The crystal structure of tetrameric copper(II) complexes, Hirshfeld surface analysis, and vector analyses of Cu4OCl6L4 complexes with N-donor ligands

Abstract

It is known, that in the Cu4OX6L4 (X = Cl, Br) complexes can be present many different ligands L, including bioligands. The synthesis and characterization of Cu4OBCl6(ron)4 (1) and Cu4OCl6(3-Mepy)4 (2) (where ron is ronicol or 3-methanolpyridine and 3-Mepy is 3-methylpyridine) are reported. The complexes under study were X-ray structure analysis and Hirshfeld surface analysis. Tetranuclear Cu4OX6L4 complexes with molecular structure (Fig. 1) can help to better understand the role of donor–acceptor and electron-transfer properties in copper proteins. The coordination sphere about each copper(II) atom is trigonal bipyramidal with three chlorine atoms in the equatorial plane. The apical positions are occupied by the central oxygen atom and the nitrogen atom of the respective ligand (CuCl3ON). Here are studied chloridocomplexes of some N-donor ligands, L = chloro-promazine, ronicol (3-pyridylmethanol), 2-ethylpyrazine, seven derivatives of pyrazol and for comparisons 3-methylpyridine. The Cu4OCl6L4 molecule is regarded as a supramolecular model of interactions between bioligand L and hypothetical “round-shaped” coordination tetra-receptor Cu4OCl6. Vector calculations applied usualy to mechanical and electrical macroconstructions are here applied to microconstructions represented by structures of Cu4OX6L4 molecules. For vector calculations each Cu4OX6L4 structure is placed (Fig. 1) into the three-dimensional Cartesian coordinate system with the central oxygen atom O1 placed in its origin 0. Studied bioligands are compared and described by molecular structural dynamics and corresponding shifts of electron densities by means of bond lenghts (O1–Cu, Cu–L, Cu–X) and structural distances (O1···X, O1···L).

Structure of the Cu4OX6L4 molecule

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Acknowledgements

The authors would like to thank Grant agencies of the Slovak Republic (VEGA 1/0639/18, APVV-18-0016) are gratefully acknowledged for their financial support. This article was created with the support of the MŠVVaŠ of the Slovak Republic within the Research and Development Operation Program for the project “University Science Park of STU Bratislava” (ITMS project no. 26240220084) cofounded by the European Regional Development Fund.

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Ondrejovič, G., Moncol, J. & Koman, M. The crystal structure of tetrameric copper(II) complexes, Hirshfeld surface analysis, and vector analyses of Cu4OCl6L4 complexes with N-donor ligands. Chem. Pap. (2020). https://doi.org/10.1007/s11696-020-01257-4

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Keywords

  • Crystal structure
  • Tetramers
  • Vector analyses
  • Copper(II) complexes
  • Hirshfeld surface