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Abstract <p>The tetranuclear mercury(II) dithiocarbamatо-chloridо complex [Hg<sub>4</sub>(S<sub>2</sub>CNMe<sub>2</sub>)<sub>4</sub>Cl<sub>4</sub>] (<b>I</b>), whose molecule includes the centrosymmetric 16-membered metallacycle [Hg<sub>4</sub>S<sub>8</sub>C<sub>4</sub>], was prepared by the reaction of solutions of HgCl<sub>2</sub> and sodium dimethyldithiocarbamate (Me<sub>2</sub>Dtc). The crystal, molecular, and supramolecular structures of <b>I</b> were established using direct method of single-crystal X-ray diffraction (CCDC no. 2364847). In complex <b>I</b>, the non-equivalent μ<sub>2</sub>-bridging dithiocarbamate ligands link neighboring mercury atoms in pairs, thus forming a tetranuclear macrocyclic molecule. The intramolecular Hg···S and Hg···Cl secondary bonds stabilize the spatial configuration of this macrometallacycle. The supramolecular self-organization of the complex is due to the relatively weak, pairwise S···Cl and Hg···Cl secondary interactions, which combine the tetranuclear molecules of <b>I</b> into 2D pseudo-polymer layers; numerous non-classical C–H···Cl and C–H···S hydrogen bonds connect these layers to form a 3D framework. According to simultaneous thermal analysis data, the thermal decomposition of <b>I</b> is accompanied by the formation of HgS and release of HgCl<sub>2</sub>.</p>

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The Tetranuclear Macrocyclic Mercury(II) Complex of [Hg4{S2CN(CH3)2}4Cl4]: Preparation, Molecular and Supramolecular Structures, and Thermal Behavior

  • 期刊论文

  • 发表日期：

    2025年1月1日

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  • O. V. Loseva,
  • T. A. Rodina,
  • A. I. Smolentsev,
  • S. V. Zinchenko,
  • A. V. Ivanov

摘要

Abstract

The tetranuclear mercury(II) dithiocarbamatо-chloridо complex [Hg4(S2CNMe2)4Cl4] (I), whose molecule includes the centrosymmetric 16-membered metallacycle [Hg4S8C4], was prepared by the reaction of solutions of HgCl2 and sodium dimethyldithiocarbamate (Me2Dtc). The crystal, molecular, and supramolecular structures of I were established using direct method of single-crystal X-ray diffraction (CCDC no. 2364847). In complex I, the non-equivalent μ2-bridging dithiocarbamate ligands link neighboring mercury atoms in pairs, thus forming a tetranuclear macrocyclic molecule. The intramolecular Hg···S and Hg···Cl secondary bonds stabilize the spatial configuration of this macrometallacycle. The supramolecular self-organization of the complex is due to the relatively weak, pairwise S···Cl and Hg···Cl secondary interactions, which combine the tetranuclear molecules of I into 2D pseudo-polymer layers; numerous non-classical C–H···Cl and C–H···S hydrogen bonds connect these layers to form a 3D framework. According to simultaneous thermal analysis data, the thermal decomposition of I is accompanied by the formation of HgS and release of HgCl2.