Synthesis, properties, and crystal structures of mononuclear nickel(II) and copper(II) complexes with 2-oximino-3-thiosemicarbazone-2,3-butanedione

Abstract

The tridentate ligand 2-Oximino-3-thiosemicarbazone-2,3-butanedione (Hotsb) reacts with MCl2 (M = Ni2+ or Cu2+) to give rise to the mononuclear complexes [Ni(Hotsb)2]Cl2 · H2O (1) and [Cu(Hotsb)Cl2] · H2O (2). These complexes have been characterized by X-ray crystallography, spectroscopy, and cyclic voltammetry. The nickel(II) ion in (1) is in a six-coordinate octahedral environment being bonded to the two protonated tridentate ligands which occupy mer positions. The copper(II) ion in (2) is in a five-coordinate square-pyramidal geometry, in which the basal plane is made up the two nitrogens, sulfur, and chloride atom, while the other chloride atom is coordinated at the axial position. The cyclic voltammogram of the complexes displays two one-electron waves corresponding to MII/MIII and MII/MI processes. The electronic as well as infrared spectral properties of the title complexes are reported and discussed.