Organotin(IV) complexes with the formulas [(C6H5)(3)Sn(mbzt)] (1), [(C6H5)(3)Sn(cmbzt)] (3), and [(C6H5)(2)Sn(cmbzt)(2)] (4) (Hmbzt = 2-mercaptobenzothiazole and Hcmbzt = 5-chloro-2-mercaptobenzothiazole) have been synthesized and characterized by elemental analysis; FT-IR, Raman, H-1, C-13, and Sn-119 NMR, and Mossbauer spectroscopic techniques; and X-ray crystallography at various temperatures. The crystal structures of complexes 1, 3, and 4 were determined by X-ray diffraction at room temperature [295(1) or 293(2) K]. The complexes [(C6H5)(3)Sn(mbzo)] (2) and [(n-C4H9)(2)Sn(cmbzt)(2)] (5) (Hmbzo = 2-mercaptobenzoxazole) were synthesized by new improved methods, and their structures were determined at low temperature [100(1) K] and compared to those solved at room temperature. Comparison with {(CH3)(2)Sn(cmbzt)(2)]} (6), already reported, was also attempted. The influence of temperature on the geometry of the complexes is discussed. In the cases of complexes 1-3, three carbon atoms from phenyl groups and one sulfur atom and one nitrogen atom from thione ligands form a tetrahedrally distorted trigonal-bipyramidal geometry around the five-coordinate tin(IV) ion. In complexes 4-6, two carbon atoms from aryl groups and two sulfur atoms and two nitrogen atoms from thione ligands form a distorted tetrahedral geometry, tending toward octahedral, around the six-coordinate tin(IV) ions, with trans-C-2, cis-N-2, and cis-S-2 configurations. Although the C-Sn and S-Sn bond distances are found to be constant in compounds 1-6, their N-Sn bond lengths vary significantly (from 2.635 to 3.078 angstrom), with the longer distances found in the cases of five-coordinate complexes 1-3.