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Crystal Structure and Hirshfeld Analysis of a Poorly Water Soluble Bis(ligand)copper(II) Complex Containing the Metallophore Pyridine-2-Carboxaldehyde 2-Furoyl Hydrazone

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Abstract

The crystal structure of a novel bis(ligand)copper(II) complex of the pyridine-2-carboxaldehyde 2-furoyl hydrazone (HPCFur) metallophore is described, altogether with its Hirshfeld surface analysis. The isolated compound crystallizes in the monoclinic system, space group P21/c, with four [Cu(PCFur)2] molecules in the asymmetric unit. Symmetry around copper is distorted octahedral. HPCFur coordinates in its deprotonated, iminolate form, which impacts the O1−C7 and N2−N3 distances in both ligand units. The complex exhibits a variety of weak, non-conventional intermolecular hydrogen bonds. Hirshfeld analysis and fingerprint plots indicate that, overall, hydrogen bond interactions are responsible for almost 50% of the crystal 3D arrangement, while nondirectional H···H contacts account for 38.0%. To the best of our knowledge, this is the first description of a copper(II) complex containing this ligand. The structural characterization of this poorly water soluble species contributes to a better understanding of the intricate equilibria that take place in biologically relevant ternary peptide/protein-copper-hydrazone systems.

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Scheme 1
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Data Availability

CCDC 2176002 contains the supplementary crystallographic data for 1. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_request@ccdc.cam.ac.uk, or by contacting Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336,033.

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Acknowledgements

All authors are grateful to the scientific Brazilian agency CNPq (Conselho Nacional de Desenvolvimento Científico e Tecnológico) for the research fellowships and scholarship awarded. NAR is also grateful to FAPERJ (Fundação Carlos Chagas Filho de Amparo à Pesquisa do Estado do Rio de Janeiro) for the “Cientista do Nosso Estado” fellowship granted. We would like to acknowledge Ministério da Ciência e Tecnologia (MCT) and Financiadora de Estudos e Projetos (FINEP)—Grant # Convênio: 01.11.0100.00. We thank Centro Nacional de Biologia Estrutural e Bioimagem (CENABIO) for the support with the X-ray diffraction facility (D8-Venture). The authors are also thankful to Prof. Csilla Kallay, for providing the decapeptide. CBPL acknowledges the Brazilian Chemical Society and Royal Society of Chemistry for the prize “Young Researcher of Royal Society of Chemistry—RASBQ 2021”.

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Authors and Affiliations

  1. Departamento de Química, Pontifícia Universidade Católica do Rio de Janeiro, Marquês de São Vicente, 225, Rio de Janeiro, RJ, 22451-900, Brazil

    Daphne S. Cukierman & Nicolás A. Rey

  2. Departamento de Química Inorgânica, Universidade Federal Fluminense, Campus do Valonguinho, Outeiro de São João Batista, s/n, Niterói, RJ, 24020-141, Brazil

    Carolina B. P. Ligiero

  3. Departamento de Engenharia Química e de Materiais, Pontifícia Universidade Católica do Rio de Janeiro, Marquês de São Vicente, 225, Rio de Janeiro, RJ, 22451-900, Brazil

    Roberto R. de Avillez

Authors
  1. Daphne S. Cukierman
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  2. Carolina B. P. Ligiero
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  3. Roberto R. de Avillez
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  4. Nicolás A. Rey
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Contributions

DSC and NAR conceived the experiments, interpreted the data, and wrote the paper. DSC also performed the syntheses of 1. CBPL and RRA performed the XRD measurements, structure refinement and analyses, and wrote the paper for the crystallography part.

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Correspondence to Daphne S. Cukierman or Nicolás A. Rey.

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Cukierman, D.S., Ligiero, C.B.P., de Avillez, R.R. et al. Crystal Structure and Hirshfeld Analysis of a Poorly Water Soluble Bis(ligand)copper(II) Complex Containing the Metallophore Pyridine-2-Carboxaldehyde 2-Furoyl Hydrazone. J Chem Crystallogr 53, 8–15 (2023). https://doi.org/10.1007/s10870-022-00955-z

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