Add time:08/29/2019 Source:sciencedirect.com
The syntheses and tin-119m Mössbauer 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 Mössbauer quadrupole 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) Å, β 107.40(1)°; 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) Å and sulfidotin (Sn ⋯ S 3.016(1) Å, disorting somewhat the tetrahedral geometries at both tin sites.
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