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Journal of the Serbian Chemical Society 2022 Volume 87, Issue 3, Pages: 307-320
https://doi.org/10.2298/JSC211127112R
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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]

Rodić Marko V. ORCID iD icon (University of Novi Sad, Faculty of Sciences, Novi Sad, Serbia), marko.rodic@dh.uns.ac.rs
Radanović Mirjana M. ORCID iD icon (University of Novi Sad, Faculty of Sciences, Novi Sad, Serbia)
Gazdić Dragana V. ORCID iD icon (University of Novi Sad, Faculty of Sciences, Novi Sad, Serbia)
Leovac Vukadin M. ORCID iD icon (University of Novi Sad, Faculty of Sciences, Novi Sad, Serbia)
Barta-Holló Berta ORCID iD icon (University of Novi Sad, Faculty of Sciences, Novi Sad, Serbia)
Raičević Vidak ORCID iD icon (University of Novi Sad, Faculty of Sciences, Novi Sad, Serbia)
Belošević Svetlana K. ORCID iD icon (Faculty of Technical Sciences, University of Priština, Kosovska Mitrovica, Serbia)
Krüger Biljana ORCID iD icon (University of Innsbruck, Institute of Mineralogy and Petrography, Innsbruck, Austria)
Vojinović-Ješić Ljiljana S. ORCID iD icon (University of Novi Sad, Faculty of Sciences, Novi Sad, Serbia)

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.

Keywords: copper(I), Schiff bases, tridentate coordination mode, X-ray crystallography, DFT

Project of the Serbian Ministry of Education, Science and Technological Development, Grant no. 451-03-02141/2017-09/14 and Grant no. 451-03-9/2021-14/ 200125

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