Ionothermal Synthesis of Sulfidobismuth spiro-Dicubane Cations

Bi2S3 was dissolved in the presence of NaCl in the ionic liquid [BMIm]Cl ⋅ 4AlCl3 (BMIm=1-n-butyl-3-methylimidazolium) through annealing the mixture at 180 °C. Upon cooling to room temperature, orange, air-sensitive crystals of Na(Bi7S8)[S(AlCl3)3]2[AlCl4]2 (1) precipitated. X-ray diffraction on single-crystals of 1 revealed a triclinic crystal structure that contains (Bi7S8)5+ spiro-dicubanes, [S(AlCl3)3]2− tetrahedra triples, isolated [AlCl4]− tetrahedra, and sodium cations. © 2021 The Authors. Published by Wiley-VCH Gmb