Structural studies of diorganotin(IV) sulphonates - The crystal structuresof [(eta-C4H9)(2)Sn{mu-OSO2C6H2(CH3)(3)}(2)](n) and its partially hydrolyzed product [(n-C4H9)(2)Sn{(mu-OH)(mu-OSO2C6H2(CH3)(3))}](n)

The X-ray crystal structures of [(n-C4H9)(2)Sn{mu -OSO2C6H2(CH3)(3)}(2)](n) (1) and [(n-C4H9)(2)Sn{(mu -OH)(mu -OSO2C6H2(CH3)(3))}](n) (2) were determ ined to delineate the coordination behaviour of the sulphonate group with t in(IV) and to evaluate the metal sulphonate bonding interactions. The synth esis of 1 has been achieved by azeotropic dehydration of di-n-butyltin(IV) oxide and mesitylenesulphonic acid. 1 is polymeric containing six-coordinat e tin and crystallizes from anhydrous toluene in the orthorhombic space gro up P2(1)2(1)2 with unit cell dimensions a = 12.555(1), b = 21.238(1), c = 5 .415(1)Angstrom; Z = 2; R, 0.0236 and wR, 0.0607 for 1281 observed reflecti ons. The structure exhibits highly symmetrical bridging bidentate mesitylen esulphonate groups and is made up of an infinite array of (n-C4H9)(2)SnO4 m oieties. Compound 1 hydrolyzes very slowly to [(n-C4H9)(2)Sn {(mu -OH)(mu - OSO2C6H2(CH3)(3))}](n) (2), when kept in CH OH-CHCl3, mixture at room tempe rature for 35 days. Crystals of 2 are monoclinic with space group P2(1)/m a nd unit cell dimensions a = 10.040(1), b = 14.500(1), c = 13.978(1) Angstro m; beta = 91.58(1)degrees; Z = 4; R, 0.0226; wR, 0.0592 for 2725 observed r eflections. The crystal structure is built of polymeric chains in which [{( n-C4H9)(2)Sn}(2)(OH)(2)] units are joined by bridging bidentate meistylenes ulphonate groups. The crystal lattice is stabilized by a network of hydroge n bonds running through the sheets, in which an oxygen atom of the sulphona te group and the hydroxyl group attached to tin participate in a symmetrica l fashion. In DMSO solutions, chemical shift (Sn-119) and (1)J(Sn-119-C-13) values for both 1 and 2 suggest a distorted octahedral geometry around tin in which DMSO may also be involved. (C) 2001 Elsevier Science B.V. All rig hts reserved.