Multiple isomerization of structural units in ion-polymeric heteronuclear gold(III)–zinc(II) complex ([Au{S2CN(C4H9)2}2]2[ZnCl4])n: Chemisorption-based synthesis, supramolecular structure (self-organization of long-period cation–cationic polymer ... View Full Text


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Article Info

DATE

2017-08

AUTHORS

A. V. Ivanov, O. V. Loseva, T. A. Rodina, A. I. Smolentsev

ABSTRACT

Chemisorption of gold(III) from solutions in 2 M HCl with freshly precipitated binuclear zinc dithiocarbamate [Zn2{S2CN(C4H9)2}4] resulted in the formation of a polymeric heteronuclear gold(III)–zinc(II) dithiocarbamato-chlorido complex ([Au{S2CN(C4H9)2}2]2[ZnCl4])n (I), which was characterized by MAS 13C NMR, X-ray diffraction (CIF file CCDC no. 1526616), and simultaneous thermal analysis. Compound I isolated on a preparative scale was found to have a highly intricate supramolecular structure composed of 13 centrosymmetric and non-centrosymmetric isomeric complex cations, [Au{S2CN(C4H9)2}2]+, with 24 structurally non-equivalent BuDtc ligands, and six isomeric [ZnCl4]2– anions. The isomeric gold(III) cations perform different structural functions. Four and six cations are involved in the formation of two sorts of long-period cation–cationic chains (via pair non-valence secondary Au···S bonds): (···A···B···C···D···C···B···)n and (···F···G···H···I···J···K···)n. The discrete E, L, and M cations and the [ZnCl4]2– complex anions are located alongside of the polymer chains and do not take part in the secondary interactions. According to simultaneous thermal analysis, thermolysis of I includes destruction of the dithiocarbamate moiety with reduction of gold to the metal in the cation and liberation of zinc chloride with partial conversion to ZnS in the anion. More... »

PAGES

512-525

References to SciGraph publications

  • 2014-08. Structural organization and thermal behavior of the heteropolynuclear complex [Au2{S2CN(CH3)2}4][ZnCl4] and the heterovalent complex ([Au{S2CN(CH3)2}2][AuCl2])n obtained in the chemisorption system [Zn2{S2CN(CH3)2}4]-Au3+/2 M HCl in RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
  • 2005. Natural Abundance 15N and 13C CP/MAS NMR of Dialkyldithiocarbamate Compounds with Ni(II) and Zn(II) in NEW TECHNIQUES IN SOLID-STATE NMR
  • 2016-01. Preparation, structural organization, and thermal behavior of the ion-polymeric gold(III)–zinc(II)–dibutylammonium complex ([NH2(C4H9)2][Au{S2CN(C4H9)2}2][ZnCl4)]n in JOURNAL OF STRUCTURAL CHEMISTRY
  • 2014-12. Interaction of binuclear zinc diethyldithiocarbamate with H[AuCl4]/2 M HCl: The preparation, supramolecular self-organization, and thermal behavior of the heteropolynuclear complex ([Au{S2CN(C2H5)2}2]2[ZnCl4] · 1/2CO(CH3)2 · 1/2CHCl3)n in RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
  • 2014-12. Polymeric complexes ([Au{S2CN(CH2)4O}2]2[ZnCl4] · 2H2O)n and ([Au{S2CN(CH2)4O}2]Cl · 2H2O)n as individual gold(III)-binding forms in the [Zn2{S2CN(CH2)4O}4]n-[AuCl4]−/2M HCl chemisorption system: Supramolecular self-organization and thermal behavior in RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
  • 2005-10. Structural Organization of Nickel(II), Zinc(II), and Copper(II) Complexes with Diisobutyldithiocarbamate: EPR, 13C and 15N CP/MAS NMR, and X-Ray Diffraction Studies in RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
  • 2014-09. Synthesis, supramolecular self-organization, and thermal behavior of the heteropolynuclear complex ([H3O][Au{S2CN(CH2)6}2][Au2{S2CN(CH2)6}4][ZnCl4]2)n in JOURNAL OF STRUCTURAL CHEMISTRY
  • 2013-06. A fixation mode of gold(III) in the [Zn2{S2CN(iso-C3H7)2}4]-[AuCl4]−/2 M HCl chemisorption system: Supramolecular structure and thermal behavior of the heteropolynuclear complex ([H3O][Au3{S2CN(iso-C3H7)2}6][ZnCl4]2 · H2O)n in RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
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    41 schema:description Chemisorption of gold(III) from solutions in 2 M HCl with freshly precipitated binuclear zinc dithiocarbamate [Zn2{S2CN(C4H9)2}4] resulted in the formation of a polymeric heteronuclear gold(III)–zinc(II) dithiocarbamato-chlorido complex ([Au{S2CN(C4H9)2}2]2[ZnCl4])n (I), which was characterized by MAS 13C NMR, X-ray diffraction (CIF file CCDC no. 1526616), and simultaneous thermal analysis. Compound I isolated on a preparative scale was found to have a highly intricate supramolecular structure composed of 13 centrosymmetric and non-centrosymmetric isomeric complex cations, [Au{S2CN(C4H9)2}2]+, with 24 structurally non-equivalent BuDtc ligands, and six isomeric [ZnCl4]2– anions. The isomeric gold(III) cations perform different structural functions. Four and six cations are involved in the formation of two sorts of long-period cation–cationic chains (via pair non-valence secondary Au···S bonds): (···A···B···C···D···C···B···)n and (···F···G···H···I···J···K···)n. The discrete E, L, and M cations and the [ZnCl4]2– complex anions are located alongside of the polymer chains and do not take part in the secondary interactions. According to simultaneous thermal analysis, thermolysis of I includes destruction of the dithiocarbamate moiety with reduction of gold to the metal in the cation and liberation of zinc chloride with partial conversion to ZnS in the anion.
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