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

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.