Crystal structure, solid-state 13C and 15N NMR characterisation, chemisorption activity and thermal behaviour of new mercury(II) dipropyldithiocarbamate: Binuclear, pseudo-binuclear and heteronuclear complexes of [Hg2(PrDtc)4], [Hg(PrDtc)2]2 and [Au(PrDtc)2]2[Hg2Cl6]

Tatyana A. Rodina, Olga V. Loseva, Anton I. Smolentsev, Oleg N. Antzutkin, Alexander V. Ivanov

Research output: Contribution to journalArticle

Abstract

Two polymorphs of a new mercury(II) N,N-dipropyldithiocarbamate represented by centrosymmetric binuclear and pseudo-binuclear molecules, [Hg2(PrDtc)4] (1) and [Hg(PrDtc)2]2 (2), have been isolated, identified using heteronuclear (13C, 15N) CP-MAS NMR and structurally characterised by single-crystal X-ray diffraction analysis. There are two pairs of inequivalent PrDtc ligands playing either terminal chelating or tridentate bridging structural functions in the former compound; while the latter complex comprises two pairs of structurally inequivalent chelating PrDtc ligands. The reaction of freshly precipitated mercury(II) N,N-dipropyldithiocarbamate (HgPrDtc) with a [AuCl4]/2 M HCl solution results in the formation of the ionic complex [Au(PrDtc)2]2[Hg2Cl6] (3). There are two inequivalent centrosymmetric cations, [Au(PrDtc)2]+ (‘A’ and ‘B’), and a binuclear centrosymmetric anion, [Hg2Cl6]2− in the structure of 3. In the cationic part of the complex, each of the gold(III) cations has two pairs of the relatively weak inequivalent secondary Au···S bonds with two neighbours, therefore forming linear supramolecular cationic chains (⋯‘A’⋯‘B’⋯‘A’⋯‘B’⋯)n. To study the thermal behaviour of the compounds, simultaneous thermal analysis was also performed. The formation of HgS and reduced elemental gold was established during the thermolysis of 1/2 and 3, respectively.

Original languageEnglish
Article number119630
Number of pages11
JournalInorganica Chimica Acta
Volume508
DOIs
Publication statusPublished - 1 Aug 2020

Keywords

  • Chemisorption activity
  • Heteronuclear (C, N) CP-MAS NMR spectroscopy
  • Ionic double gold(III)-mercury(II) compound
  • Mercury(II) dipropyldithiocarbamate's binuclear and pseudo-binuclear polymorphs
  • Secondary (Hg⋯S, Au⋯S) interactions
  • Thermal behavior
  • CENTER-DOT-S
  • MOLECULAR-STRUCTURE
  • CHEMICAL-SHIFTS
  • X-RAY-DIFFRACTION
  • HG(II) COMPLEXES
  • SELF-ORGANIZATION
  • Secondary (Hg center dot center dot center dot S, Au center dot center dot center dot S) interactions
  • SUPRAMOLECULAR STRUCTURE
  • Heteronuclear (C-13, N-15) CP-MAS NMR spectroscopy
  • CP/MAS C-13
  • CYCLIC DITHIOCARBAMATE LIGANDS
  • MAS NMR

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