Syntheses and Characterization of a Series of Silver−Thioantimonates(III) and Thioarsenates(III) Containing Two Types of Silver−Sulfur Chains

Three framework silver−thioantimonates, K₃Ag₉Sb₄S₁₂(1), Rb₃Ag₉Sb₄S₁₂(2), and Cs₃Ag₉Sb₄S₁₂(3), and one layered silver−thioarsenate, CsAg₂AsS₃(4), have been synthesized solvothermally in the presence of thiophenol as a mineralizer. Compounds 1, 2, and 3 are isostructural and contain infinite silver−sulfur chains [Ag₉S₁₂]¹⁵⁻. These chains are connected to one another by the antimony atoms to generate wide channels along the [001] direction where the alkali metal cations reside. The structure of 4 consists of helical chains [Ag₂S₃]⁴⁻ linked by the arsenic atoms to form layers with potassium ions between the layers.