Add time:07/23/2019 Source:sciencedirect.com
A systematic investigation of the CuCl2/Mebta (Mebta = 1-methylbenzotriazole) reaction system is described, involving the determination of the influence of the CuII:Mebta ratio, the nature of solvent and the presence of counterions on the identity of the reaction products. As a consequence, complexes [Cu2Cl4(Mebta)4] (1), [CuCl2(Mebta)2] (2), {[Cu2Cl4(Mebta)2]}n (3), [Cu4OCl6(Mebta)4] · 0.25H2O (4 · 0.25H2O) and [Cu2Cl2(Mebta)6](ClO4)2 (5) have been isolated and structurally characterized by single-crystal X-ray studies. Mebta behaves as a monodentate ligand binding through N(3). 1 is a dinuclear complex, the structure of 2 consists of discrete monomeric units, and that of 3 is composed of linear, well-separated polymeric chains of CuII atoms. The molecules of 4 · 0.25H2O have a central μ4-oxide ion surrounded tetrahedrally by four CuII atoms. In the cations of 5 the two CuII centres are asymmetrically bridged by two chloro ligands, with three Mebta molecules completing five coordination at each metal. Complexes were characterized by spectroscopic (IR, far-IR, solution UV/Vis) and thermal decomposition (TG, DTG, and DTA) techniques. Variable-temperature magnetic susceptibility data for 1, 3 and 5 showed intramolecular (1, 5) and intrachain (3) ferromagnetic exchange interactions. Estimates of the Jparameters, experimentally derived, were in close agreement with a new magneto-structural criterion developed by us, holding for bis(μ-chloro) copper(II) dimers. A comparison between the CuCl2/Mebta and CuBr2/Mebta systems is also presented.
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