Abstract: | The Novel cis‐[Bi3I12]3?‐Anion in Tri(n‐butyl)methylammoniumdodecaiodo‐tribismutate By reaction of equivalent amounts of BiI3, KI and I2 in [N(CH3) (n‐C4H9)3][N(SO2CF3)2] as Ionic Liquid, transparent reddish crystals with the composition [N(CH3)(n‐C4H9)3]3[Bi3I12] are formed. Concerning to X‐ray diffraction investigations based on single crystals as well as powders, [N(CH3)(n‐C4H9)3]3[Bi3I12] crystallizes monoclinic (P21/c; a = 2383.0(5); b = 1241.0(3); c = 2493.0(5) pm; β = 97.50(3)°; Z = 4). The anion consists of distorted (BiI6)‐octahedra, which are face‐shared via cis‐oriented octahedral faces. With the cis‐[Bi3I12]3?‐anion such a connectivity is firstly described. |