Abstract: | (Acetonitrile‐1κN)μ‐1H‐benzimidazole‐2(3H)‐thione‐1:2κ2S:S]1H‐benzimidazole‐2(3H)‐thione‐2κS]bis(μ‐1,1‐dioxo‐1λ6,2‐benzothiazole‐3‐thiolato)‐1:2κ2S3:N;1:2κ2S3:S3‐dicopper(I)(Cu—Cu), Cu2(C7H4NO2S2)2(C7H6N2S)2(CH3CN)] or Cu2(tsac)2(Sbim)2(CH3CN)] tsac is thiosaccharinate and Sbim is 1H‐benzimidazole‐2(3H)‐thione], (I), is a new copper(I) compound that consists of a triply bridged dinuclear Cu—Cu unit. In the complex molecule, two tsac anions and one neutral Sbim ligand bind the metals. One anion bridges via the endocyclic N and exocyclic S atoms (μ‐S:N). The other anion and one of the mercaptobenzimidazole molecules bridge the metals through their exocyclic S atoms (μ‐S:S). The second Sbim ligand coordinates in a monodentate fashion (κS) to one Cu atom, while an acetonitrile molecule coordinates to the other Cu atom. The CuI—CuI distance 2.6286 (6) Å] can be considered a strong `cuprophilic' interaction. In the case of μ‐1H‐benzimidazole‐2(3H)‐thione‐1:2κ2S:S]bis1H‐benzimidazole‐2(3H)‐thione]‐1κS;2κS‐bis(μ‐1,1‐dioxo‐1λ6,2‐benzothiazole‐3‐thiolato)‐1:2κ2S3:N;1:2κ2S3:S3‐dicopper(I)(Cu—Cu), Cu2(C7H4NO2S2)2(C7H6N2S)3] or Cu2(tsac)2(Sbim)3], (II), the acetonitrile molecule is substituted by an additional Sbim ligand, which binds one Cu atom via the exocylic S atom. In this case, the CuI—CuI distance is 2.6068 (11) Å. |