Copper(II) and copper(I) complexes with a bidentate hydrazinic dithiocarbazate: synthesis and crystal structures

In this work, we explored the ability of N-methyl-S-methyl dithiocarbazate ([H2N-N(CH3)C(=S)SCH3]; DTCZ) to form coordination complexes with copper starting from different copper (II, I) sources. Data proved that the type of used salt affects the stoichiometry and structure of the obtained coordination complexes. Copper complexes of general empirical formula [Cu(DTCZ)Cl2] (1), [Cu(DTCZ)2NO3]NO3 (2), [Cu(DTCZ)2(OH2)]SO4 (3), [Cu(DTCZ)2]PF6 (4), [Cu(DTCZ)(PPh3)2]NO3 (5) and [Cu(DTCZ)2]Br (6) were synthesized in high yield and characterized by elemental analysis, UV-Vis and IR spectroscopy. Molecular structures of 1-6 and also of sideproducts [Cu(DTCZ)2SO4] (3a), [Cu(DTCZ)2](PF6)(OH) (4b) and [CuBr(C3H7NS2)]n (6a) were determined by single crystal X-ray diffraction (XRD). In all cases, DTCZ binds the metal in the neutral form through the hydrazine nitrogen (NH2) and thione sulphur (S) atom set, forming monosubstituted and disubstituted complexes having tetrahedral, square planar, or square pyramidal geometries, depending on the copper source. In addition, two one-dimensional (1D) coordination polymers and water channels have been observed in the crystal states.