 . 5 _25 . T 5.7_ 1. 2 1 0 125 9*. . 1 _4 -L 11 1 0.3 1. 5 .3. 1 -8 . 9 0 . 0 -8 . 5 17 9. .7 5 2 2 . 9 2 4 . 2 -2. 4 14 6.9 6 2 0. .3 7 22.5 2 4 . 4 1 . 24 1 7 . 6 11 7. .6 5 35 7. 0 . 8 28 5. . 2 0 111 .8 -1 1 . 3 2 3 . 22 1. .6 5 2 6 . 3 2 4 1 9 . 9 1 9 . 2 17 6. . 12 17 5. .0 0 2 5 1 6 . 2 1 7 . 0 3. 1.0 _*8 -6 0 2 . 3 . 4 2 1 . 4 2 0 .9 7 2 9 . 2 3 0 . 6 . 5 2 7 . 4 41 4. .0 4 "28 3. .6 1 "' 34.7 18 2. 0 . 4 14 8. . 9 3 3 0 . 0 6 .7 16"34.5 ~3 3 1 4 . 23 13 . 6 3 4 . 0 4 . 4 6 . 3 6 . 0 1 5 . 9 1 6 . 1 14.7 14.4  1 2. .8 5 1 7 . 5 18 9 55 6. .5 52 5 . 0 2 5 . 10 9. .5 62 1 9. .4 4 3 9 4 _! _ 7 . 0 _ _ 1 * 1 _ 5 9 . 4 5 8 . 4 3 0 . 44 22 8. .1 7 4 2 . 1 1 . 9 23 5. .6 7 24 . 5 1 5 . 4 4 3 . 8 31 5. .3 0 2 20 .1 0 _ 8. .60 3 . 2 21. 0  v e * 5 _  t  1.2  31 3 6. . 7 33 7 . 6 3 2 . 7 . T 1 4 . 0 1 1 . 8 1 5 . 6 1 4 . 6 4 8 0 1 1.. .47 85 1 1. .5 7 1 4 1 2 . 0 1 5 . 4 1 5 .1 0 -1 0 . 5 1 2 . 10 . 5 1. .T 7 6 . 01 5 _ U 4 _ _ 1 0 . 0 6.9 140.. 4 05.1 1 4 . 6 1 .41 11. 6. 18 1. 54 _-9.4 8.59. -1 0 . 1 8 1 5 . 6 1 5. . 8 1 1 . 6 1 3 1 1 1 . 0 1 0 . 0 7 . 0 13 4. . 5 1 0 . 8 25.7 0 -7 . 3 8 . 3 9 . 1 3 . .0.0 17 5.0 5 . 3 5 . 5 3 . 2 -3 . 3 2. .6 9 4 . 5 1 0 . 22 9.0 4 . 4 7.2 39. 2 4 3 . 44 1 . 4_ 2 0 . 3 1 8 . 9 6 9 . 4 3 1 . 1 8 5 . 8 3 4 . 9 34 5^9 _ 2 . 22 34 5 . 8 36. .1 8 4 8 . 4 4 26 3. .3 7 24 4 .. 12 5 " 0.7 3 8. .9 83 9. .21 0 2 2 2 5 1 3 . 5 1 3 . 0 1? 0. .3 1__ 6 . 5 _Z 1 1 .4 2 0 . 62 0 . 7 2 3 . 1 2 2 . 1 2 1 . 2 2 1 . 4 14.1 13.1  1? 5. 4 .3 8 3 5. . 3 2 0 8 2 0 . 8 13 12 3. .6 3_5.8 0." 7 2 4 . 3 1 . 2 5 5 .9 22 . 5 6 . 0 5 6 5 . 1 5 0 7 _ 5 3. .0 1_4 1 6 . 3 3 5 6 3 7 . 3 5 6 . 3 2 8 0 2 8 . 8 1 0 5 2 4 . 9 2 4 . 2 1 7 8 .1 6 5 8 5 3 1 5 1 6. .5 75 17 7. .5 8 16 7 . 3 . 8 . 2 10 7. .3 7 17.4 2 6 . 4 1 36 1. . 5 0 . 0 2 1 . B -1 0 . 2 27 2. .3 1 _ 0-2 2 . 0 _r2-8 _ 3 8 . 2 2 9 . 2 2 . 9 49 . 7 3 5 . 7 7.6 3 2 . 2 49 . 9 60 1. .5 3 8 . 8 30 . 4 _4 3 9 . 2 6 2 . 2 3 5 . 3 31 8. .29 4 33 6. .T 3 _6 809 .2 40 . 8. .6 3 2 7 45 . T 6 . 2 1 4 . 1 2 3 . 5 3 0 . 0 2 0 . 9 . 1 4 , _ _ 8. .8 l 2 1 . 4 1 4 1 1 5 . 6 -1 12 3 1 16 3. .6 4 8 0.28.2. _. . 4 9 . 1 -4 . 7 3. .3 3 20 2 . _ 2 _ 2 0 . 4 1. .6 3 21.3 2 2 5 1 6 . 1 1 8.5 3_ 16.7 1 2 4 4 . 8 32. .1 0 3 3 . 44 4 7 . 5 27 3 . 8 2 5 . 3 2 . -4.9 . _4 3 6 _28 0 . 7 -0 6. . 7 0 . 5 0 8 . 3 8 . 9 5 . 9 5 . 91 5 . 4 1 5 . 3 1 4 . 2 1 5 . 9 8 . 8 6 . 7 3 2. .1 9 33.3 7 2 9 . 5 2 3 . 8 20.6 1 6 . 1 1 4 . 2 _1 3 . ' >. 4 . 9 3 4 . 6 30 3. 9 .0 5 70. 21.2  53 T A B L E  continued h k I FO F 43.6 13.8  0  c  13.6 1.0 25.6 29.0 13.8 14.0 33.3__ ...33.4 _ 22.1 21.3 -6.0 17.2 9.5 16.0 _ 2 l.._9__ 19.5  4.5  38.3  25.3  70.9  14.5 9.0 47.6 12~. 3 0.2 35.2 26.1  38.7 43.2 70.1 30.6 55.3 0.0 -3.5 30.4 38.2 33.2 10.3 20.8 -10.7 9.6 22.3 _-7  1.5.9  148.  24.3 -3.3  18.5 21.7 -4.7 41.2 27.0  16.2  0.0 -6.0 25.7 -11.2 24.2 0.9 12.6 8.3 13.4 -5.1 -10.0 20.3 0.0 10. B 41.8 33.1  13 .5 6.0  29.9 -5.7 38.7  10.0 38.5 10.1  6.7 8.6 12.8  8.8 13.7 14.0 16.3 7.5 26.5 21.6 10.6 12.2 48.5 12.3 -3.V 10  -12  22.8  -9.3 -8.0  22.2 26.6  3.0 22.8 26.3  2.5 14.3 39.5 23.0 8.4 41.4 17.5  0.0 7.7  6.3 9  15.8 26.  -4.5 13.4 30.5  50.8 11.2 6.6  1.6 2124 . 4 .0 9.6  20.8 48.9 19.5  12.0 II^LL  0.0  11.0 13.1_  2.  ( c o n t i n u e d )  -2.9 -4.4 23.8 31.0 11.8 -5.0 11.4 65.4 5.4 20.1 18.7 -2.3 7.5 -4.9 29.9 -6.2 11.1 -6.5 15.4 -4.2 15.0 -9.5 10.0 10.9 30.7 27.6 9.9  2.1 3.0 23.2 29.3 11.3 5.2 11.8 64.7 6.9 17.5 17.8  5.1 52.7 29.4 19.8 -4.0 -4.7 14.0 -2.8 -5.3 30.0 17.0 26.4 13.0 10.9 -2.7 21.4 15.0 -9.3 38.0 30.7 -5.8 19.6 9.0 8.0 5.7 9.3 24.4 25.9 61.1 20.8 30.0 5.5 61.6 18.0 15.0 24.3 -4.4 15.6 0.0 11.3 11.4 12.9  4.5 49.3 26.0 19.3 3.1 3.5 14.0  7.0  33.2 16.9 36.7  17.5 15.2 39.5  18.7 0.0 9.7 14.5 0.0 -5.7 -8.3 -3.0 12.9 39.5 22.0  X I I  7.6 17.3 -9.3 20.2 30.5 35.2 8.7 -5.2 -4.9. 46.5 8.3 41.7 12.4 40.2 35.6 43.5 -l.fi 10.8 -2.9 -2.9  C.9  7.4 28.1 6.0 11.0 5.1 16.6 8.6 15.0 8.8 9.2 11.6 31.5 26.9 8.5  l.T  7.0 31.7 16.2 27.5. 16.2 11.1 l.l 20.5 16.8 12.0 35.9 30.6 5.7 20.2 9.3 6.9 5.7 9.8 25.0 26.5 58.0 20.1 27.4 5.9 61.2 20.0 15.3 24.7 l.l 15.6 1.7 10.5 10.2 13.Q 8.7  27.5 30.5 18.4 9.2 8.5 8.8 29.5 23.2 44.4 34.3 1.5 21.7  11.4 16.2 6.7 62.9 51.3 \2.B -1.7 17.4 40.9 23.6 31.1 24.9 10.3 26.3 25.2 24.9 14.5  11.2 17.7 4.4 62.0 50.5  P^O  51 .1 16.1 28.4 -2.9 6.8 8.7  6 6 27.8 1.6 6.6 7.0 29.8 31.8 9.2 21.9 36.3 29.9 21.1  31 .0  20.2 36.5 21.4 18.3 0.0 12.6  24.4 12. 1  6 6 6 6 6  6  2.5  6 6 6 6 6  1.1 46.3 70.0 27.2 28.0 20.7 24.5 26.7 19.4 59.8 46. 1 20.7 35.3 33.4  20.5 25.0 27.1 19.6 59.3 48.0  .T 122 4 5..0  -38.6 6.4 -9.7  34.0 27.1 14.1 10.1 31.5 16.9  2.8  20.5 39.6  6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6  6 6 6 6 6 6 6  19.2 Z9.3 21.2 12.2 7.6 5.2 11.6 9.0 15.8 49.5 19.8. 42.5 17.1  1..3.9 15.7 51.2  -7.2 -5.6  6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6  38. 8  10.B  14.6 6.4  0.0  13.6  144.2.8  11 11 11  1 111 1 111 11 11 11 11 11 11  11  11 12 1? 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 13 14 14 14 14 14  2 3 4 5 6 7 8 9 10 -10  -7.5  21.7 20.7 38.9 12.5 20.8 24.8 13.1 -6.7 13.9 14.5 -5.6 17.0 12.0 1 1 .4 13.9  -8 -5 -4 -3 -2 -1 0 1 2 3 4 5  3  20.1 56. 41 .3 22.8 -8.7 29.5 16.3 1 1.6 -8.4 -4.9 11.0 13.3 -3.8 32.9 23.8  7 8 9 10 -10 -9 -8 -6 -5 -4 -3 -2 -1 0 1  1?.T  40.5 29. 1 0.0 72.4 -4.4 16.1 16.7 -10.9 -9.7 39. 1  2  3 4 5 6 7 8 9 -9 -a -7 -5  25.5  34.8 19.0 18.4 7.6 10.3 8.9 -1 .9 -2.8 -5.6 -10.0 0.0 -8.3 -9.8 22.8 -9.6 47.9 21.3  7 7 7  -2  0 1 ?  5 6 7 3 -8 -7 -6  27.3 -4.6 -2.1 -1.7 -5.8 7.7 -3.6 0.0 -6.1 17.0 19.2 38.7 -a.2 25.8 -3.8 27.4 17.4 21.6 -5.3  -5 14  14 14 14 14 14 14 14 14 14 14 15  -4 -3 -2 -1 0  2  3 6 21.5 4 5  7 -6 -5 -4 -3 -2 -1 0  15  15 15 15 15 15 15 15 2 15 3 4 15 15 16 -3 16 16 -2 16 16 0 16 16 2 16 3 0 -13 0 -1 1 -9 0 -7 0 0 -5 0 -3 -1 0 0 1 0 3 0 7 0 9 0 0 1 1 -13 -12 1 -11 -10 -9  7 7 7  9.4 4.7 16.9 24.5 21.9  11 11  63.1 14.9 44.8 40.8 -8.3 27.9 13.6 13.6 15.8 39.4 14.4  -5 -4 -3 -2 -1 0  -3 -1 3 6 13 6 6 6  ,.  10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 11 11 11 11  6 6  25.1 24.7  LU*_  4.8 16.7 41.5 23.7 30.5 Zl.,38.5 26.5 26.1 25.5 14.9 USL. 5.1 13.4 0.3 29.0  6 6  6  -3.0 117.  18.4 5.5 2C.7 30.6 35.5 8.8 4.5 2.0 48.6 7.6 40.9 12.1 40.4 35.9 41.4 0.5 10.2 0.1 1.6  25.4 30.6 18.6 9.0 -6.6 -8.1 27.8 23.7 44.2 34.R 0.0 . 21.4  7.4 13.8 0.0 27.3  0.0  -8.4  1  5  8.4  -5.3  17.6 0.0 13.2 34.6 -2.7 36. 1 16.5 46.0 Mo. 1 -3.4 -3.6 17.0 9.4 8.7 -6.2 10.4 0.0 9.5 10.0 -3.2 27.4 14.7 16.0 13.9 22.1 13.4 20.0 7.8 15.6 28.4  5  T  22.3  0.0 9.9 0.0 -5.1) 29.8  6 68. 15.7 45.0 40.8 6.7 27.4 13.5 10.9 15.5 40.2 13.5 4.6 19.7 20. 1 36.8 14.0 21.5 24.6 13.8 14.6 14.9 5.5 16.4 9.4 13.2 55.4 22.0 40. a  1  2 2 2 2 2  -10 -9  30.4 -4.4 12.3 -4.1 7.9 6.6  -8  -7 -6 -5  24.6  5.6 30. 1 14.5 11.5 6.7 3.6 11.5 12.3 4.8 32.6 23.1 10.7 41.5 30.2 3.4 73.2 4.7 17.3 17.0 9.8 9.4 39.4 26.4 34.9 18.4 18.6 6.5 10.8 2.4 4.8 3.4 10.7 0.6 7.9 10.7 22.8 8.7 47.1 19.3 6. 1 27.3 5.8 2.9 0.0 7.5 6.6 3.6 2.8 3.5  9.1  21.0 39.4 8.5 27.2 0.3 28.3 18.6 21.1 2.6 21.5  15.P  8.1  3.8 17.5 2.6 14.6 35.0 2.9 35.B 16.4 46. 7 10.0 1 .3 0. 1 16.6 8.1 7.1 4.5 10.0 2.4 1.2 4.2 26.6 14.9 15.7 15.2 20.8 13.8 19.2 8.5 17.6 28.6 23.2 2.2 9.5 0.9 5.7 28.9  tj.  10 -II -9  4 4 II 4 12 5 -12 5 5 -10 5 5 -8 5 -7  36.1 -6. 0  e  14.5 18.4 20.0 27.7 23.2 -2.4 -4.8  59 T A B L E  continued h k I F o F« -6.0 0  19.9 10.3  -174..73  18.0  4136..36 31.3  ?175..21  19.6  10.7 580..50 4153..53 -I7.01.8 4-25..80 160..00 0.0  38.2 -22711...614 14.5 10.07._0  2.3  -31494...053 1 1 .0  1152..7 1 0.0  180..60 0.0  230..38 16.9 3540..95 20.5  18.3 .,16.. 12.5 100..29 13.1  511073...980 519..50 44. 3180..071 16.2  2771..96 1303..07 3112..00 28.7 164..60 ,13.020.3 2367..50 -125..97  31699...574  X I I  ( c o n t i n u e d )  2116...320 0.0 , 1165..39 18.1 24.6 220..94 47.7 -11999...112 27.0 2.2 2308...190 21.5 241135...487 -6.9 1122..50 15.7  2241..42 21.5 21790...553  21.4 241036...06 1 1103..00 16.4  32.7 30.6 223891...163 422018...558 215..06 ,2114..47, 1103..19 2 4.8 -11546...848 11365...173 2104.,78 1139..94 2290..70 -39..72 26.7 -102.05.4 --1950...537 -1011.46.51.7  31910...070 -21712...317 24.0  8 10 4 -4.9 5.2 88 1100 5 -15..12 97..94 88 110 -77 112..10 11..62 88 1 -5 --1606...186 1741...861 8 1 -3 25.4 25.3 888 11 --210 -2155..457. 121672...676 88 111 21 170..50 171.7.9 88 1 43 160..10 160..59 88 •56 2130..93 2130..42 88 12 --56 -18..73 8.5 88 1122 --43 1153..04 1153..44 888 111222 --210 --1535...323 1631...249 a8 1122 21 218.1.6B 218..13 88 12 3 157..46 177..02 88 13 -45 --53..49 55..68 B 13 -3 9.9 10.5 8B -2 106..68 9.7 68 1 3 02 -I0B9...854 1891...727 88 14 -143 -11334...113 1123S3....87B4 8 ft 0 7.3 99 00 --57 4368.7.6.09 4337.8..929 99 "000 --131 4321..70 431116...507 99 00 53 2344..45 2342..98 99 00 9 4-46..54 453..71 99 1-1-09 2I0B..74 2107..76 99 1 --B7 -I7B..22 161..45 99 -5 113847...420 31197...367 99 --23 -257..30 2160..47 999 11 0 -51404...925 4195.1.7.55 9 23 6103..43 6104..27 999 1 456 2104..65 11945...021 99 e7 -375..74 365..30 99 -109 149..04 138..15 9 22 --89 1196..39 2107..37 999 222 --65 -11044...351 1134.1..607 99 2 --43 -136..12 164..91 99 22 --12 5146..50 5145..75 99 22 01 410.0 41.19.3 99 2 32 2260..69 2260..64 99 22 46 2259..6 1 2285..89 99 22 7a 118.7.0 199..14 99 37 -109 2104..94 2113..21 99 33 --98 98..87 109..97 9 33 -7 10.01 .4141..80 3 -5 -5.5 6.0 999 333 ---243 -11945...980 1157..163. 5 99 33 -10 -396..30 357..20 99 13 21 252..6 3 2479..99 9 33 3 4-62..05 511..0I 99 333 657 111084...967 11499...760 9 33 98 2263..60 7236..41 9 44-1--098 111549...303 111592...959 99 4 --76 -168..71 186..01 99 44 --45 -25.9.1 236..80 99 444 ---321 23115...228 231126...820 9 4' 0 14.5 12.8 999 444 231 300..40 21900...945 9 4 4 -9.5 7.9 999 444 657 211176...065 211166...022 9 44 89 107..75 17..91 ?  i  .2  2540..15 2292..37  -144..52 -130..41 13.6 -69..59  --1533...663 8.5 21420...720. 2170...758 3113.6..0 , ,13.5 7169..67 -266..50 37.7  05..85 79..90 1142...690 1.7 21472...297 32.21  .IS.  2110..79 -1330...560 -153..70  1 6 . 7 ..  -90..30 0.0  2 2 < • _  44.2 -103.21.4  32.9  17.5 214..56 -146..75 18.7  -11578...030  120..30 139..80  4.4  1042...42B 13.5  18.6 231362...075  -260.9.4.87  174..47 160..17 _ .13  18.7 -252..64 2.5 185..42 1123..70 11435...000 6.3 106..44 2186..24 18.7 ..3206..574.8. 2134..59 13.21..4 2156.4.2.63  -742..44 1160..02 146..37 q ? 1 .5 000 --3I1 01 -43 1 -32 D11 23 43 1 I  L59..59 8.9 -1647...347 -3.7 111397...030 --1575...680 1-1923...969 21.1 --26..00 1177...690 --1440...344  1.7 168..69 33..99 2.7 11475...749 21.13.4 17..68 2216...352 115..33 186..30 119.50.9 111198...730  6 1  TABLE X I I I F i n a l p o s i t i o n a l parameters  (x 10^) and a n i s o t r o p i c  thermal  parameters i n the form: exp- 10~ (b 4  + £33^  +  £12--  +  -13--  f o r the P, N, 0, and C atoms, with standard d e v i a t i o n s i n parentheses. Atom P(D P(2) P(3) N(l) N(2) N(3) 0(1) 0(2) 0(3) 0(4) 0(5) 0(6) C(l) C(2) C(3) C(4) C(5) C(6) C(7) C(8) G(9) G(10) C(ll) C(12) C(13) C(14) C(15) C(16) G(17) C(18) C(19) G(20) G(21) C(22) C(23 )  X  Y.  2202(1) 0546(1) 2921(1) 0872(4) 1601(4) 3163(4) 2570(3) 2251(3) -0322(3) -0289(3) 3414(4) 3831(4) 3624(5) 3625(6) 4637(7) 5627(7) 5606(6) 4592(6) 1522(5) 1569(6) 0842(7) 0121(6) 0104(6) 0805(5) -1477(5) -1618(6) -2802(8) -3734(7) -3563(7) -2414(6) -0383(5) -1435(6) -1554(7) -0647(8) 0383(8)  0832(1) 1622(1) 2014(1) 0980(2) 2084(2) 1413(2) 0118(2) 0622(2) 2150(2) 1375(2) 2725(2) 1998(2) -0261(3) -0899(4) -1301(4) -1072(4) -0433(4) -0025(3) 0927(3) 1626(3 ) 1886(3) 1463 (3 ) 0766(3) 0439(3) 1948(3) 1594(4) 1420(4) 1625(5) 1983(5) 2152(4) 0687(3) 0349(4) -0334(4) -0613(4) -0253(5)  1265(1 2049(1 2111(1 1501(3 2410(3 1479(3 1687(2 0325(2 1577(2 2759(2 1769(2 2886(2 1613(3 1979(5 1949(6 1546(6 1181(5 1211(4 -0306(3 -0457(4 -1093(4 -1566(4 -1407(4 -0772(4 1293(3 0573(5 0317(6 0799(7 1490(6 1760(5 3033(4 2851(4 3173(5 3644(5 3323(5  62  TABLE X I I I  (cont.) x  Atom G(24) C(25) C(26) C(27) C(23) C(29) C(30) G(3D C(32) C(33) C(34) C(35) C(36)  Atom  P(D P(2) P(3) N(l) N(2) N(3) 0(1) 0(2) 0(3) 0(4) 0(5) 0(6) C(l) C(2) C(3) C(4) C(5) C(6) C(7) C(8) C(9) C(10) C(ll) C(12) C(13)  y_  0520(7) 3040(6) 1913(6) 1601(7) 2413(3) 3513(9) 3848(6) 3671(5) 3161(7) 30H6(8) 3404(8) 3916(7) 4063(6)  hi  ^22  55(1) 61(1) 67(1) 47(4) 75(5) 58(4) 61(3) 75(4) 62(3) 93(4) 108(4) 82(4) 66(5) 114(7) 162(9) 133(8) 97(7) 87(6) 64(5) 109(7) 149(8) 118(7) 95(6) 88(6) 57(5)  18(1) 19(1) 20(1) 20(1) 23(2) 20(1) 20(1) 27(1) 20(1) 25(1) 22(1) 27(1) 22(2) 32(2) 44(3) 48(3) 41(3) 29(2) 22(2 ) 20(2) 22(2) 28(2) 28(2) 21(2) 25(2)  z  0406(4) 2971(3) 3252(3) 3521(4) 3501(4) 3219(4) 2949(3) 1517(3) 1754(4) 1285(5) 0611(4) 0390(4) 0848(3)  33 26(1) 29(1)  k  3KD  31(2) 35(2) 34(2) 35(2) 24(2) 43(2) 39(2) 38(2) 36(2) 30(2) 80(4) 125(5) 110(5) 74(4) 55(3) 26(2) 39(3) 48(3) 40(3) 37(3) 32(3) 56(3)  *12 5(1) 8(1) -10(1) - 1(4) - 2(5) - 9(4) 5(4) 28(4) 10(4) 13(4) -31(4) -25(4) 17(5) 39(7) 36(8) 89(8) 44(7) 27(6) 14(5) -12(6) 2(7) 11(7) -13(6) 0(6) 9(6)  3514(5) 0982(4) 0863(4) 0088(4) -0535(4) -0399(5) 0361(4) 3526(4) 4231(4) 4880(5) 4800(5) 4096(5) 3440(4)  *13 8(2) 12(2) - 8(2) 10(5) - 3(5) 9(5) 16(4) 3(4) 1(5)  5K5)  - 25(5) - 32(4) 13(6) 62(9) 120(12) 91(11) 71(9) 45(8) 11(6) - 16(8) - 32(9) - 29(8) - 13(7) 6(7) 8(7)  ^23 - 2(1) - 4(1) 0(1) - 7(3) -16(3) 0(2) 11(2) - 9(2) 3(3) 1(3) 8(3) 7(3) 0(4) 51(5) 90(6) 59(7) 26(6) 15(5) - 1(4) - 2(4) 8(5) - 1(5) - 6(4) 0(4) 19(4)  63  TABLE X I I I Atom C (14) c [15) c [16) c [17) c (18) c [19) c [20) G (21) C (22) G (23) G (24) G [25) C [26) C [27) c (28) C (29) G (30) C(3D C (32) C (33) C (34) C (35) C (36)  (cont.)  b -11 102(7) 171(10) 85(7) 81(3) 78(6) 87(6) 103(7) 138(8) 202(11) 163(10) 126(3) 106(6) 107(7) 150(3) 205(10) 173(9) 113(7) 82(6) 126(8) 157(9) 173(10) 163(9) 130(8)  ^22 31(2) 39(3) 48(3) 87(5) 67(4) 25(2) 39(3) 49(3) 41(3) 50(3) 35(2) 18(2) 24(2) 25(2) 34(3) 44(3) 30(2) 29(2) 44(3) 71(4) 54(3) 37(3) 31(2)  ^33 67(4) 110(5) 164(8) 125(6) 75(4) 37(3) 58(4) 83(5) 84(5) 83(5) 57(3) 37(3) 49(3) 61(4) 50(4) 56(3) 55(3) 35(3) 41(3) 47(4) 67(4) 63(4) 47(3)  b -12 6(7) 3(9) -17(9) 26(10) 55(8) 2(6) -16(7) -5K9) - 7(10) 11(10) 0(8) -19(6) 1(7) - 3(7) -40(9) -40(9) -22(7) -19(6) - 8(8) -23(11) -47(10) - 8(9) 3(3)  ^13 - 45(9) -121(12) - 43(13) 45(12) 33(9) 43(7) 37(9) 63(11) 101(12) 10(12) 7(9) -15(7) 8(8) - 52(10) - 32(11) 50(9) 29(8) - 28(7) 12(8) 13(10) - 53(11) - 68(11) - 48(9)  ^23 -11(5) - 7(7) 46(9) 60(9) 33(7) - 2(4) - 9(5) -19(7) 27(6) 45(7) 27(5) 6(4) 1(5) 15(5) 32(5) 37(5) 18(5) 9(4) 2(5) 17(7) 48(6) 24(6) - 3(5)  64  a n d  f o r  a n d  v a l e n c y  2 . 4  t h e  h y d r o g e n a n g l e s  a t o m s  a r e  i n  g i v e n  T a b l e i n  X I V .  T a b l e  B o n d  l e n g t h s  X V .  D i s c u s s i o n T h e  b u t  s i x - m e m b e r e d  s i g n i f i c a n t l y ,  t h r o u g h  s i x  +"he  n o n - p l a n a r .  a t o m s  0 . 1 3 1 3  p h o s p h o n i t r i i i c  X '  o f  -  t h e  T h e r i n g  0 . 5 4 6 7  Y  +  r i n g  e q u a t i o n  i s  o f  s l i g h t l y ,  t h e  p l a n e  i s  0 . 8 2 7 0  Z  =  T  1 . 1 0 8 7  o w h e r e  X ' ,  Y ,  g o n a l  a x e s  Z  a ,  f r o m  t h i s  K(I)  - 0 . 0 2 0 ,  c o - o r d i n a t e s  are  f  b ,  p l a n e  c * , a r e  a n d P(l)  phosphorus atoms a n d w i t h  a n a  N(2)  N ( 3 )  a n d  U{1)  r e f e r r e d  A  d i s p l a c e m e n t s  0 . 0 1 9 ,  0 . 1 3 2 ,  U(2)  t h e  i n  t h u s f r o m  o f  - 0 . 0 1 4 ,  - 0 . 1 6 9  K(3)  a r e  d i s p l a c e d  P ( 2 )  t o t h e  a t o m s  P ( 3 )  A.  p l a n e  0 . 0 0 3 , t h r e e  The  a p p r o x i m a t e l y t h e  o r t h o -  i n  c o p l a n a r , o p p o s i t e  o d i r e c t i o n s b y r i n g t h u s h a s P(3  ) • • • N ( 1 )  a n a n  a v e r a g e o f 0 . 1 5 A ( a b o u t 4 0 a p p r o x i m a t e s y m m e t r y a x i s  d i r e c t i o n .  O f  t h e  o t h e r  ( P W X ^ ) ^  T h e t h e  CT ). a l o n g  m o l e c u l e s  56 w h o s e a  s t r u c t u r e s  p l a n a r  r i n g ,  d e r i v a t i v e s  b u t  e a c h  r i i i c  r i n g  f r o m  t h r e e  c o m p o u n d s  h a v e the  s h o w e x a c t e a c h  b e e n  s t u d i e d ,  c h l o r o , s m a l l  57  b r o m o ,  d e v i a t i o n s  p l a n a r i t y ; h a v e  t h e  s l i g h t  t h e  f l u o r i d e  58 o f  r i n g s  c h a i r  h a s  59  a n d  p h e n y l  t h e  p h o s p h o n i t -  i n  t h e  l a t t e r  c o n f o r m a t i o n s ,  t h e  6 5  TABLE XIV 3  Final positional  (x 10 ) and thermal parameters f o r the  hydrogen atoms, w i t h standard d e v i a t i o n s i n parentheses. The atom numbers are those o f the carbon atoms t o which the  hydrogens are bonded. X  H(2) H(3) H(4) H(5) H(6) H(8) H(9) H(10) H(ll) H(12) H(14) H(15) H(l6) H(17) H(l8) H(20) H(21) H(22) H(23)  H(24)  H(26) H(27) H(28) H(29) H(30) H(32) H(33) H(34) H(35) H(36)  294(6) 468(7) 635(6) 634(7) 461(6) 209(5) 086(6) -033(5) -038(5) 080(6) -090(6) -234(7) -456(8) -421(8) -221(7) -207(5) -237(8) -071(7) 113(7) 125(6) 139(6) 084(7) 216(6) 415(6) 465(6) 284(6) 254(7)  33K7) 411(7) 451(5)  B(A  Z -110(3) -180(4) -135(4) -025(4) 045(3) 192(3) 238(3 ) 166(3) 045(3) -002(3) 148(4) 122(4) 148(5) 221(5) 236(4) 057(3) -048(4) -117(4) -050(4) 069(4) 326(4) 375(4) 366(3) 322(4) 276(3) 225(4) 147(4) 022(4) -016(4) 070(3 )  225(4) 220(5) 155(4) 089(4) 096(4) -017(4) -117(4) -202(3) -172(4) -067(4) 025(4) -023(5) 055(6) 190(5) 232(5) 249(4) 291(5) 393(5) 418(5) 365(4) 131(4) 001(5) -114(4) -078(4) 050(4) 429(4) 535(5) 533(4) 396(5) 292(4)  j  8.3(20 11.1(23 9.9(21 9.3(20 7.7(18 6.1(16 7.9(18 5.7(15 6.5(16 6.5(16 8.8(20 11.3(23 14.1(29 14.0(28 10.6(23 6.6(16 12.7(25 11.1(23 11.3(23 9.5(21 8.4(19 11.3(23 8.3(18 8.8(20 7.5(18 9.8(21 11.4(24 10.1(22 11.9(25 6.6(16  66  TABLE XV o Bond l e n g t h s (A) and v a l e n c y a n g l e s (degrees), w i t h standard d e v i a t i o n s i n parentheses. P ( l ) -N(l) P ( l ) -N(3) P(2) - N ( D P(2) - N ( 2 ) P(3) -N(2) P(3 )- N ( 3 ) Mean P=N  1.574(4) 1.581(5) 1.572(5) 1.573(5) 1.574(5) 1.575(5) 1.575(2)  0(1) - C ( l ) 0(2) -C(7) 0(3) -C(13) 0(4) - C ( 1 9 ) 0(5) - C ( 2 5 ) 0(6) -C(31) Mean o-c  1.395(7) 1.412(6) 1.409(7) 1.406(7) 1.407(7) 1.406(7) 1.406(3 )  N(l) -P(l)-N(3) N ( l ) -P(2)-N(2) N(2) -P(3)-N(3)  117.3(2) 117.9(2) 116.6(2)  P(D -N(l)-P(2) P(2) -N(2)-P(3) P ( D -N(3)-P(3)  121.3(3) 122.4(3) 122.1(3)  0(1) - P ( l ) - 0 ( 2 ) 0(3) -P(2)-0(4) 0(5) -P(3)-0(6)  100.1(2) 100.1(2) 94.1(2)  P(l)-Od)-C(l) P(D - 0 ( 2 ) - C ( 7 ) P(2) - 0 ( 3 ) - C ( 1 3 ) P(2) -0(4)-C(19) P(3) -0(5)-C(25) P(3) -0(6)-C(31)  128.7(3) 123.5(3) 121.3(4) 124.8(4) 120.8(4) 120.0(4)  P(D-0(1) P(l)-0(2) P(2)-0 3 ) P(2)-0(4) P(3)-0(5) P(3)-0(6) Mean P-0 C-C  1.583(4) 1.576(4) 1.583(4) 1.578(4) 1.584(4) 1.585(4) 1.582(2)  1.33-1.43 ( * -•= 0.010-0.019), mean 1 . 3 7  0(1)-P(1)-N(3) 0(2)-P(l)-N(3) 0(1)-P(1)-N(1) 0(2)-P(l)-N(l) 0(3 )-P(2)-N(l) 0(4)-P(2)-N(l) 0 3 )-P(2)-N(2) 0(4)-Pl2)-N(2) 0(5)-PO)-N(2) 0(6)-P(3 )-N(2) 0(5)-P(3)-N(3) 0(6)-P(3)-N(3)  110.9(2) 110.2(2) 106.6(2) 110.3(2) 112.5(2) 109.2(2) 104.6(2) 110.9(2) 112.0(2) 109.9(2) 109.8(2) 112.2(2)  0-C-C  115-123, mean 118.4  C-C-C  116-124, mean 120.0  67  m a x i m u m  d i s p l a c e m e n t s  f r o m  p l a n a r i t y  b e i n g  0 . 0 9 ,  0 . 1 4 ,  0  a n d  0 . 0 7  r e s p e c t i v e l y .  A  i o u s l y a s c r i b e d 56-59 e f f e c t s . T h e a r e  a l s o  b u t  t h e  a  t o  i n  p h e n o x y  s y m m e t r i c a l  r e l a t i v e  t o  i n t r a -  o x y g e n  r e l a t e d  t h e  l o c a l  d i f f e r e n t  i n  -che  c r y s t a l l i n e  o f  t h e  s l i g h t l y  p l a n e  a t i o n  o f  p h e n o x y  o n  A t  t h e  a n d  s a m e  a n d  ( F i g u r e p h e n y l a r e  t h e  i t i o n  t h e  a m o u n t s s a m e T h e s e  s i d e  o t h e r  b o n d s ( c a .  25  d i r e c t i o n  t h r e e  a s  t h e  p h o s p h o r u s  T h i s  r i n g s  a t  A t  a r e  t h e  0 . . . 0  l i n e  o p p o s i t e  s i d e  -  45°),  a n a  t h e s e  P(2),  a n a  i n  a n d  t h e  t h e  a n d  P(2)  a s  t h e  ( F i g u r e  0 P 0  p l a n e s  g r o u p  s o  t h a t  d e v i a t e s  t h e  s a m e  a n d f r o m  a n d t h a t  d e v i a t e t h e  t h e  o r i e n t -  t h e  t w o  a x i s  o n e  0 - H  12); b y  o f  b o n d  p h o s p h o r u s  d i s p l a c e m e n t s  o p p o s i t e  p h e n y l  o n  a t o m ,  s u c h  a r e  c h e m i c a l  a p p r o x i m a t e  P ( l )  f r o m  a r r a n g e m e n t s  b o t h  a r r a n g e m e n t  d e v i a t e  a t  a r e  t h e  d i r e c t i o n s  P(3)  b y  a t o m s ,  b y  b o n d s  o p p o s i t e  f r o m  o r i e n t a t i o n s  m o l e c u l e  i n d i c a t e d  12).  t h e  t h e  a x i s ,  d e v i a t i o n s  p h o s p h o r u s  0 - C  r i n g .  v a r -  a r r a n g e m e n t s  t h e  i n  t h e  T h e  l e a s t  C_2  s h o w s  12  p l a n e s .  r e l a t e d  o f  o n  F i g u r e  a t  b e e n  s t e r i c  a p p r o x i m a t e  s i g n i f i c a n t  s y m m e t r y  l i n e  9°)  g r o u p s  t h e  h a v e  t h e t h e  s h o w  s t a t e  p h o s p h o n i t r i l e t h e  b y  0 P 0  F(3)  0 . . . 0  ( c a .  O - P - O  t h e  a t  t h r e e - f o l d  f o r m u l a t i o n . s i d e  p a i r s  d e v i a t i o n s  i n t e r m o l e c u l a r  o f  a r r a n g e m e n t .  f a c t  t h e  a n d  a t o m s  g r o u p s  i n  f r o m  T h e s e  i n  i s  a t o m , a d d -  s i g n i f i c a n t a r e  d i r e c t i o n s  i n a t  o r i e n t a t i o n s  t h e P ( l ) . a r e  68  0(5)  s h o w i n g  a r r a n g e m e n t  d i s p l a c e m e n t s p h e n y l  0(6)  r i n g  o f  t h e  o f  t h e  f i r s t  f r o m  t h e  0 P 0  p h e n o x y c a r b o n  p l a n e s  g r o u p s . a t o m  a r e  T h e  o f  e a c h  g i v e n  ( % } .  6 9  s u c h  t h a t  t h e  t h a t  a t  r i n g  ( F i g u r e  p h e n o x y o n  0(4)  P ( 2 ) b y  1 1 ) ,  b u t  s i d e r a b l y  d i s p l a c e d  o f  o t h e r  o n e  a n d  0(3)  p l u s t h e  o r  a b o u t  s o m e  f o l d T h e  b o n d  s y m m e t r y , m o s t  =  0 . 2  a n g l e s  a t  N - P ( 3 ) - N o f  t h i s  d i f f e r e n c e f r o m  121.3(3)° P - N - P  i s  a n g l e s  a t  s e v e r a l  a b l y  i n f l u e n c e d  s y m m e t r y  c o n f o r m  i n  i s  6  a  v e r y  t o t a l  o f  t o  t h e  a r e  c o n -  R o t a t i o n  g r o u p s  a t  0 ( 1 )  a b o u t  c h a n g e s  TT/2,  w o u l d  g i v e  o f  2 . 7  m o r e b y &  d e g r e e s , t h e  c o n t r a s t  a n d  t h a t  i s  4  P ( l ) a n d d o u b t f u l  o n l y  2 . 5  t h e  s y m m e t r y .  0 - P ( 3 ) - 0  s m a l l e r  o f  w h i c h  ff"  s m a l l e r  a n g l e ,  t h a n  i s  t h e  1 0 0 . 1 ° . t h a n  t h e  P ( 2 ) , 1 1 7 . 6 ° ,  cr  T h e  . t h a n  a l t h o u g h  o f  t h e  m e a n  v a l u e s t h e  N - P ( 3 ) - N  P - N ( l ) - P , o f  t h e  P - O - C v a r y a r e  p h e n o x y  t o  t h e  d e v i a t i o n s  f r o m  c o n f o r m a t i o n  a n d  i n  a n g l e s ,  v a l e n c y  a s  T h e a n g l e  0 - P - Na n d  d e t a i l e d  o r i e n t a t i o n s  t h r e e -  s i g n i f i c a n c e ,  s m a l l e r N ( 3 ) .  )  f r o m  t o  t h e  0"  P ( 2 ) , e a c h  a t  n i t r o g e n  v a r i a t i o n s  2 0  1 1 6 . 6 ( 2 ) °  a n d  c l o s e l y  i s  ( a b o u t  U  N ( 2 ) a n d  b y  g r o u p s  p h o s p h o r u s  f e a t u r e  N - P ( l ) - N a b o u t  p h e n o x y  b y  o f  a r r a n g e m e n t .  s i g n i f i c a n t  P ( l ) a n d  i s  t h e  a t  N - P - N a n g l e s  o v e r  I n  )  a n  r e l a t e d  a x i s  0  0(3)  c o n f o r m a t i o n a l  a n g l e s  a n g l e ,  m e a n  d i f f e r s  t h e  U  P ( l ) i s  s y m m e t r y .  s h o w b u t  a n d  s u c h o f  o n  a p p r o x i m a t e  P - 0 b o n d s  s i g n i f i c a n t  ( &  O - P - 0  b o t h  0 ( 2 )  0 ( 1 )  f r o m  m i n o r  X V ) a l s o  9 4 . 1  T h e  t h e  a t  t h e  t h e  e x a c t  T h e ( T a b l e  o r  o t h e r  m o l e c u l e  g r o u p  p r o b g r o u p s .  t h r e e - f o l d t h e r e  a r e  7 0  no  s i g n i f i c a n t d i f f e r e n c e s among  bond l e n g t h s .  chemically-equivalent  The P-N bonds a r e i n the range 1.572 -  1.581(5) A , mean 1.575(2) 1 (Table XV); P-0, 1.576 1.535(4) A , mean 1.582(2) A ; and 0 - C , 1.395 - 1.412(7) A , mean 1.406(3) A .  The standard  d e v i a t i o n s g i v e n i n parenth-  eses are those from the l e a s t - s q u a r e s dard  d e v i a t i o n s obtained  equations;  the s t a n -  from the v a r i a t i o n s among  chemically-  e q u i v a l e n t bonds are i n a l l cases s m a l l e r , so that the least-squares fact  f  s appear t o be a reasonable,  s l i g h t l y p e s s i m i s t i c , estimate  the a n a l y s i s . lengths  and i n  o f the accuracy o f  The e q u a l i t y o f c h e m i c a l l y - e q u i v a l e n t  bond  suggests t h a t there i s no great v a r i a t i o n i n the  character of chemically-equivalent  bonds, so t h a t the an-  g u l a r d e v i a t i o n s from t h r e e - f o l d symmetry are probably a r e s u l t of s t e r i c  i n t e r a c t i o n s among the bulky s u b s t i t u -  ent phenoxy groups. Intramolecular  steric  to r e s u l t i n minimum energy with  e f f e c t s would be expected three-fold  symmetry, so t h a t the very approximate  molecular  symmetry a c t u -  a l l y observed must be a t l e a s t p a r t l y a r e s u l t o f i n t e r molecular  interactions.  There a r e no u n u s u a l l y  short  i n t e r m o l e c u l a r d i s t a n c e s , and most o f the s h o r t e r  contacts  i n v o l v e the phenoxy groups which are o f course on the outs i d e o f the m o l e c u l e .  The s h o r t e s t d i s t a n c e s a r e two  7 1  0 . . . C  c o n t a c t s  m o l e c u l e c u l e  +  0 ( 2 9 ) ,  c o n t a c t  3 * 4 0  ( F i g u r e  a t  a n d  o f  x,  i  ( - |  i s  1 1  3 . 4 4  a n d  -  +  A ,  b e t w e e n  T a b l e  y_, ~  x , A.  -  I n  X I I I )  z),  +  +  t h e  T h e  t h e r e  s t a n d a r d  C ( 1 0 )  b e t w e e n  z ) .  a d d i t i o n  o f  a n d  a n d  |-  y_,  0 ( 6 )  o f  t h e  0 ( 4 ) ,  s t a n d a r d  c l o s e s t  a r e  m o l e -  C . . . C  s e v e r a l  C . . . N  o c o n t a c t s , s t a n d a r d -  t h e  s h o r t e s t  m o l e c u l e  b e i n g  a n d  C ( l l )  o f  A  b e t w e e n  t h e  N ( l )  m o l e c u l e  a t  o f  (-  t h e  x ,  -  y_,  z ) I t  t h e  i s  o b s e r v e d  m e n t s  o f  t i o n s  w o u l d  g e o m e t r y  o f  c o u r s e  c r y s t a l  p h e n o x y  m o l e c u l a r  a n d  g r o u p s  r e s u l t  i n  a d o p t e d  s t e r i c  s h i p s  o b v i o u s l y  T h e T a b l e  t r i m e r s , r e s u l t s  t h o s e  ( P N X ^ ) f o r  m i n e d  w i t h  c o m p a r i s o n  a n d  o f  a n d  o t h e r  O n l y h e x a m e r i c  ,  f o r  o f  t h e  o t h e r  t h e  t h a t ,  g i v e n  a n y  s h o r t  i n t r a -  o b s e r v e d  o p t i m i z e t h e  q u i t e  o r i e n t a o r  m o l e c u l a r  b o t h  i n t r a -  e n e r g y  a n d  r e l a t i o n -  c o m p l e x .  m o l e c u l e  c o m p o u n d s p h e n y l  m e t h o x i d e s  t r i m e r i c  i n t e r -  a r e  c o m p a r e d  i n  s y m m e t r i c a l l y - s u b s t i t u t e d  t r i m e r i c  a c c u r a c y  d i s p l a c e -  s y m m e t r i c a l  m e t h o x y - d e r i v a t i v e s ,  p h e n o x y  s u f f i c i e n t t h e  b e i n g  w i t h  o c t a m e r i c  w i t h  m o r e  T h e t o  n o t e  s t r u c t u r e ,  i n t e r a c t i o n s ,  d i m e n s i o n s  X V I w i t h  m o l e c u l a r  c o n t a c t s .  p r o b a b l y  i n v o l v e d  t o  u n a c c e p t a b l y  n o n - b o n d e d i s  p o s s i b l e  t o w a r d s  i n t e r m o l e c u l a r  n o  3 . 5 4  t o  a r e a l l o w  p h e n o x i d e .  b e i n g  ^ P N ( 0 M e ) ^ " |  a v a i l a b l e .  d e r i v a t i v e t h e  a n d  d i m e n s i o n s  m e a n i n g f u l ( R e c e n t l y  t h e d e t e r  d e t a i l e d t h e  T A B L E  o Bond l e n g t h s (A) and a n g l e s  PN (NPF ) 2  a  3  (WPGJ? ) 2  (NPBr )  3  (NPPh )  3  2  2  [NP(OMe) J  6  2  2  a  -  -  -  -  -  120  £  1.58  121  117  d  1.597(6)  122.1(4)  117.8(3)  1.575(2)  121.9(3)  117.3(3)  1.582(2)  1.406(3)  1.57  132  120  1.58  1.567(3)  134.4(3)  118.6(2)  1.561(5)  136.7(5)  116.7(4)  a r e f . 56  e r e f . 33  b r e f . 57  f r e f . 38  c r e f . 58  r e f . 39  d ref. 59  POC  120  f  [NP(0Me) J  -  0P0  00  1.59  e 4  2  P0  NPN 119  3  [NP(OMe) J  PNP 121  b  2  2  1.56  3  [NP(OPh) |  X V I _ , (degrees) i n j^NP(OPh) J ^ and r e l a t e d m o l e c u l e s .  -  -  98  123  1.47  105  120  1.534(3)  1.444  103  120  1.576(5) -  1.440  101  121  73  ( N P B r a t  )  a n d  t h i s  T h e i s  t i m e  m e a n  h a v e  y e t  i n  t h e  h e x a m e r i c  A l t h o u g h  t h e y  a r e  a l l i n  f r o m  a  w i t h  h a s  i n  t h e  m o r e  p r e v i o u s  i n t h e  J N P ( 0 P h )  d i r e c t i o n s o f  t h e  a r e  )  ( N P P h  l o n g e r  w o u l d I n  t h e  e l e c t r o n e g a t i v e  i n  b a r e l y  b o n d i n g .  )  )  ,  t h a n  t h e  r e s p e c -  s i g n i f i c a n t ,  b e  e x p e c t e d  t h e  t w o  p h e n o x y  t r i m e r s ,  c o m p o u n d ,  s u b s t i t u e n t s ,  o b s e r v a t i o n s ,  6 2  A ,  m e t h o x i d e s ,  w h i c h  b u t  1 . 5 7 5 ( 2 )  b o n d s  a r e  i n  r e f i n e d , l i t e r a t u r e .  ,  ( 2 . 6 c  f o u n d  e x p e r i m e n t a l  }  2  t h e  d i f f e r e n c e s  P - N b o n d s t h e  b e e n  a n d o c t a m e r i c  t h e  c o n s i d e r a t i o n  s h o r t e r  w h i c h  l e n g t h  a p p e a r e d  <r ) s h o r t e r t h a n 0 ( 2 . 2 <r ) a n d 0 . 0 1 4 A  t i v e l y .  t h e  n o t  h a v e  ( 3 . 5 0 A  0 . 0 0 8  b o n d s  s t r u c t u r e s  P - N b o n d o A  0 . 0 2 2  a n d  ( N P C S ^ )  i n  a c c o r d  a n d w i t h  t h e o r e -  2 4 - 2 8 t i c a l  e x p e c t a t i o n s .  T h e P H P a n g l e s  i n t h e  t r i m e r s ,  o m e a n t h e  1 2 2  a r e  l a r g e r  l a r g e r m o r e  a n g l e s ,  r i n g s  r e s u l t  l a r g e r  r i n g s .  c o m p o u n d s  s i m i l a r  1 3 4  l e a d  i n  T h e v e r y  c o n s t r a i n e d o  p - c h a r a c t e r  w o u l d  f o u r '  ,  t o i n  T h e  a n  t h e  i n  t h e  r i n g ,  m o r e  b o t h  a n d  o f w h i c h  P - N b o n d s  r a t h e r  a n d  f l e x i b l e  1 T - b o n d i n g ,  s h o r t e r a r e  o f  i n  s i m i l a r  t o  e f f e c t s t h e i n  t h e  X V I ) .  P - 0 b o n d  l e n g t h s  t r i m e r i c  a n d  o c t a m e r i c  m e t h o x i d e s o  a r e  a l l a b o u t  0 . 1 3 A  s u g g e s t i n g  i n  a ' - b o n d s ,  N P Na n g l e s  i n t h e  s i z e  ,  i n c r e a s e  o b s e r v e d  ( T a b l e  t h e o  a n d 1 3 7  t h e  t h e  b y  p h e n o x i d e  ( T a b l e  s h o r t e r  c o n s i d e r a b l e  a n d t h e  X V I ) .  t h a n  e x o c y c l i c  t h e  P O C a n g l e s a n d t h e  a r e  h e x a m e r i c  T h e P - 0 b o n d s  s i n g l e  b o n d  TT"-bonding,  b u t  ( 1 . 5 8  d i s t a n c e , t h e  74  a m o u n t  o f  t o  c o n f o r m a t i o n a l  t h e  t h c x y T h e  TV-bond  g r o u p s ,  s h o r t e r  c o m p o u n d  c h a r a c t e r  s i n c e 0 - C  a r e  s e e m s  t o  a r r a n g e m e n t s  n o  p r o b a b l y  o f  v a r i a t i o n s  d i s t a n c e s ,  a  o f  i n s e n s i t i v e  t h e P - 0  p h e n o x y  a n d  m e -  d i s t a n c e  a r e  f o u n d .  o 1.406(3) A ,  m e a n  m a i n l y  b e  r e s u l t  o f  i n  t h e  s p  t h e 2  p h e n o x y h y d r i d i -  3 z a t i o n  a t  i n  m e t h o x y  t h e  a r e  c a r b o n ,  v e r y  p h e n o x y  t h e  C - G  t h e  t h e  s h o w  t o  t h e  T h e  t h r e e  s p  m e a n  h y d r i d i z a t i o n  0 F 0  a n d  c o m p o u n d s ,  v a r i a t i o n s ,  a s  P O C  a n g l e s  a l t h o u g h  n o t e d  t h e  a b o v e  f o r  t h e  d e r i v a t i v e .  r i n g s  c a r b o n  t h a n  i n  a n g l e s  T h e p h e n y l  c o n t r a s t  d e r i v a t i v e s .  s i m i l a r  i n d i v i d u a l  i n  b o n d h a v e  a t o m s  a t o m s  d i s t a n c e s b e e n  a r e o f  a n d  d e t e r m i n e d  u n d e r g o i n g  t h e  b o n d l e n g t h s v a r y o A ), t h e m e a n d i s t a n c e i n 1 . 0 2  t h e  r a n g e o A .  w i t h  a n g l e s  l e s s  l a r g e r  0  b e i n g 0.93  -  1.37 1 . 1 8  i n  .  o A  A . (  t h e  a c c u r a c y ,  t h e r m a l  p h o s p h o n i t r i i i c r i n g . o o f r o m 1.33 A t o 1.43 A  0 . 0 1 9  d i s t a n c e s a r e . o . 0 . 0 8 A ; , m e a n  v a l e n c y  s i n c e  v i b r a t i o n s T h e  m e a s u r e d  (  Cf  =  0 . 0 1 0  T h e  C - H  b o n d  u  =  0 . 0 6  -  -  P A R T  T H E  C R Y S T A L  A N D  I I I  M O L E C U L A R  S T R U C T U R E  OF  D O D E C A ( D I M E T H Y L A M I N O ) C Y C L 0 H E X A P H O S P H 0 N I T R I L E C H L 0 R 0 C O P P E R  D I C H L O R O C U P R A T E  (I)  ( I I )  76  I n t r o d u c t i o n  3.1  Kost o f t h e X - r a y p h o s p h o n i t r i l e s  w h i c h  a s  p h e n o x y  t h et r i m e r i c  a n d  m o r e  r e c e n t l y  t w o  d i f f e r e n t  f l u o r i n e  r e p o r t e d  a r eh o m o g e n e o u s l y c o m p o u n d  l i g a n d s ,  s u c h  h a sb e e n  i  i  s u c h  n p a r t I I ,  o f p h o s p h o n i t r i l e s  w i t h  a s t h et w o t e t r a m e r i c  d e s c r i b e d  o n  s u b s t i t u t e d ,  d e s c r i b e d  s t r u c t u r e s  on  c o m p o u n d s  w o r k  n p a r t  I .  m e t h y l t y p e  Another  o  f  * 64,65 p h o s p h o n i t r i l e a t o m  f o r m s  t e r e s t  h a s been c o m p l e x  a  w i t h  i s t h em a n n e r  t h e  p h o s p h o n i t r i l e ,  t h e  b o n d i n g  i  w h i c h t o  w i t h i n  o p p o s i t e  a  n w h i c h  t h e r i n g .  t h em e t a l  n i t r o g e n  a n d a  a t o m s  a t o m  t h em e t a l  h a v e  C u C J ^  a  metal  r i n g .  T h e s t r u c t u r e s  c o m p l e x e s  p r o t o n  n w h i c h  p h o s p h o n i t r i i i c  O f i n -  i s b o n d e d a t o m  t o  has o n  o f t w o  r e c e n t l y  c y c l o t e t r a p h o s p h o n i t r i l i u m  c o n t a i n s  t r i i i c  a  i  a n d t h e e f f e c t  m e t a l - p h o s p h o n i t r i l e o c t a m e t h y l  d e s c r i b e d  b e e n  s u c h  r e p o r t e d :  t r i c h l o r o c o p p e r ( I I ) ,  g r o u p  c o v a l e n t l y  o f a n e i g h t - m e m b e r e o  b o n d e d  p h o s p h o n i -  a n d b i s - ( o c t a m e t h y l c y c l o t e t r a p h o s p h o n i t r i l i u r n 3 7 t e t r a c h l o r o c o b a l t a t e ( I I ) , a n i o n i c s t r u c t u r e c o n t a i n i n g t w o I n  p r o t o n a t e d b o t h  t r i i i c  a  t h e s e r i n g  p a i r s by  r i n g ,  p h o s p h o n i t r i i i c s t r u c t u r e s  i s p e r t u r b e d  o f e l e c t r o n s p r o t o n  s t r u c t u r e s  a n aa  by  a  c o p p e r  t h e e f f e c t  r i n g s  t h e by  TT-system  t h e r e m o v a l  p r o t o n i  a n d a  i  i o  4  i o n .  p h o s p h o n i -  f n i t r o g e n  i  l o n e  c o m p l e x ,  c o m p l e x .  l e n g t h s  2-  n t h e  n t h e c o b a l t  n t h ec o p p e r  o n t h eb o n d  C o C X  I n  o r b o t h  n t h e p h o s p h o n i -  24-28 t r i l i c  rings  i s t h a t  p r e d i c t e d  by  r f - b o n d i n g  t h e o r y .  )  77  A new  c o p p e r - p h o s p h o n i t r i l e complex has been  prepared by the r e a c t i o n o f  dodeca(dimethylamino)cyclohexa-  p h o s p h o n i t r i l e w i t h anhydrous c u p r i c c h l o r i d e i n methyl e t h y l 66 ketone  nn< manner t o the p r e p a r a t i o n o f the 67 complex. E v a p o r a t i o n o f the r e s u l t -  i n an analagous  [(NPMe„) h i CuCi 2 4 J 3  i n g s o l u t i o n y i e l d e d b r i g h t orange c r y s t a l s of the  copper-  p h o s p h o n i t r i l e complex.  sug-  gested the formula  I n i t i a l chemical a n a l y s i s  [NPUMe^ J  6  » 2 C u C ^ , but the  X-ray  2  s t r u c t u r e a n a l y s i s has e s t a b l i s h e d the formula  as  f N.P (NMe ) CuCJl 1 CuC& ~. L 6 6 2 12 J 2 +  T h i s s t r u c t u r e d e t e r m i n a t i o n was  undertaken  to compare the manner i n which the copper i s bonded to the r i n g , and the e f f e c t i t has on the ' r i n g , with the two 3.2  previously reported structures.  Experimental Crystals of  ^N^P^ (NMe  b r i g h t orange p l a t e s w i t h b.  TT-system i n the  U n i t - c e l l and  j^CuCJ!, "j  ^ ~  a  r  e  2  (101*) developed,  elongated a l o n g  space-group data were determined  v a r i o u s r o t a t i o n , vVeissenberg, and and on a  + G u C  precession  from  photographs,  spectrogoniometer.  C r y s t a l Data.  C  H 2 4  72 V 2 18 6' ~ G  U  N  P  =  1  0  3  2  5  m o n o c l i n i c , a = 19.352(8), b = 8.690(6), c = 14.069(7) A, o (2 =91.04(4) (standard d e v i a t i o n s i n p a r e n t h e s e s ) ,  78  U = 23c-5.6  , D  ~  — m  = 1.45  ™~  ( f l o t a t i o n i n CKBr, / C H . ), Z = 3 ^ o — A  ,  D = 1.450, F ( 0 0 0 ) = 1 0 8 2 . ~x -1 —  =13.5  cm.  — J-  .  Mo-K ~  Space  group  from s y s t e m a t i c absences: from s t r u c t u r e  (Mo-K  ^  s  hp 4. when  o = 0.7107 A,  v  4  (C^),  (h+J?) i s o d d ;  P2/n  analysis.  The 2 &  radiation, 2 P n ( C ) o r P2/n  A  ^  2,  i n t e n s i t i e s of a l l )  ^.  40°  reflexions  (minimum i n t e r p l a n a r s p a c i n g , 1.04  were m e a s u r e d on a D a t e x - a u t c m a t e d  Mo-K  ^  radiation  h e i g h t a n a l y s e r ) , and a  8-2  0  of f o u r degrees per minute  i n 2 9.  XiiD  General E l e c t r i c  Spectrogoniometer, with a s c i n t i l l a t i o n a t e l y monochromatic  with  6  counter, approxim(Zr f i l t e r  scan a t a scan Background  and  pulse-  speed counts  f o r t e n s e c o n d s w e r e made a t t h e b e g i n n i n g and  end o f  each  scan.  I , was  cal-  culated  The  standard d e v i a t i o n of an i n t e n s i t y ,  from the  expression  <5^(1) = S + B +  w h e r e 3 and  3 a r e t h e scan ana  flexions with  I  <  2  <T* ( I )  (O.C5S)  2  background  c o u n t s , and r e -  were c l a s s i f i e d  as  unobserved;  t h e s e r e f l e x i o n s were a s s i g n e d s t r u c t u r e f a c t o r s e q u a l t o t h e i r m e a s u r e d v a l u e s , b u t v/ere e x c l u d e d f r o m t h e ment.  Of 2300 r e f l e x i o n s w i t h 2 Q  were c l a s s i f i e d  A)  as observed.  The  ^  4 0 ° , 1103  c r y s t a l u s e d was  refine(48'/*) a  thin  7 9  plate,  with  0.28  length  0.10  x  3•3  Structure  gested t h a t  the  elemental  compound  atoms, of  b , a n d cross-section  to  correction w a s m a d e .  Analysis  Initial  density  parallel  H o absorption  0.03  chlorine  mm.  and  1.50  contained  "* a g r e e d  g.cm.  two  copper  p h o s p h o n i t r i l e .  the  XVII)  ( T a b l e  analysis  The  s u g -  f o u r  atoms,  calculated w i t h  the  formulation  was  approximately  rnea-  ~3  s u r e a  value  cepted  of  g.cm.  1.4-5  initially.  The  suggested  that  per  situated  atoms  the  and  indicated  perpendicular  this  P a t t e r s o n  three-dimensional  P 2 / n , v / i t h  s p a c e - g r o u p was cn  phorus atoms a r f - n d vectors  , ana  separate o f the  one  the  axes,  presence  w i t h  and  function c o p -  two the  phos-  copper atoms.  T h e Cu-Cj?  of  both  Cu-CJ? b o n u s  axes, w h i c h  to  the  a c -  s u g g e s t e u  along  the  possible  zp r e s e n c e  of  however the the of  uuGJ,  first  the  atoms of in  presence two  tially  the of  ion.  In  the  centre  only  bonaed  to  of  three  the  The  T h i s and  not  to  bias  map  was  atoms,  map  finally  copper also  one  structure by  analysis only  revealed  v/ith a  the  the  phased  T h i s mar;  ring;  chlorine  Cu(I).  procedures.  atoms.  phosphonitrile,  b y block-diagonal,  squares  order  electron-density  p h o s p h o r u s  c o p p e r and  C u ( 2 ) ,  ana  a  a l l atom,  s h o w e d  bonded  was  to  the C u ( 2 ) ,  refined,  full-matrix  scattering factors  on  from  inileast-  t h e  9 national  T a b l e s  w e r e u s e d , ana  the  function  m i n i m i z e d  I n t e r -  80  TABLE XVII Comparison o f elemental a n a l y s e s f o r t h e p o s t u l a t e d and a c t u a l formula f o r the complex. Element  Analysis  {%)  Initial  Final  Cu  11.40  12.33  CJP  12.99  10.24  P  13.22  N  23.52  24.15  C  27.33  28.18  H  6.78  6.86  Element  Theoretical [ N P (NMe ) 6  6  2  1  2  J . 2CuCi  2  Composition (NMe ) 2  1 2  • CuClJ * CuC* "  Cu  11.90  12.31  CX  13.28  10.30  P  17.41  18.00  N  23.61  24.43  C  26.99  27.92  H  6.81  7.04  2  81  was  >  w(F -F ) , w i t h w t a k e n a s t h e r e c i p r o c a l o f — —o — c —  v a r i a n c e i n F, a s d e t e r m i n e d  from the c o u n t i n g  statistics.  Isotropic refinement with a n i s o t r o p i c thermal for  the copper,  R o f 0.083. listed  phosphorus,  M e a s u r e d and  parameters  c h l o r i n e atoms gave a  calculated  final  structure factors  are  i n Table X V I I I . A final o-3  oi  and  the  j u.5  e.A  .  i t i o n s f o r methyl  d i f f e r e n c e map  had  maximum f l u c t u a t i o n s  Many o f t h e p e a k s w e r e i n r e a s o n a b l e  pos-  g r o u p h y d r o g e n a t o m s , b u t no a t t e m p t  made t o i n c l u d e t h e s e atoms i n t h e a n a l y s i s . no f e a t u r e s on t h e map  was  There were  t o i n d i c a t e the presence  of a  fourth  c h l o r i n e a t o m , so t h a t p r e p a r a t i o n o f t h e compound must i n v o l v e r e d u c t i o n o f one  o f the C u ( I I ) atoms t o C u ( I ) .  s t r u c t u r e o f t h e compound i s shown i n F i g u r e 1 3 ; and  The  chemical  s t r u c t u r a l c o n s i d e r a t i o n s (see D i s c u s s i o n } i n d i c a t e  t h e o u ( I I ) atom i s b o n d e d t o t h e p h o s p h o n i t r i i i c r i n g , t h a t t h e compound i s  N •P / - ( N M e )  L o o p o s i t i o n a l and  C u  2 12  thermal parameters  X  x  G H  \  J  Cu^CiL"". 2  are g i v e n ir; Table  unusual f e a t u r e i s a high thermal  that so  Final XIX.  The  only s l i g h t l y  for  t h e CuCfl,. g r o u p i n g , w i t h t h e r.m.s. d i s p l a c e m e n t f o r A i n the b - d i r e c t i o n , t h a t i s at  CJJ.-] ) b e i n g n e a r l y 0.5  a n g l e s t o t h e Cu~C£ b e n d . that the i s o l a t e d vibrations,  CuC$  motion  2  Although  i t i s not  unreasonable  does undergo t h e s e l a r g e  i t seemed d u r i n g t h e c o u r s e o f t h e  right  thermal  analysis  8 2  TKBLE M e a s u r e d  and f i n a l  U n o b s e r v e d  h k I 0  ^  0 10  F„ 116.65  F  c a l c u l a t e d  r e f l e x i o n s  l  l  i  i -7  7  -15.J?  ?l-lr> **.7*  X V I I I  h a v e  A. L  6  ? a  "-Q., , o . o  a  s t r u c t u r e n e g a t i v e  iq.ao  2  4  4.30  i  t, -5  £  115.71  -?<J 6 .L il.Z"  fc5.51  -*.!2  in.;  ?2.?3 50.04 18.95  5 ]<..«()  f a c t o r s . F .  83  TABLE  XVXIX  (continued)  8 4  TABLE X V I I I  (continued)  86  T A B L E F i n a l  p o s i t i o n a l  U ^ j  nA  o2 i  Cu(2)  ) , w i t h  10  a n d  4(gJ:  C*(2) i +  ( x ,  X  N ( l )  0.7349(10) 0.6561(9) 0.6426(9) 0.6503(11) 0.6036(12) 0.5703(12) 0.5380(12) 0.7223(10) 0.6603(11) 0.6876(13 ) 0.6302(15 ) 0.5315(14) 0.6164(14) 0.5162(13 ) 0.5992(16) 0.4784(15) 0.5456(14) 0.6881(17) 0.7596(15) 0.6001(17) 0.6951(15)  C ( l )  C(2 ) C(3)  C(4) C(5) C(6) 0(7) C(8) C(9) 0(10)  C ( l l )  C(12)  A t o m C u ( l )  Cu(2) CX(1) 01(2) P ( l )  P(2) P(3)  s t a n d a r d  P2/n((£.  A t o m  N (2 ) N(3) N(4) N(5) N(6) N(7) N(3) N(9)  a n d  t h e r m a l  p a r a m e t e r s  °2  (B i n  A  ;  2, x  S p a c e - g r o u p  i n  ( f r a c t i o n a l )  X I I  ); C u ( l ) i n  <dn n2 ( f ) :  y_,  d e v i a t i o n s  z ; ^  -  2(e):  +  ( f y , ~ ) ;  x  , y_,  ;  i  i  n p a r e n t h e s e s .  +  (f,y,f);  ~ A Ao t h e r a t o m s  - z )  B  0.2326(23)  0.3145(24) 0.3858(22) 0.4852(24)  0.2090(28) 0.5487(28) 0.2546(26) 0.3687(24) 0.1095(24) 0.6103(30) 0.5259(34) 0.2543(28) 0.0464(34) 0.5720(31) 0.6367(40) 0.2979(36) 0.0908(33 ) 0.5038(37) 0.2690(34) 0.1175(38) -0.0413(34) X  1/4 3 A 0.1490(5) 3/4 0.6599(3) 0.6045(4) 0.6974(4)  0.3907(14) 0.2657(13) 0.0838(12) 0.4220(15) 0.4357(16) 0.1951(15) 0.1850(16) -0.0568(14) 0.0122(14) 0.3765(18) 0.5195(20) 0.4335(18) 0.4499(19) 0.2645(18) 0.1478(22) 0.1153(20) 0.1974(19) -0.0968(22) -0.1260(21) -0.0564(23) 0.0080(20)  2.79(50) 2.63(45) 1.94(43) 2.65(50) 3.95(53) 4.15(57) 4.18(59) 2.71(47) 3.07(49) 2.89(61) 4.30(73) 3.57(70) 3.27(65) 3.16(64) 5.95(35) 4.94(71) 3.61(69) 5.61(87) 4.75(77) 6.09(36) 3.97(72)  y.  z  0.1417(7) 0.1937(6) 0.1427(16) -0.0684(12) 0.3138(9) 0.3763(9) 0.2778(9)  1/4 1/4 0.2005(7) 1/4 0.3793(5) 0.1833(5) 0.0413(5)  37  T A B L E  Atom  X I X  (cont.}  11  Cu(l)  hi 10.38  -22 8.03  Cu(2)  1.36  C*d) CA(2)  ^33  hz  %3  ^23  0.89  0  0  -0.33  0  7.30  2.46  -0.05  1.14  5.30  0  -I.64  0  4.76  0  3.37  2.20  8.64  22.96  9.60  -0.23  P(D  1.91  3.03  3.02  0.78  -0.11  0.04  P(2)  2.65  2.33  3.49  0.07  -0.56  0.01  P(3)  2.62  3.60  1.69  -0.12  -1.03  0.47  88  that of  t h e l a r g e v i b r a t i o n s might r e a l l y  t h e C$(1) p o s i t i o n .  represent disorder  However, r e f i n e m e n t  o f two h a l f -  c h l o r i n e atoms, d i s p l a c e d a l o n g b, converged position, to  t o t h e mean  so t h a t t h e l a r g e thermal v i b r a t i o n ooes appear  oe H r f i a i  e11ect.  Bond d i s t a n c e s a n d v a l e n c y a n g l e s a r e g i v e n i n i ' a b i e i.X.  3 • /»• D i s c u s s i o n The  compound s t u d i e d i n t h e p r e s e n t X - r a y  s i s w a s o b t a i n e d by r e a c t i o n o f N .F . (UKe ) . w i t h 6 o 2 1-c i n methyl the  formula u n i t  ition of  The X-ray  results  CuCJfc 2  indicate  arid t h r e e c h l o r i n e a t o m s , s o t h a t  elemen-  ( T a b l e X V I I ) o f t h e p r o d u c t was i n a g r e e m e n t  w i t h t h r e e c h l o r i n e atoms p e r f o r m u l a u n i t T h e susceptibility  magnetic  was m e a s u r e d , and a l t h o u g h i t i s d i f f i c u l t  t o make a n a c c u r a t e d i a m a g n e t i c of  half  i n t h e c o m p l e x must h a v e b e e n r e d u c e d t o  The p r e p a r a t i o n was r e p e a t e d , a n d a c a r e f u l  analysis  that  c o n t a i n s t h e p h o s p h o n i t r i l e w i t h t h e add-  c f two c o p p e r  the- c o p p e r  Cu(I). tal  ethyl ketone.  analy-  correction for a  substance  t h i s c o m p l e x i t y , t h e r e s u l t s were i n a g r e e m e n t w i t h one  C u ( I I ) atom p e r f o r m u l a The  presence  unit. o f C u ( I I ) a n d C u ( I ) ' i n t h e complex 6 6  was  confirmed  by t h e f o l l o w i n g  out  i nacetoriitriie,  i n which  series of reactions, r e d u c t i o n was n o t t o be  carried expected:  8 9  T A B L E  o  XX  Bond l e n g t h s (A) and valency angles  (degrees), w i t h  standard d e v i a t i o n s i n parentheses. Cu(2 )-N(l) Cu(2)-N(2) Cu(2)-Cl(2j  2.03(2 2.11(2 2.28(1  Cu(l)-CA(1) 2.06(1) [2.11(1) c o r r e c t e d f o r l i b r a t i o n ]  N(l)-P(l) N(l)-P(3 ) N(2)-P(l) N(2)-P(2) N(3)-P(2) N(3)-P(3) P(l)-N(4) P(l)-N(5) P(2)-N(6) P(2)-N(7) P(3)-N(8) P(3)-N(9)  1.62(2) 1.65(2) 1.60(2) 1.61(2) 1.53(2) 1.57(2) 1.62(2) 1.64(2) 1.65(2) 1.67(2) 1.67(2) 1.68(2)  N 4) -G (1) N< 4) -C ( 2 ) N [5) -C (3) N \5) -G (4) N [6) -C (5) N 6) -C (6) N [7) -C (7) N 7) -C (3) N 8) -C (9) N iS) -C (10) N|[9) -C ( I D N 9) -C (12)  1.46(3) 1.48(3) 1.45(3) 1.45(3) 1.46(3) 1.49(3) 1.55(3) 1.44(3) 1.46(3) 1.50(3) 1.50(3) 1.47(3)  N(2)-Cu(2)-N(l) N(2)-Cu(2)-N(l» ) N(2)-Cu(2)-N(2» ) N(l ) - C u ( 2 ) - N ( l ' ) Cl(2 )-Cu(2)-N(2) CA(2 )-Cu(2)-N(l)  71.2(7) 99.1(8) 120.5(11) 160.9(12) 119.8(5) 99.6(6)  N [1) -P (1)-N(2) N (1) -P (D-N(4) N [1) -p (1)-N(5) N [ 2 ) -p (1)-N(4) N 2 )-p (D-N(5) N i4) -P (1)-N(5)  97.2(10 118.2(11 108.2(12 111.3(11 117.9(11 104.5(12  f  CA(1)-CU(1)-CJI(1» ) 179.5(9) P(l)-N(l)-P(3') P ( l J-MliJ-Gui2) P(3 )-N(D-Cu(2) P(l)-N(2)-P(2) P(l)-N(2)-Cu(2) P(2)-N(2)-Cu(2) P(2)-N(3)-P(3) T  130.7(13) 96.9(10) 118.4(11) 137.6(13) 94.5(9) 127.9(11) 132.4(13)  C-N-G  111-118,  mean 114  P-N-C  114-127,  mean 120  N (2) -p (2)-N(3) N 2) -p (2)-N(6) N 2) -P (2)-N(7) N [3) -p (2)-N(6) N -p (2)-N(7) N [6) -p ( 2 ) - N ( 7 ) N (3) -p ( 3 ) - N ( l M N (3) -p (3)-N(8) N (3) -p (3)-N(9) N (1* )-P(3)-N(8) N (1' )-P(3)-N(9) N -P(3)-N(9)  IB)  110.0(10 118.5(12 104.3(11 103.8(12 115-5(12 105.2(12 115.4(10 .106.0(11 109.6(11 110.7(10 105.3 (11 109.8(10  9 0  ( i )  p h o s p h o n i t r i l e a  w i t h  c r y s t a l l i n e  a p p e a r a n c e e t h y l  s o l i d ,  f r o m  k e t o n e ,  m e n t a l  c o p p e r  t h e  a n d  a n a l y s i s  w h i c h  w h i c h  f o r  p h o s p h o n i t r i l e a  ( i i i )  p h o s p h o n i t r i l e a n d  s o l i d ,  i d e n t i c a l  t h e  a n  a n d  b y  m e t h y l  ( I )  e l e -  • C u „ C X . ;  r  2 It  2  4  c h l o r i d e  e q u i m o l a r  c h l o r i d e s  w i t h  a n a l y s i s ,  a n a l y s i s ,  i n  g a v e  s o l i d ;  c u p r o u s  X - r a y  i n  s a t i s f a c t o r y  b  c o p p e r  w i t h  c u p r i c  p r o d u c e d  g i v e  g a v e  d i f f e r e n t  N ^ P ^ ( N M e „ ) ,  w i t h  p o o r l y - d e f i n e d  c h l o r i d e  w a s  m a t e r i a l  o ( i i )  ( I I )  t h a t  a s  m i x t u r e  g a v e  a  c r y s t a l l i n e  p r e v i o u s l y  i n d i c a t e d  V / e i s s e n b e r g  b y  a n d  o f  u s e d  i n  e l e m e n t a l  p r e c e s s i o n  p h o t o g r a p h s . I t a t o m s  i n  t h e  r e m a i n e d  o n l y  c o m p o u n d  c o m p o u n d s  o f  s t r u c t u r e  r a t h e r  r e a s o n a b l e ,  C u ( I )  i t  i s  i s  h a v e  t h a n  a  S i n c e  t h a t  C u C J ^ t h e  2  a n d ~,  c o o r d i n a t e d r i n g ,  a n d  t o t o  a  c u p r i c f o u r  c o p p e r  a n d  s i n c e  a n  s e e m s  a t o m  i s  i o n i c m o r e  b o n d e d  t h a t t h e c o m p o u n d i s d o d e c a ( d i m e t h y l a m i n o ) ( I I )  a t o m ,  Cu(2)  n i t r o g e n  a t o m s  o f  a t o m  t h e  f i v e - c o o r d i n a t e d  a d d u c t  c o p p e r  c h l o r i n e  o f  n o  G u ( I I )  c y c l o h e x a p h o s p h o n i t r i l e c h l o r o c o p p e r T h e  w h i c h  r e p o r t e d ,  s i m p l e  r i n g , C u ^ C X  +  d e c i d e  C u ( I ) . b e e n  l i k e l y  t o t h e p h o s p h o n i t r i i i c [ I] P , ( N K e ) C u ^ C j ? ~\ L 6 o 2 1 2 J  t o  ( F i g u r e  d i c h l o r o c u p r a t e i n  t h e 1 4 ) -  F i g u r e  1 3 ,  ( I ) . i s  p h o s p h o n i t r i i i c T h e  f i v e f o l d  2.28  F i g u r e  1 4 .  G e n e r a l a t o m  v i e w  o  ft h e  c o o r d i n a t i o n  N ? (NMe 6  ( N M e  6  2  2  g r o u p s  ^ CuC* 2  o m i t t e d  i o n , f o r  s h o w i n g  t h e  c l a r i t y ) .  c o p p e r  ( I I )  92  coordination i s probably square pyramid, w i t h i t i o n , although  best  described  as a d i s t o r t e d p o s -  t h e c h l o r i n e atom i n t h e a p i c a l  a n a l t e r n a t i v e and e q u a l l y s a t i s f a c t o r y w i t h  d e s c r i p t i o n i s as a d i s t o r t e d t r i g o n a l bipyramid, } and i-i{1' ) i n a x i a l  p o s i t i o n s  ( F i g u r e  14).  pounds w i t h f i v e - c o o r d i n a t e C u ( I I ) i n s i m i l a r have b e e n r e p o r t e d ,  com-  O t h e r  configurations  e.g. d i m e t h y i g l y o x i m a t o c o p p e r ( I I ) . o  The C u ( 2 )-C£.bond d i s t a n c e , 2 . 2 8 ( 1 ) A ( T a b l e  XX a n d  Figure  i s s i m i l a r t o t h e l e n g t h f o u n d i n v a r i o u s C u ( I I ) corno 69 p o u n d s , e . g . 2.28 A i n CuC*2*2H 0 2.22 - 2.26 A i n  14),  }  £(NrMe^)  Hj C u C S ^ . ^  The s m a l l d i f f e r e n c e b e t w e e n  ^  t h e two  o  Cu(2 )-N bond d i s t a n c e s , 2.03(2) and 2.11 (2 ) A, may b e s i g n i f i c a n t , and t h e d i f f e r e n c e i s n o t s u r p r i s i n g , s i n c e effects doubtless  play a part i n determining  c o n f i g u r a t i o n a t C u ( 2 ); t h e C u ( 2 ) - N l e n g t h s t h o s e i n r e l a t e d compounds,  steric  t h e exact are similar to  e . g . 2.04(2) A i n £ ( I J F M e  0  )^HJCuCA  The c u p r o u s c o p p e r a t o m , C u ( l ) i n F i g u r e 1 3 , is  i n the l i n e a r anion  in  solution, ^  not  C u C X  .  This anion  but i t s occurrence,  p r e v i o u s l y been d e f i n i t e l y  has been  i n the s o l i d  established.  detected  state h a s The Cu — CJZ  bona l e n g t h , c a l c u l a t e d f r o m t h e f i n a l a t o m i c c o o r d i n a t e s , o i s 2,06(1) A ; c o r r e c t i o n f o r thermal l i b r a t i o n , assuming 72 a riding m o d e l , increases t h i s distance t o a f i n a l value o o f 2 . 1 1 ( 1 ) i i . Few o t h e r r e l i a b l e v a l u e s a r e a v a i l a b l e  93  f o r comparison.  The Cu-Cft d i s t a n c e  i s g i v e n a s 2.16 ±  o *Z 3 C.015 ft i n t h e CuCJJ t r i m e r , ' w h e r e t h e C*-Cu~C4  1L  O  i s about 150 .  The sum o f t h e c o v a l e n t  ( 0 . 9 9 A) ana o f Cu(I) o i s 2.17 A. is  r a d i i ' ^ of chlorine  i n a linear coordination  (1.18 A)  The o b s e r v e d d i s t a n c e i n t h e p r e s e n t  s l i g h t l y l e s s than these  values.  are linear.  structure  The r e l a t e d i o n s AgCfi,,",  AuCJ?2~? a n d nutsr,," have b e e n f o u n d i n t h e s o l i a all  angle  s t a t e , and  F o r A g G J ^ " a n d A u C 8 ~ t h e sum o f t h e c o v a l 0  o  ent r a d i i a r e 2.38 and 2.33 A, r e s p e c t i v e l y , a n d t h e m e a s u r e d 75  Ag-CJt a n d Au-Cfc d i s t a n c e s , are, w i t h i n r a t h e r wide l i m i t s o.t e r r o r , 2.36 a n d ^ .31 A r e s p e c t i v e l y . f o r t h e more a c c u r „ • 9 a t e l y m e a s u r e d AuBr, , t n e c o v a l e n t r a d i u s sum i s 2.45 A, 76  2  and  t h e measured Au-3r d i s t a n c e  o  i s 2 . 3 5 ( 1 ) A.  i n g s i t u a t i o n i n Cudft^" i s o b v i o u s l y v e r y i n these  to that  related ions. T h e r e a r e two d i s t i n c t  i n the p h o s p h o n i t r i i i c r i n g P-N bend l e n g t h s  types  o f P-N bond  distance  ( T a b l e XX a n d F i g u r e 1 5 ) .  The  i n v o l v i n g n i t r o g e n atoms w h i c h a r e b o n d e d  t o c o p p e r a r e i n t h e r a n g e 1.60 mean 1.62  similar  The b o n d -  these  - 1.65(2)  A (Figure 15),  distances are close to the lengths of  s i m i l a r b o n d s , 1 . 6 3 ( 2 ) A, i n [ ( N P M e ) h i CuCS The 2 4 J 3 P-N bond d i s t a n c e s i n v o l v i n g N ( 3 ) , w h i c h i s n o t bonded t o 0  L  o  c o p p e r , a r e .1.53 a n d 1 . 5 7 ( 2 ) A , mean 1.55 o t h e bono l e n g t h , 1 . 5 6 ( 1 ) A, i n t h e p a r e n t  o  A, s i m i l a r t o 77  N,P,(NMe_) , . b o 2 12  95  These bend l e n g t h d i f f e r e n c e s c a n he i n t e r p r e t e d 24-28 oi  fT-oonaing theory.  n i t r o g e n atom w h i c h  i n terms  The l o n e - p a i r e l e c t r o n s o f a  i s bonded t o c o p p e r a r e u t i l i z e d  Cu-N b o n a , a n d a r e t h u s removed f r o m  the P - N  i n the  ft -bonding  _  24-28  TT-system i s s t i l l o p e r a t i v e , o a n a ' t h e n e t r e s u l t i s a P - N b o n a l e n g t h o f 1.62 A a t t h o s e n i t r o g e n atoms b o n d e d t o c o p p e r , a d i s t a n c e i n t e r m e d i a t e system.  A second  053 b e t w e e n a s i n g l e bond l e n g t h o f 1.77 A .0 77 of I . 5 0 A i n N P { N k e j 6 6  ana a normal  length  2 12  The v a l e n c y a n g l e s i n t h e r i n g  ( T a b l e XX a n d 77 F i g u r e 15 i d i f f e r g r e a t l y f r o m t h o s e i n t \ L P , ( N M e ~ ) ^  and  „  i n other phosphonitriles,  6 b  and t h e unusual  t h e p r e s e n t compound a r e d i r e c t l y a t t r i b u t a b l e tortion of the phosphonitriiic t o t h e copper atom. at P ( l ) ,  2  r i n g caused  12  angles i n t o the d i s -  by t h e b o n d i n g  The d i f f e r e n c e s a r e most p r o n o u n c e d  where t h e N(1 )~P(1 ) - N ( 2 ). a n g l e o f 9 7 . 2 ° i s t h e  s m a l l e s t e n d o c y c l i c angle a t phosphorus which ported i n a p h o s p h o n i t r i i i c  compound.  has been r e -  The c o r r e s p o n d i n g  a n g l e s a t P ( 2 } a n a P ( 3 ) , 110.0° a n d 115.4° r e s p e c t i v e l y , o 77 a r e a l s o s m a l l e r t h a n t h e 120 a n g l e f o u n d i n i \ L - P , ( N R e ) , _ , 00 2 12 2.1 and i n o t h e r p h o s p h o n i t r i l e s . The a v e r a g e P - N - P a n g l e o o i n t h e r i n g , 134 , i s much s m a l l e r t h a n t h e a n g l e o f 1 4 7 . 5 77 found i n t h e parent N ^ P , ( N M e „ ) 6"6'2'12*  The e x o c y c l i c  P-N bond d i s t a n c e s ( T a b l e XX)  o 63 e a l l she, r t e r t h a n t h e P-N s i n g l e - b o n d l e n g t h o i 1.77 A ,  96  ana  this  suggests the existence  ing,  utilizing  n i t r o g e n p_TT  this  indication  o f e x o c y c l i c P-N ; 1T-bond-  orbitals.  Consistent  ff-bonding, t h e dimethylaraino  of  v/ith groups  a r e a l l n o t f a r f r o m p l a n a r , t h e sums o f t h e v a l e n c e  angles  a t t h e n i t r o g e n atoms v a r y i n g f r o m 3 4 4 ° a t N(9) t o 360° at N(6).  The e x o c y c l i c P-N d i s t a n c e s a t P ( l ) , 1 . 6 2 ( 2 ) and o o 1.64(2) A, mean 1 . 6 3 ( 1 ) A, a r e . s l i g h t l y s h o r t e r t h a n t h o s e o  0  a t P ( 2 ) a n d P (3 ), 1.65  - 1 . 6 8 ( 2 ) A, mean 1 . 6 7 ( 1 ) A. A l -  though the d i f f e r e n c e i s b a r e l y expected d i r e c t i o n ,  significant,  since withdrawal  i ti s i n the  of the lone-pair elec-  t r o n s a t i'J(l) a n a N ( 2 ) b y t h e c o p p e r a t o m s h o u l d donation  f r o m K ( 4 ) a n d N(5 ) t o P ( l ) ( F i g u r e 1 3 ) , a n d  in greater cyclic  enhance  exocyclic  TT-bonding ana hence s h o r t e r  r e s u l t  exo-  p-K bonds a t P ( l ) . The  i n t h e dimethylamino groups o a r e i n t h e r a n g e 1 . 4 5 ( 3 ) t o 1 . 5 5 ( 3 ) A ( T a b l e X X ) , t h e mean o d i s t a n c e o f I.48 A not d i f f e r i n g s i g n i f i c a n t l y from the value  C-N bond l e n g t h s  o f I . 4 6 t\ f o u n d i n N,P^ ( M e 6  Steric determining ring, sent  and t h e d e t a i l s  conformation of the Cu(II)  ing  12  part i n  of the phosphonitrilic coordination i n the pre-  The c o p p e r c o n f i g u r a t i o n c o u l d be made  more n e a r l y s q u a r e p y r a m i d a l , at P ( l ) could  )... 2  e f f e c t s must p l a y a n i m p o r t a n t  the exact  structure.  6  be i n c r e a s e d  and t h e e n d o c y c l i c  N-P-N  angle  t o a more n o r m a l v a l u e , b y b r i n g -  P ( l ) ana P ( i ' ) c l o s e r t o g e t h e r .  T h i s w o u l d however  97  cause i n c r e a s e d s t e r i c i n t e r a c t i o n s between NMe^ The  conformation  o f the p h o s p h o n i t r i l i c r i n g  groups.  (Figure  14)  bears l i t t l e resemblance to those of known p h o s p h o n i t r i l i c structures.  The r i n g can be regarded  from a completely  as being  p l a n a r arrangement, which i s f o l d e d about  the N(1)...N(1') d i r e c t i o n to g i v e two o s e c t i o n s at a d i h e d r a l angle of 129 The  packing  i n Figure 16.  The  c h l o r i n e atoms.  approximately  o f the i o n s i n the u n i t c e l l i s shown  shorter i n t e r i o n i c distances involve  The  between methyl groups  s h o r t e s t CH^  CI d i s t a n c e i s  3.54 A* between C£(2) o f the standard formula (:*> Y.> £ ) ^(1) °f i° (^J Y_ l> £ ) • a  n  d  planar  (Figure 14).  c o n t a c t s between methyl groups, and and  derived  t  n  e  n  a t  _  u n i t at Theise are  s e v e r a l CH  OH c o n t a c t s l e s s than the sum o f the van , o 50 o der Waals r a d i i (40 A) , the s h o r t e s t being 3.50 A between 3 i ° C(10) a t (x, y_, z) and C(10) at (~-x, y_, - ~ z ) , and 3.61 A 3  v  between C(6) a t  (x, y_, z ) and  C(12)  at  (x, l+y_, z).  These  are not to be c o n s i d e r e d unduly compressed, however, s i n c e CH  •"•CH- c o n t a c t s o f l e s s than 4.0 % are not uncommon o ' 7 3 and c o n t a c t s as s m a l l as 3.13 A have been r e p o r t e d . 3  3  V/ith n o n - r o t a t i n g methyl groups these need not  involve  unreasonably small H****H d i s t a n c e s . T h i s i s the- t h i r d m e t a l - p h o s p h o n i t r i l e  complex  whose s t r u c t u r e has been e l u c i d a t e d , and a l l t h r e e are o f d i f f e r e n t types.  [(NFMe ) H 1 2 4 ^ 2 +  CoC* ~ 4 2  i s an  ionic  99  compound, 37 i n which the c o b a l t atom i s not d i r e c t l y bonded to the p h o s p h o n i t r i i i c r i n g ; CuCiJ  group with the copper atom c o v a l e n t l y bonded t o one  43 n i t r o g e n o f the r i n g ;  and the s t r u c t u r e d e s c r i b e d above  i s i o n i c and has a copper bonded t o f o u r n i t r o g e n atoms of a p h o s p h o n i t r i i i c r i n g .  There i s no apparent  for t h i s variety of metal-phosphonitrile  explanation  complexes, thus  making t h i s a f i e l d where f u r t h e r work would be very profitable.  REFERENCES  101  1.  W . L  . B r a g g ,  2.  G .H . S t o u t a n dL . H . J e n s e n , " X - R a y S t r u c t u r e D e t e r m i n a t i o n " , T h e M a c m i l l a n C o m p a n y , New Y o r k , 1968.  3.  M .J . B u e r g e r , " V e c t o r N e w Y o r k , 1959.  4.  M .J . B u e r g e r , a n d S o n s I n c . ,  5 .  H . L i p s o n a n d W . C o c h r a n , " T h e C r y s t a l l i n e S t a t e . V o l . I l l : T h e D e t e r m i n a t i o n o fC r y s t a l S t r u c t u r e s " , 3rd e d . , G . B e l l a n d S o n s L t d . , L o n d o n , 1966.  6.  M .J S o n s  . B u e r g e r , I n c . , Nev/  " T h e P r e c e s s i o n Y o r k , 1964.  M e t h o d " ,  J  . W i l e y  a n d  7.  M .J S o n s  . B u e r g e r , I n c . , N e w  " X - R a y C r y s t a l l o g r a p h y " , Y o r k , 1942.  J  .W i l e y  a n d  8.  M . M. W o o l f s o n , " D i r e c t M e t h o d s O x f o r d U n i v e r s i t y P r e s s , 1961.  9.  " I n t e r n a t i o n a l T a b l e s f o r 1952; V o l . I I , 1959; V o l . B i r m i n g h a m .  10.  H .R o s e ,  11.  J . L i e b i g  12. 13.  P r o c .  C a m b r i d g e  S p a c e " ,  J  S o c . ,  A n n . , 11, 131 F  .W o h l e r ,  H . N  . S t o k e s ,  J  .A m .  J  . K e t e l a a r  a n d  T  17,  . W i l e y  " C r y s t a l S t r u c t u r e Nev; Y o r k , I960.  a n d  . A  P h i l .  a n d  43  S o n s  A n a l y s i s " ,  i  (1913).  J  I n c . ,  . W i l e y  n C r y s t a l l o g r a p h y " ,  X - R a y C r y s t a l l o g r a p h y " , V o l . I I l l , 1962, K y n o c h P r e s s ,  (1834). A n n . ,  C h e m . .A  11,  S o c . ,  . de  139  18,  V r i e s ,  (1834).  629  R e c .  (1896). T r a v .  C h i m . ,  58, 1081 (1939). 14.  L  . E  .A u d r i e t h ,  R  .S t e i n m a n ,  a n d  A  . D  .T r a y ,  C h e m .  R e v . , 3.2, 109 (1943). 15.  N . L . P a d d o c k a n d H . T . S e a r l e , " A d v a n c e s i n I n o r g a n i c C h e m i s t r y a n d R a d i o c h e m i s t r y " , V o l . I , H . J . E m e l e u s a n d A . G . S h a r p e , e d s . , A c a d e m i c P r e s s I n c . , Nev/ Y o r k ,  1959. 16.  N  . L  . P a d d o c k ,  E n d e a v o u r ,  19,  134  (I960).  ,  102  17.  I . A. Gribova and U. Ban-Yuan, Russ. Chem. Rev., 3_0, 1 (1961).  18.  N. L. Paddock, Roy. I n s t . Chem. L e c t u r e S e r i e s , No. 2, (1962).  19.  C. D. Schmulbach, "Progress i n Inorganic Chemistry", V o l . IV, F. A. Cotton ed., I n t e r s c i e n c e P u b l i s h e r s , London, 1962.  20.  R. A. Shaw, R. Keat, and C. Hewlett, " P r e p a r a t i v e I n o r g a n i c R e a c t i o n s " , V o l . I I , W. L. J o l l y ed., I n t e r s c i e n c e P u b l i s h e r s , London, 1965.  21.  N. L. Paddock, Quart. Rev., 18, 168 (1964).  22.  R. A. Shaw, B. W. Fitzsimmons, and B. C. Smith, Chem. Rev., 62, 247 (1962).  23.  D. £. C. C o r b r i d g e , "Topics i n Phosphorus Chemistry", V o l . I l l , E. J . G r i f f i t h and M. Grayson eds., I n t e r s c i e n c e P u b l i s h e r s , New York (1966).  24.  D. P. C r a i g and N. L. Paddock, Nature, 181, 1052 (1958).  25.  D. P. C r a i g , J . Chem. S o c , 997 ( 1 9 5 9 ) .  26.  D. P. C r a i g and N. L. Paddock, J . Chem. S o c , 4118 (1962).  27.  D. P. C r a i g , A. M a c c o l l , R. S. Nyholm, L. E. O r g e l , and L. E. Sutton, J . Chem. S o c , 332 (1954).  28.  D. P. C r a i g and N. L. Paddock, i n p r e s s .  29.  M. J . S. Dewar, E. A. C. Lucken, and M. A. Whitehead, J . Chem. S o c , 2423 (I960).  30.  M. W. D o u g i l l , J . Chem. S o c , 1075 (1961).  31.  G. J . B u l l en, J . Chem. S o c , 3193 (1962).  32.  R. Hazekamp, T. Migchelsen, and A. Vos, Acta G r y s t . , 15, 539 (1962).  33.  G. B. A n s e l l and G. J . B u l l e n , Chem. Comm., 430 (1966); G. J . B u l l e n , p e r s o n a l communication.  34.  A. J . Wagner and A. Vos, Acta G r y s t . , B24, 707 (1963).  35.  G. J . B u l l e n and P. R. M a l l i n s o n , Chem. Comm., 691 (1969).  36.  H. McGeachin and F.  Tromans, J . Chem. S o c , 4777 (1961).  1  103  37.  J. T r o t t e r  38.  M  .W .D o u g i l l  39.  N  .L  40.  a n d  (1970).  V  a n dN  .P a d d o c k ,  S o c . , N.  S . H  .W h i t l o w ,  . L.  J. C h e m .  :  P a d d o c k ,  J. T r o t t e r ,  C h e m .  a n dS . H  S o c ,  A  C o m m . ,  i  . W h i t l o w ,  F  n  p r e s s . C h e m .  J.  A , 2227 (1968). . M a n i ,  , 460  "  . R . A h m e d ,  a n dW . H  . B a r n e s ,  A c t a  a n dW . H  .B a r n e s ,  A c t a  C r y s t . ,  19, 693 (1965). 41.  N  . V  . M a n i ,  21, 375 42.  C . W.  . R . A h m e d ,  A l l e n ,  I n o r g . 43.  F  J. B  C h e m . ,  .F a u g h t ,  8, 1719  J. T r o t t e r  a n d  44.  N  a n d  45-  N. L . P a d d o c k , T . N C o m m . , i n p r e s s .  46.  S . H . ' W h i t l o w , P h . D . C o l u m b i a , 1969.  47.  A .J. C . W i l s o n ,  48.  R e f e r e n c e  49.  I . L  . M a n i  S . H  12,  A  T . M o e l l e r ,  . ' W h i t l o w ,  .J. W a g n e r ,  K  T h e s i s ,  15C  C h e m .  U n i v e r s i t y  151  658  o  , 455  (1968).  .T o d d ,  C h e m .  f B r i t i s h  a n dS . A  . B r e n n e r ,  A c t a  (1965).  N . L .P a d d o c k c a t i o n .  a n d  T . N  .R a n g a n a t h a n ,  52.  C  a n d  H  .L o n g u e t - H i g g i n s ,  53-  . P a u l ,  (1942).  51.  A,  A  ~  a n dS . M  L .P a u l i n g , " T h e E d i t i o n , C o r n e l l I960, p a g e 260.  C o u l s o n  S o c . ,  C o m m . ,  50.  . A.  a n dI. C  320.  .S . D r a g o n e t t e ,  713  J. C h e m .  .R a n g a n a t h a n ,  N a t u r e ,  p a g e  2,  .K a r l e ,  C r y s t . ,  ,  (1969).  (1970). . V  C r y s t .  (1966).  N a t u r e o ft h e C h e m i c a l B o n d " , U n i v e r s i t y P r e s s , I t h a c a , N e w  . C  p e r s o n a l  P r o c .  3rd Y o r k ,  c o m m u n i -  R o y .  S o c . ,  191 (1947).  J . N .M u r r e l l , S . F . A . K e t t l e , a n dJ . M .T e d d e r , e n c e T h e o r y " , J o h n ' W i l e y a n d S o n s L t d . , N e w Y o r k , p a g e 280.  " V a l 1965,  104  54.  C  55.  N. L. P a d d o c k ,  p e r s o n a l  56.  M .  J  57.  A  . W i l s o n  a n d  D . F  58.  E  .G i g l i o  a n d  R  F  .R  59.  .A .C o u l s o n a n d A . S t r e i t w i e s e r T r . , " D i c t i o n a r y o f • f T - E l e c t r o n C a l c u l a t i o n s " , W . H. F r e e m a n a n d C o m p a n y , S a n F r a n c i s c o , 1965.  W .D o u g i l l ,  .A h m e d ,  P  c o m m u n i c a t i o n .  .C h e m .  S o c ,  3211  .C a r r o l l ,  .P u l i t i , . S i n g h ,  J  A c t a  a n d  (1963).  . C h e m . C r y s t . ,  W . H  2548 (I960).  S o c . , 22,  .B a r n e s ,  304  (1967).  A c t a  C r y s t . ,  B25_, 316 (1969). 60.  G J.  .A l l e n , D .J . O l d f i e l d , N . L .P a d d o c k , F . R a l l o , S e r r e ^ i , a n dS . M . T o d d , C h e m . & I n d . , 1032 (1965).  61.  R  .F  J .  .S t e w a r t ,  C h e m .  F  P h y s . ,  . L. P a d d o c k ,  .R  .D a v i d s o n  42, 3175  62.  N  63.  D. « v . J . C r u i c k s h a n k ,  64.  J. D y s o n  65.  M  a n d  p e r s o n a l  W . T  .  S i m p s o n ,  c o m m u n i c a t i o n . J  . G h e m .  N. L . P a d d o c k ,  . F. L a p p e r t  a n d  (1965).  S o c ,  C h e m .  5486 (1961).  C o m m . ,  a n d  G  .S r i v a s t a v a ,  J  a n d  G  .J  p e r s o n a l  191  . C h e m .  (1966).  S o c . ,  A  , 210  (1966). 66.  N  . L  .P a d d o c k  67.  J  .D y s o n ,  P h . D .  . S t e w a r t ,  T h e s i s ,  V i c t o r i a  c o m m u n i c a t i o n .  U n i v e r s i t y  o  f  M a n c h e s t e r ,  1964. 68.  E .F r a s s o n , 201 (1959);  (A),  69.  R A  . B a r d i , a n dS . B e z z i , A c t a C r y s t . , 12, .V a c i a g o a n d L. Z a m b o n e l l i , J . G h e m . S o c  213 (1970).  S . W .P e t e r s o n  a n d  H . A  .  L e v y ,  J  . C h e m .  P h y s . ,  26,  220  (1957). 70.  F .A .C o t t o n a n d G .W i l k i n s o n , " A d v a n c e d I n o r g a n i c i s t r y " , I n t e r s c i e n c e P u b l i s h e r s , 1962, p a g e 750.  71.  A .F . . v e i l s , " S t r u c t u r a l e d i t i o n , C l a r e n d o n P r e s s ,  I n o r g a n i c O x f o r d ,  C h e m i s t r y " , 3rd 1962, p a g e 859.  C h e m -  105  72.  W. R. Busing and H. A. Levy, Acta C r y s t . , 17,  142  (1964).  73.  C.-H. Wong and V. Schomaker, J . Phys. Chem., 6 1 , 358 (1957).  5 0 , pp. 246 and 2 5 3 .  74.  Reference  75.  N. E l l i o t and L .  Pauling,  76.  P. T. Beurskens, J . J . Steggerda,  H. J . A. Blaauw, J . A. Cras, and Inorg. Chem., 7 , 805 ( 1 9 6 8 ) .  77.  A. J . Wagner and A. Vos, Acta C r y s t . , B 2 4 , 1423 ( 1 9 6 8 ) .  78.  A. W. Hanson, Acta C r y s t . , B24, IO84  (1938).  J . Am. Chem. Soc., 60, 1846  (1968).  

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