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 (1H and 13C) 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.