Synthesis, Supramolecular Self-Organization, and Thermal Behavior of the Double 3D Pseudo-Polymer Complex [Au{S2CN(CH2)6}2]4[Ag5Cl9] Comprising the New Type Silver(I) Anion

Мұқаба

Дәйексөз келтіру

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Ашық рұқсат Ашық рұқсат
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Аннотация

New crystalline pseudo-polymer complex [Au{S2CN(CH2)6}2]4[Ag5Cl9] (I) was prepared by inding gold(III) with silver(I) dithiocarbamate from an AuCl3/2.5 M NaCl solution. Complex I is isolated in a preparative yield and structurally characterized. The X-ray diffraction (XRD) data (CIF file CCDC no. 2205197) show that the isomeric cations [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 leading to 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.

Толық мәтін

Рұқсат жабық

Авторлар туралы

E. Korneeva

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

Email: alexander.v.ivanov@chemist.com
Ресей, Blagoveshchensk

O. Loseva

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

Email: alexander.v.ivanov@chemist.com
Ресей, Blagoveshchensk

A. Smolentsev

Nikolaev Institute of Inorganic Chemistry, Siberian Branch

Email: alexander.v.ivanov@chemist.com
Ресей, Novosibirsk

A. Ivanov

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

Хат алмасуға жауапты Автор.
Email: alexander.v.ivanov@chemist.com
Ресей, Blagoveshchensk

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2. Fig. 1. Size, particle shape, and energy dispersive spectra of the complexes of [Ag(S2CNHm)] (a) and [Au(S2CNHm)2]4[Ag5Cl9] (b).

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3. Fig. 2. Packing of structural units in crystal I (projection on the xz plane), hydrogen atoms of CH2-groups are omitted for clarity. Alternative positions of Ag(3) and Cl(5) atoms in the composition of [Ag5Cl9]4- anions are not shown.

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4. Fig. 3. Structure of three non-equivalent complex cations of the composition [Au(S2CNHm)2]+ (a-c) and the pentanuclear anion [Ag5Cl9]4- (d); ellipsoids of 50% probability. Uncoloured ellipsoids show alternative positions of Ag(3) and Cl(5) atoms. Symmetric transformations: a2 - x, 1 - y, 1 - z; b1 - x, 2 - y, 1 - z; c2 - x, 1 - y, -z.

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5. Fig. 4. Fragment of the supramolecular ribbon in structure I formed due to secondary Ag---S, Cl---S and Cl---Cl interactions between silver(I) anions and isomeric Au3+ B cations (shown by dashed lines). Symmetric transformations: b1 - x, 1 - y, 1 - z; c2 - x, 1 - y, -z; d1 + x, y, -1 + z.

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6. Fig. 5. Fragment of 2D coordination grid: unification of supramolecular ribbons by isomeric A cations due to pairwise secondary Cl---S interactions (shown by dashed lines). Symmetric transformations: a2 - x, 1 - y, 1 - z; b1 + x, y, -1 + z; c3 - x, 1 - y, -z.

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7. Fig. 6. Spatial orientation of isomeric gold C cations upon binding of neighbouring pseudopolymer layers into a 3D framework. Anagostic C-H∙∙∙∙∙Ag interactions and C-H∙∙∙∙∙Cl hydrogen bonds between silver(I) anions and gold(III) C and B cations (shown as dashed lines). Symmetric transformations: a2 - x, 1 - y, 1 - z; b1 - x, 1 - y, 1 - z; c2 - x, 1 - y, -z; d1 + x, y, -1 + z; ex, y, -1 + z; fx, -1 + y, z.

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8. Fig. 7. TG (a) and DSC (b) curves of complex I. Photograph of the bottom of the crucible after completion of thermolysis (c).

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