Synthesis, structure, and thermal properties of benzene-solvated forms of bis(dimethyldithiocarbamato)piperidinezinc and -copper(II)

Solvated adducts of zinc and copper(II) dimethyldithiocarbamate complexes with piperidine of the general formula [M{NH(CH2)5}{S2CN(CH3)2}2] · C6H6 (M = Zn (I), 63Cu (II)) were isolated on a preparative scale. According to X-ray diffraction data, compound I has a clathrate type structure: the benzene molecules located between the coordinated piperidine rings of neighboring adduct molecules are held by hydrogen bonds. Thermal destruction of I studied by simultaneous thermal analysis includes the desorption steps of benzene solvate molecules and inner-sphere piperidine molecules and thermolysis of the “dithiocarbamate part” of the adduct to give ZnS as the final product. The triaxial anisotropy pattern of EPR parameters of the isotope-substituted magnetically diluted adduct II indicates that the geometry of the copper coordination polyhedron is intermediate between a tetragonal pyramid (TP) and trigonal bipyramid (TBP). It was shown solvation of the adduct [63Cu{NH(CH2)5}{S2CN(CH3)2}2] resulting a considerable increase in the contribution of the TBP component.