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Co(NCS)2 Chain Compound with Alternating 5- and 6-Fold Coordination: Influence of Metal Coordination on the Magnetic Properties

  • Michael Böhme
    Michael Böhme
    Institut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität Jena, Humboldtstraße 8, Jena 07743, Germany
  • Michał Rams*
    Michał Rams
    Institute of Physics, Jagiellonian University, Łojasiewicza 11, Kraków 30348, Poland
    *Email: [email protected]
    More by Michał Rams
  • Christoph Krebs
    Christoph Krebs
    Institut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, Max-Eyth-Straße 2, Kiel 24118, Germany
  • Sebastian Mangelsen
    Sebastian Mangelsen
    Institut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, Max-Eyth-Straße 2, Kiel 24118, Germany
  • Inke Jess
    Inke Jess
    Institut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, Max-Eyth-Straße 2, Kiel 24118, Germany
    More by Inke Jess
  • Winfried Plass*
    Winfried Plass
    Institut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität Jena, Humboldtstraße 8, Jena 07743, Germany
    *Email: [email protected]
  • , and 
  • Christian Näther*
    Christian Näther
    Institut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, Max-Eyth-Straße 2, Kiel 24118, Germany
    *Email: [email protected]
Cite this: Inorg. Chem. 2022, 61, 42, 16841–16855
Publication Date (Web):October 11, 2022
https://doi.org/10.1021/acs.inorgchem.2c02813
Copyright © 2022 American Chemical Society

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    Abstract

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    The reaction of Co(NCS)2 with 3-bromopyridine leads to the formation of discrete complexes [Co(NCS)2(3-bromopyridine)4] (1), [Co(NCS)2(3-bromopyridine)2(H2O)2] (2), and [Co(NCS)2(3-bromopyridine)2(MeOH)2] (3) depending on the solvent. Thermogravimetric measurements on 2 and 3 show a transformation into [Co(NCS)2(3-bromopyridine)2]n (4), which upon further heating is converted to [{Co(NCS)2}2(3-bromopyridine)3]n (5), whereas 1 transforms directly into 5 upon heating. Compound 5 can also be obtained from solution, which is not possible for 4. In 4 and 5, the cobalt(II) cations are linked by pairs of μ-1,3-bridging thiocyanate anions into chains. In compound 4, all cobalt(II) cations are octahedrally coordinated (OC-6), as is usually observed in such compounds, whereas in 5, a previously unkown alternating 5- and 6-fold coordination is observed, leading to vacant octahedral (vOC-5) and octahedral (OC-6) environments, respectively. In contrast to 4, the chains in 5 are very efficiently packed and linked by π···π stacking of the pyridine rings and interchain Co···Br interactions, which is the basis for the formation of this unusual chain. The spin chains in 4 demonstrate ferromagnetic intrachain exchange and much weaker interchain interactions, as is usually observed for such linear chain compounds. In contrast, compound 5 shows almost single-ion-like magnetic susceptibility, but the magnetic ordering temperature deduced from specific heat measurements is twice as high as that in 4, which might originate from π···π stacking and Co···Br interactions between neighboring chains. More importantly, unlike all linear Co(NCS)2 chain compounds, a dominant antiferromagnetic exchange is observed for 5, which is explained by density functional theory calculations predicting an alternating ferro- and aniferromagnetic exchange within the chains. Theoretical calculations on the two different cobalt(II) ions present in 5 predict an easy-axis anisotropy that is much stronger for the octahedral cobalt(II) ion than for the one with the vacant octahedral coordination, with the magnetic axes of the two ions being canted by an angle of 84°. This almost orthogonal orientation of the easy axis of magnetization for the two cobalt(II) ions is the rationale for the observed non-Ising behavior of 5.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.2c02813.

    • Tables with crystal data, bond lengths and angles, and hydrogen-bonding parameters, ORTEP plots, IR spectra, PXRD patterns, Rietveld plot, TG–DSC curves, additional plots and tables for the DFT calculations, and drawings of different magnetic measurements (PDF)

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    CCDC 21592572159260 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    Cited By

    This article is cited by 1 publications.

    1. Christoph Krebs, Inke Jess, Christian Näther. Synthesis, crystal structure and thermal properties of bis(acetonitrile-κ N )bis(3-bromopyridine-κ N )bis(thiocyanato-κ N )cobalt(II). Acta Crystallographica Section E Crystallographic Communications 2023, 79 (1) , 14-18. https://doi.org/10.1107/S2056989022011380

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