Preparation and characterization of triorganotin(IV) derivatives of mercaptocarboxylic acids. Crystal structure of

Article abstract of DOI:10.1016/0022-328X(89)87021-4

The syntheses and tin-119m Moessbauer spectroscopic data are reported for the tri-n-butyl, tricyclohexyl- and triphenyltin(IV) derivatives of mercaptoacetic and 2-mercaptobenzoic acids.A four-coordinate tetrahedral geometry at tin is assigned for (cyclo-C6H11)3SnSCH2C(O)OH and for the (C6H5)3SnSCH2C(O)O^- and (C6H5)3SnSC6H4C(O)O^- anions, isolated as the dicyclohexylammonium and iso-S-benzylthiuronium salts, respectively.The sulfidotin in R3SnSCH2C(O)OSnR3 and R3SnSC6H4C(O)OSnR3 is also four-coordinate, but the carboxylatotin is four-coordinate for R=C6H5 and five-coordinate for R=n-C4H9.The Moessbauer quadropole splitting in the butyltin case indicates a trans-C3SnO2 trigonal bipyramidal configuration.The coordination assignment for the two tin atoms in bis(triphenyltin)-2-mercaptobenzoate is confirmed by X-ray crystallography.The compound crystallizes in space group P2₁/c with a 14.293(4), b 17.456(2), c 15.624(1) Angstroem, β 107.40(1) deg; Z=4.The structure was refined to an R factor of 0.035 for 5837 observed reflections.The carbonyl oxygen of the molecule is positioned roughly halfway between the carboxylatotin (Sn***O 2.765(3) Angstroem) and sulfidotin (Sn***S 3.016(1) Angstroem), distorting somewhat the tetrahedral geometries at both tin sites.