- The reaction of Bi, BiCl₃, and TlCl in the ionic liquid [BMIm]Cl·4AlCl₃ (BMIm = 1-n-butyl-3-methylimidazolium) at 180 °C yielded air-sensitive black crystals of (Bi₈)Tl[AlCl₄]₃. X-ray diffraction on single crystals at room temperature revealed a structure containing [Tl(AlCl₄)₃]∞12−
strands separated by isolated Bi₈²⁺ square antiprisms. The thallium(I) ion is coordinated by twelve Cl⁻ ions of six [AlCl₄]⁻ groups, resulting in a chain of face-sharing [TlCl₁₂]¹¹⁻ icosahedra. The Bi₈²⁺ polycation is disordered, simulating a threefold axis through its center and overall hexagonal symmetry (space group P6₃/m). Slowly cooling the crystals to 170 K resulted in increased order in the Bi₈ cluster orientations. An ordered structure model in a supercell with a’ = 2a, b’ = 2b, c’ = 3c and the space group P6₅ was refined. The structure resembles a hexagonal perovskite, with complex groups in place of simple ions.