The tetranuclear macrocyclic mercury(II) complex of [Hg4{S2CN(CH3)2}4Cl4]: preparation, molecular and supramolecular structures, and thermal behavior

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The tetranuclear mercury(II) dithiocarbamato-chlorido complex [Hg4(S2CNMe2)4Cl4] (I), the molecule of which includes a 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 by direct single crystal X-ray diffraction (CCDC no. 2364847). In complex I, the non-equivalent μ2-bridging dithiocarbamate ligands join 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.

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作者简介

O. Loseva

Institute of Geology and Nature Management, Far Eastern Branch, Russian Academy of Sciences

Email: alexander.v.ivanov@chemist.com
俄罗斯联邦, Blagoveshchensk, 675000

T. Rodina

Amur State University

Email: alexander.v.ivanov@chemist.com
俄罗斯联邦, Blagoveshchensk, 675027

A. Smolentsev

Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences

Email: alexander.v.ivanov@chemist.com
俄罗斯联邦, Novosibirsk, 630090

S. Zinchenko

Favorsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences

Email: alexander.v.ivanov@chemist.com
俄罗斯联邦, Irkutsk, 664033

A. Ivanov

Institute of Geology and Nature Management, Far Eastern Branch, Russian Academy of Sciences

编辑信件的主要联系方式.
Email: alexander.v.ivanov@chemist.com
俄罗斯联邦, Blagoveshchensk, 675000

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2. Fig. 1. Tetranuclear macrocyclic molecule [Hg4{S2CN(CH3)2}4Cl4]. Ellipsoids 50% probability.

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3. Fig. 2. Spatial configuration of the 16-membered metallocycle [Hg4S8C4] in the tetranuclear molecule I.

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4. Fig. 3. Fragment of the 2D pseudopolymer layer in structure I. The secondary bonds S Cl and Hg Cl are shown by the dotted line. Alkyl substituents are not shown. Symmetric transformations: a 1 – x, 1 – y, 1 – z; b –½ + x, ½ – y, –½ + z.

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5. Fig. 4. Hydrogen bonds in the supramolecular pseudopolymer 3D framework I.

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6. Fig. 5. TG (a) and DSC (b) curves of complex I.

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7. Fig. 6. TG (a) and DSC (b) curves of the mononuclear mercury(II) complex [Hg{S2CN(CH3)2}2].

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8. Supplementary Material
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