SYNTHESIS, CRYSTAL STRUCTURE, THERMAL STABILITY AND HIRSHFELD SURFACE ANALYSIS OF AZAMETALLOCROWN COPPER(II) COMPOUNDS WITH 4-IODOPYRAZOLE

Authors

DOI:

https://doi.org/10.15421/jchemtech.v32i3.305413

Keywords:

copper, copper complexes, crystal structure, pyrazole, X-ray structure analysis, metallacrown, thermal analysis, Hirshfeld surface analysis

Abstract

The reaction of copper(II) chloride and copper(II) bromide with 4-iodopyrazole (HIpz or C3H3IN2) in the presence of copper powder in acetonitrile leads to the formation of the corresponding trinuclear copper(II) pyrazolates, [Cu3(OH)(C3H2IN2)3Cl2 ·2CH3CN]2 (1), and [Cu3(OH)(C3H2IN2)3Br2]n (2), respectively. Both complexes maintain the [Cu₃(μ₃-OH)(μ-Ipz)₃]²⁺ core, but they exhibit relevant differences in their molecular structures, as well as in their supramolecular arrangements. The crystal structure of complex 1 comprises trinuclear 9-azaMC-3 units linked by chlorine anions into dimers and arranged into polymeric chains through hydrogen bonds formed between the hydrogen atoms of the OH group and the Cl⁻ anions of adjacent fragments. The crystal structure of complex 2 is built up from the parallel packing of supramolecular chains running along the c-axis direction. Within each chain, the trinuclear metallacrown-like complex subunits are interconnected by bridging bromine atoms. Analysis of the geometry of the polyhedra revealed that the coordination polyhedron geometry of the pentacoordinated copper(II) ions in both structures is intermediate between trigonal bipyramidal and square pyramidal. The process of thermal degradation of the synthesized complexes with metallocrown structure was studied with the help of differential thermal analysis and thermogravimetry. Hirshfeld surfaces analysis was performed to investigate the intermolecular atomic contacts in the crystal structure of the title complexes.

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Published

2024-10-20

Issue

Vol. 32 No. 3 (2024): Journal of Chemistry and Technologies

Section

Physical and inorganic chemistry

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