HIRSHFELD SURFACE ANALYSIS OF A MONONUCLEAR PYRAZOLE-CONTAINING COPPER(II) COMPLEX OBTAINED BY OXIDATIVE DISSOLUTION METHOD
DOI:
https://doi.org/10.15421/jchemtech.v33i2.312363Keywords:
pyrazole ligands, copper complexes, crystal structure, oxidative dissolution, Hirshfeld surface analysisAbstract
In this work, a method of oxidative dissolution was used to obtain mononuclear copper(II) complex Cu(С6H8N3O)2 with 1-carboxamide-3,5-dimethylpyrazole. The variety of techniques were used to identify and characterize the structure of the complex and the ligand, such as IR and NMR spectroscopy, microanalyses, single-crystal X-ray diffraction. Hirshfeld surface analysis was performed to visualize the close intermolecular atomic contacts in the crystal structure of the title compound. It was found that Cu(С6H8N3O)2 was formed as a result of a multistage process of oxidative dissolution of metallic copper with the participation of air oxygen and ammonium ions. This process leads to the appearance of a sufficient amount of Cu2+ ions in the solution, which partially ensures the production of the final compound, as well as the dissolution of zero-valent copper through the formation of intermediate Cu1+ compounds, which are oxidized by air oxygen to form divalent copper compounds. It has also been found that ammonium cyanate is formed in parallel through exchange reactions, which undergo dissociation in acetonitrile solutions, and the resulting HNCO undergoes hydrolysis. The hydrolysis products react with the starting ligand 3,5-dimethyl-1H-pyrazole to form 1-carboxamide-3,5-dimethylpyrazole. This acid then reacts with Cu2+ ions to form the final mononuclear complex. Single‐crystal X‐ray diffraction analysis reveals that the title compound crystallizes in the triclinic crystal system, space group P (Z = 2). For the title compound, the most significant contributions to the overall crystal packing are from H···H (47 %), H···O/O···H (19.5 %), H···C/C···H (12.1 %) and H···N/N···H (11.5 %) contacts. According to the Hirshfeld surface analysis, hydrogen bonds (H···H and H···O/O···H) and other close contacts involving hydrogen atoms make the main contribution to intermolecular interactions in the title compound. Two intermolecular NH···O contacts with a length of 2.192 Å are the shortest.
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