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Low-Temperature Ordering in the Cluster Compound (Bi8)Tl[AlCl4]3

1
Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, D-01069 Dresden, Germany
2
Chair of Inorganic Chemistry, Brandenburg University of Technology Cottbus-Senftenberg, Universitätsplatz 1, D-01968 Senftenberg, Germany
3
Max Planck Institute for Chemical Physics of Solids, Nöthnitzer Str. 40, D-01187 Dresden, Germany
*
Author to whom correspondence should be addressed.
Inorganics 2019, 7(4), 45; https://doi.org/10.3390/inorganics7040045
Received: 25 February 2019 / Revised: 18 March 2019 / Accepted: 18 March 2019 / Published: 27 March 2019
(This article belongs to the Special Issue Structure, Properties, and Bonding in Solid State Compounds)
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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 ( AlCl 4 ) 3 ] 1 2 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. View Full-Text
Keywords: bismuth; cluster compounds; hexagonal perovskite; ionic liquids; low-valent compounds; order–disorder transition; orientational disorder; polycations; pseudosymmetry bismuth; cluster compounds; hexagonal perovskite; ionic liquids; low-valent compounds; order–disorder transition; orientational disorder; polycations; pseudosymmetry
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Knies, M.; Kaiser, M.; Lê Anh, M.; Efimova, A.; Doert, T.; Ruck, M. Low-Temperature Ordering in the Cluster Compound (Bi8)Tl[AlCl4]3. Inorganics 2019, 7, 45.

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