Synthesis, structural, Continuous Shape Measure and bond valence sum characterization of bismuth(III) complexes of substituted dithiocarbamates and their solvothermal decomposition

Bismuth(III) complexes, [Bi(chmdtc)(3)] (1) [Bi(chedtc)(3)] (2) and [Bi(dchdtc)(3)] (3) (where chmdtc = cyclohexylmethyldithiocarbamate, chedtc = cyclohexylethyldithiocarbamate and dchdtc = dicyclohexyldithiocarbamate) have been prepared and characterized by electronic, IR, NMR (H-1 and C-13) spectra, and single crystal X-ray diffraction. Electronic spectra of the complexes show signature bands in the range 418-423 nm due to charge transfer transitions. The characteristic thioureide bands occur at 1474, 1467 and 1443 cm(-1) for (1), (2) and (3) respectively. Single crystal X-ray structures of [Bi(chmdtc)(3)] (1), [Bi(chedtc)(3)] (2) and [Bi(dchdtc)(3)] (3) indicate that the short Bi-S interactions between the molecules lead to dimeric structures. CShM calculations on the chromophores clearly quantify the extent of deviation from the ideal geometry. BiS6 chromophore in (1) is a distorted octahedron. The coordination geometry for both [Bi(chedtc)(3)] (2) and [Bi(dchdtc)(3)] (3) should be better described as distorted pentagonal pyramidal. The higher BVS values observed in the present set of compounds support the fact that the Bi-S bonds are more covalent. (C) 2014 Elsevier B.V. All rights reserved.