Reaction of BiI ₃ /CuI or SbI ₃ /CuI mixtures with the cyclic thioalkanes 1,3-dithiolane (DTL) or 1,4,7-trithiacyclononane (9S3) in toluene yielded the compounds BiCu ₃ I ₆ (DTL) ₃ ( 1 ), SbCu ₃ I ₆ (DTL) ₃ ( 2 ), and Bi ₂ Cu ₃ I ₉ (9S3) ₄ ( 3 ). All compounds were characterized via single crystal X-ray structure determination, powder X-ray diffraction, thermogravimetric analysis, elemental analysis, infrared, and diffuse reflectance spectroscopy. In all cases, sulfur centers bond only to Cu(I). Compounds 1 and 2 consist of isostructural 1D linear chain networks consisting of EI ₆ octahedra (E = Bi, Sb) in which three mutually cis edges are capped with Cu(I) centers via μ ₂ -I forming an ECu ₃ I ₆ cluster. All three DTL ligands are bidentate. Two DTL ligands bridge pairs of adjacent copper atoms in the ECu ₃ I ₆ cluster. Bridging by the remaining DTL links the clusters into infinite chains, …[ECu ₃ I ₆ (DTL) ₂ ](DTL)… Compound 3 displays a unique ionic structure, [Cu ₅ (9S3) ₇ ] ⁵⁺ [Bi ₄ CuI ₁₈ (9S3)] ⁵⁻ . The cation is composed of a central 9S3 ligand that bridges disordered duos/trios of [Cu(9S3)] ⁺ units, yielding [Cu _2.5 (9S3) _3.5 ] ^2.5+ . The anion consists of half-independent face-sharing double octahedron, [Bi ₂ I ₉ ] ³⁻ in which one of the trio of μ ₂ -I centers further coordinates a half [Cu(9S3)] ⁺ unit, yielding [Bi ₂ Cu _0.5 I ₉ (9S3) _0.5 ] ^2.5− . Hirshfeld analysis of 1 and 2 shows inter-chain contacts are dominated by I ^… I, H ^… I, S ^… H, and S ^… I interactions. The compounds show bandgaps in the range of 2.0–2.3 eV and thermally decompose sequentially with the loss of thioalkane, EI ₃ , then CuI. Graphical Abstract

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