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Structure and bonding in some mono- and bisfluorosulfates Mailer, Kathleen O'Sullivan

Abstract

The single crystal X-ray analyses of KSO(3)F and NH(4)SO(3)F are reported. Both are orthorhombic (space group: Pnma) with cell dimensions a =8.62 Å, b =5.84, c = 7.35 and a = 8.97 Å, b = 5.99, c = 7.54 respectively. Two of the anion ligand positions are completely disordered in KSO(3)F (i.e. SO(2)X(2)¯, X = 50% F and 50% O). A hydrogen bond between NH(4)+ and one of the SO(3)F ¯ disordered positions causes that ligand position to be occupied preferentially by oxygen in NH(4)SO(3)F. The laser Raman spectrum of CH(3)C(OH)(2)SO(3)F is determined. The vibrational spectra and SO(3)F¯ dimensions are compared in NK(4)SO(3)Fr KSO(3)F, CH(3)C(OH)(2)SO(3)F, and (CH3)2 Sn(SO3F)2. The SO(3)F¯ dimensions are surprisingly constant with only S-F in (CF3)2Sn(SO3F)2 (in which there is greatest X-OSO(2)F interaction) shorter than in the others. vS-F increases with increasing cation-anion interaction. The vibrational spectra of the fluorosulfates of Li+, Na+ , K+, NH4+, Rb+, Cs+, (CH3)4N+, and (C6H5)4As+ are reported. vS-F increases 108 cm(-1) with polarizing power of the cation (from (C6H5)4As+ to Li+) and vS-O (average) increases in the same series by 35 cm(-1). The preparation and conductivity in HSO(3)F of Sn(SO3F)2 and Pb(SO3F)2 are reported. Both are weaker bases than Ca(SO3F)2. The Mössbauer parameters of Sn(SO3F)2 (ὁ= +4.17 mm/sec, ∆ = 0.73 mm/sec) indicate it is one of the most ionic SnII compounds yet reported. A new preparative route for obtaining M(SO3F)2 {M(OOCC6H5)2 + HSO3F} is reported. The vibrational spectra of the bis-fluorosulfates of Mg(II), Ca(II), Sr(II), Ba(II), Sn(Il), Pb(II), Cu(II), Zn(II), Cd(II), Mn(II), and Hg(II) are reported. vS-O (average) and vS-F cannot be correlated with polarizing power of the cation or M2+ ionization potential but are in all cases higher than for the mono-fluorosulfates. The differences among the spectra are explained in terms of polarizing power of the cation, some multiple bonding to fluorine and different site-symmetries for the SO3 F¯ anion.

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