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Published on: October 6, 2023
Isostructural Inorganic-Organic Piperazine-1,4-diium Chlorido- and Bromidoantimonate(III) Monohydrates: Octahedral
1Faculty of Chemistry, University of Opole, Oleska 48, 45-052 Opole, Poland.
Abstract:
Halogenidoantimonate(III) monohydrates of the (C4H12N2)[SbX5]·H2O (X = Cl, 1 or Br, 2) formula, crystallizing in the same monoclinic space group of P21/n, are isostructural, with an isostructurality index close to 99%. The single crystal X-ray diffraction data do not show any indication of phase transition in cooling these crystals from room temperature to 85 K. Both hybrid crystals are built up from [SbX6]3- octahedra that are joined together by a common edge forming isolated bioctahedral [Sb2X10]4- units, piperazine-1,4-diium (C4H12N2)2+ cations and water of crystallization molecules. These structural components are joined together by related but somewhat different O/N/C-H···X and N-H···O hydrogen bonded systems. The evolution of structural parameters, notably the secondary Sb-X bonds along with the associated X/Sb-Sb/X-X/Sb angles and O/N/C-H···X hydrogen bonds, as a function of ligand exchange and temperature, along with their influence on the irregularity of [SbX6]3- octahedra, was determined. The comparison of packing features and hydrogen bond parameters, additionally supported by the Hirshfeld surface analysis and data retrieved from the Cambridge Structural Database, demonstrates the hierarchy and importance of hydrogen bond interactions that influence the irregularity of single [SbX6]3- units.
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