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Self-Assembly of Two Isomorphous Thiocyanate Complexes of Co(II) and Ni(II) with 3-Hydroxypicolinamide

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Abstract

The synthesis, thermal and spectral characterization, and crystal structure of isomorphous thiocyanate cobalt(II) and nickel(II) complexes with 3-hydroxypicolinamide (3-OHpia), [M(C6H6N2O2)2(NCS)2]·2H2O, are reported. The metal(II) ions are chelated by two cis-oriented 3-OHpia and two thiocyanate ligands in distorted octahedral geometry. The distortion within the coordination sphere is mainly imposed by formation of the chelate rings. The compounds crystallize in monoclinic space group P2/c with two symmetrically independent molecules and a = 14.4945(2) Å, b = 8.5906(1) Å, c = 16.3865(3) Å, β = 105.987(2)°, Z = 4 (1) and a = 14.4927(5) Å, b = 8.5912(3) Å, c = 16.2712(6) Å, β = 105.740(4)°, Z = 4 (2). Commonly observed supramolecular amide synthons are not robust enough to accommodate thiocyanate ions and H2O molecules. But instead, neutral complexes are linked through hydrogen bonds leading to two different hydrogen bonding ribbon motifs involving amide moieties and H2O molecules [C(8)R 22 (12) along c axis] and amide moieties and thiocyanate ions [C(8)R 22 (16) along b axis] for symmetrically related molecules labelled as 1 [Co1 (1) and Ni1 (2)] and 2 [Co2 (1) and Ni2 (2)], respectively.

Graphical Abstract

Isomorphous cobalt(II) and nickel(II) complexes with 3-hydroxypicolinamide [Co(NCS)2(3-OHpia)2] and [Ni(NCS)2(3-OHpia)2], crystallize with two symmetrically independent molecules in unit cell. The amide–amide interactions are not robust enough to accommodate usually disruptive thiocyanate ions and H2O molecule, but instead two different hydrogen bonding ribbon motifs involving amide groups are found, C(8)R 22 (12) and C(8)R 22 (16).

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Acknowledgments

The research was supported by Ministry of Science, Education and Sport of the Republic of Croatia, Zagreb (Grant No. 119-1193079-1332).

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Authors and Affiliations

  1. Laboratory of General and Inorganic Chemistry, Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, 10000, Zagreb, Croatia

    Marijana Đaković, Maja Došen & Zora Popović

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  1. Marijana Đaković
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  2. Maja Došen
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  3. Zora Popović
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Correspondence to Marijana Đaković or Zora Popović.

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Đaković, M., Došen, M. & Popović, Z. Self-Assembly of Two Isomorphous Thiocyanate Complexes of Co(II) and Ni(II) with 3-Hydroxypicolinamide. J Chem Crystallogr 41, 180–185 (2011). https://doi.org/10.1007/s10870-010-9860-1

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  • DOI: https://doi.org/10.1007/s10870-010-9860-1

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