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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

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Abstract

The interaction of the freshly precipitated binuclear zinc diethyldithiocarbamate (EDtc) [Zn2{S2CN(C2H5)2}4] with a solution of AuCl3 in 2 M HCl was studied. A water-soluble gold(III)-zinc complex was formed as a result of this interaction; it was preparatively isolated as the solvated polymeric species ([Au{S2CN(C2H5)2}2]2[ZnCl4] · 1/2CO(CH3)2 · 1/2CHCl3) n (I). According to single-crystal X-ray diffraction (XRD) analysis data, the resulting compound includes four structurally nonequivalent complex cations [Au{S2CN(C2H5)2}2]+ (with Au(1), Au(2), Au(3), and Au(4) atoms, A-D, respectively) and two [ZnCl4]2− anions (E = Zn(1), F = Zn(2)), which are related to each other as conformers. At the supramolecular level, isomeric cations are characterized by a complex structural ordering mode: complex cations B, C, and D form polymeric chains like (⋯B[⋯A]⋯ D⋯C⋯) n oriented along the crystallographic a axis, in which cation A serves as a side substituent, due to secondary Au⋯S bonds and short contacts between the nearest neighbors. Outer-sphere solvating molecules and isomeric distorted tetrahedral [ZnCl4]2− anions linked to [Au{S2CN(C2H5)2}2]+ cations by secondary Cl⋯S bonds are localized between the chains. The thermal behavior of compound I was studied by simultaneous thermal analysis. The multistage process of thermal decomposition includes the desolvation of the complex and the thermolysis of its dithiocarbamate moiety and [ZnCl4]2− with the release of gold metal and zinc chloride and the partial formation of ZnS. The final products of these thermal transformations are reduced gold and ZnS.

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Authors and Affiliations

  1. Institute of Geology and Nature Management, Far East Branch, Russian Academy of Sciences, Blagoveshchensk, 675000, Russia

    O. V. Loseva & A. V. Ivanov

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  1. O. V. Loseva
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  2. A. V. Ivanov
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Correspondence to A. V. Ivanov.

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Original Russian Text © O.V. Loseva, A.V. Ivanov, 2014, published in Zhurnal Neorganicheskoi Khimii, 2014, Vol. 59, No. 12, pp. 1737–1746.

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Loseva, O.V., Ivanov, A.V. 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 . Russ. J. Inorg. Chem. 59, 1491–1500 (2014). https://doi.org/10.1134/S0036023614120146

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  • DOI: https://doi.org/10.1134/S0036023614120146

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