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Synthesis, Supramolecular Self-Organization, and Thermal Behavior of the Double Three-Dimensional Pseudo-Polymer Complex [Au{S2CN(CH2)6}2]4[Ag5Cl9] Comprising the New Type Silver(I) Anion

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Abstract

New crystalline pseudo-polymer complex [Au{S2CN(CH2)6}2]4[Ag5Cl9] (I) was obtained by binding gold(III) with silver(I) hexamethylenedithiocarbamate from an AuCl3/2.5 M NaCl solution. Complex I was isolated in a preparative yield and structurally characterized. The X-ray diffraction (XRD) data (CIF file CCDC no. 2205197) show that the isomeric cations of [Au{S2CN(CH2)6}2]+ (A : 2B : C) and complicated pentanuclear anion [Ag5Cl9]4– are the main structural units of the compound. The supramolecular self-organization of the ionic structural units in complex I occurs due to multiple secondary interactions Cl···S and Ag···S, hydrogen bonds C–H···Cl, and anagostic interactions C–H···Ag, resulting in the formation of the 3D pseudo-polymer framework. The thermal behavior of complex I is studied by simultaneous thermal analysis to find that the thermolysis of the double Au(III)–Ag(I) compound is accompanied by the quantitative regeneration of the bound metals under comparatively mild conditions.

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Notes

  1. The solvated form of the hexanuclear silver(I) cluster [Ag6(HmDtc)6]·2CH2Cl2 was earlier prepared by the recrystallization of the complex from a dichloromethane solution and structurally characterized [20].

  2. The methodical approaches [36], which made it possible to determine the 81% contribution of the tetrahedral component to the geometry of the [AgCl4] polyhedra were used for the quantitative characterization of the Ag(1) and Ag(1)c polyhedra.

  3. The concept of secondary bonds was proposed for the description of nonvalent type interactions between atoms at the distances comparable with the sum of their van der Waals radii [37].

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ACKNOWLEDGMENTS

Elemental analysis and IR spectroscopy were carried out using the equipment of the Center for Collective Use of Physical Methods of Investigation at the Kurnakov Institute of General and Inorganic Chemistry (Russian Academy of Sciences). Electron microscopy, X-ray spectral studies, and determination of the gold content in solutions were carried out at the Center for Collective Use “Amur Center of Mineralogical and Geochemical Studies” of the Institute of Geology and Nature Management (Far Eastern Branch, Russian Academy of Sciences).

Funding

This work was supported by ongoing institutional funding. No additional grants to carry out or direct this particular research were obtained.

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Authors and Affiliations

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

    E. V. Korneeva, O. V. Loseva & A. V. Ivanov

  2. Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Novosibirsk, Russia

    A. I. Smolentsev

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  1. E. V. Korneeva
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  2. O. V. Loseva
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  3. A. I. Smolentsev
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  4. A. V. Ivanov
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Correspondence to A. V. Ivanov.

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Translated by E. Yablonskaya

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Korneeva, E.V., Loseva, O.V., Smolentsev, A.I. et al. Synthesis, Supramolecular Self-Organization, and Thermal Behavior of the Double Three-Dimensional Pseudo-Polymer Complex [Au{S2CN(CH2)6}2]4[Ag5Cl9] Comprising the New Type Silver(I) Anion. Russ J Coord Chem 50, 21–32 (2024). https://doi.org/10.1134/S1070328423600572

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