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Cation- and/or anion-directed reaction routes. Could the desolvation pattern of isostructural coordination compounds be related to their molecular structure?

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Abstract

The crystal and molecular structure of [Cu(ampf)(ClO4)(MeOH)2]ClO4, (1), ampf = N,N′-bis(4-acetyl-5-methylpyrazol-3-yl)formamidine, determined by X-ray crystallography is described and compared with the structurally related copper(II) complexes, formed under similar experimental conditions, using CuII salts with different anions. The complex formation is discussed in view of the structures of cobalt(II) and nickel(II) complexes with the same organic ligand and different anions, also formed under similar reaction conditions. Solvent molecules coordinated to the central atom play an important role in biologic systems. To get a better insight into the desolvation mechanism, in this study the desolvation pattern of 1 is presented. As in literature little attention is paid to the desolvation mechanism of solvate complexes, the desolvation mechanism of three, potentially biologically active isostructural pairs of octahedral NiII and CoII compounds with ampf and dmpc (3,5-dimethyl-1H-pyrazole-1-carboxamidine) ligands are evaluated and compared with the desolvation of 1. The results of the thermal data are discussed on the basis of structural features of the compounds. The minor differences in structures of the related compounds cannot be straightforwardly connected with the different solvent evaporation mechanism. To explain the differences found in desolvation pattern in isostructural CoII and NiII complexes the Jahn-Teller effect is proposed.

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Notes

  1. The repeatability of the measurements was also tested. Caution: Most of the perchlorates belong to explosives therefore special attention should be paid to protective measures. In the case of thermal measurements, the sample mass (<1 mg) and the heating rate (<20 °C min−1) should be kept low.

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Acknowledgments

The authors thank to the Ministry of Education, Science and Technological Development of the Republic of Serbia for financial support (Projects No. ON172014 and III45022) and Secretariat for Science and Technological Development, Autonomous Province of Vojvodina, Republic of Serbia.

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Authors and Affiliations

  1. Faculty of Sciences, University of Novi Sad, Trg D. Obradovića 3, 21000, Novi Sad, Serbia

    Berta Holló, Marko V. Rodić, Vukadin M. Leovac & Katalin Mészáros Szécsényi

  2. Faculty of Technology, University of Novi Sad, Bulevar cara Lazara 1, 21000, Novi Sad, Serbia

    Oskar Bera & Mirjana Jovičić

  3. Vinča Institute of Nuclear Sciences, University of Belgrade, P.O.Box 522, 11001, Belgrade, Serbia

    Zoran D. Tomić

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  1. Berta Holló
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Correspondence to Katalin Mészáros Szécsényi.

Electronic supplementary material

CCDC 922242 contains the supplementary crystallographic data for this paper. The data can be obtained free of charge at www.ccdc.cam.ac.uk.

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Holló, B., Rodić, M.V., Bera, O. et al. Cation- and/or anion-directed reaction routes. Could the desolvation pattern of isostructural coordination compounds be related to their molecular structure?. Struct Chem 24, 2193–2201 (2013). https://doi.org/10.1007/s11224-013-0270-9

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  • DOI: https://doi.org/10.1007/s11224-013-0270-9

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