@misc{KniesKaiserLeAnhetal., author = {Knies, Maximilian and Kaiser, Martin and L{\^e} Anh, Mai and Efimova, Anastasia and Doert, Thomas and Ruck, Michael}, title = {Low-Temperature Ordering in the Cluster Compound (Bi₈)Tl[AlCl₄]₃}, series = {Inorganics}, volume = {7}, journal = {Inorganics}, number = {4}, doi = {10.3390/inorganics7040045}, pages = {1 -- 9}, abstract = {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.}, language = {en} }