Reactions of copper(II) bromide with 2,6-diacetylpyridine bis(phenyl-hydrazone) (L)-molecular and crystal structure of L and its mixed-valence complex [CuIIL2][CuI2Br4

Abstract

Utilizing X-ray crystallography, the crystal and molecular structures of 2,6-diacetylpyridine bis(phenylhydrazone) (L) were determined. The energetics of the intermolecular interactions in the crystal structure were assessed with computational methods, revealing that dispersion interactions are dominant. The basic structural unit of the crystal packing was revealed to be the herring- bone type arrangement of L molecules. Assignation of the IR spectrum of L with the aid of DFT calculations was performed. Furthermore, new reactions of L with CuBr2 in different solvents are described, which led to the synthesis of the mixed Cu(II)?Cu(I) complex with the formula [CuIIL2][CuI 2Br4] (1), and its structural characterization. In the complex cation, two molecules of tridentate N3 ligand are meridionally arranged in a very distorted octahedral environment of a Cu(II) ion. In [Cu2Br4]2-, the bromide ions are arranged in a trigonal- -planar geometry around each copper(I) atom. Finally, for ligand, 1, and the previously synthesized complex [CuL2]Br2, the thermal properties were examined. The thermal stability of the complexes were lower than that of the ligand and decrease in the order: L (250?C) > [CuL2]Br2 (221?C) > [CuIIL2][CuI 2Br4] (212?C). The differences in thermal stability of the complexes are due to differences in the packing efficacy of the constitutional ions.