Ionothermal Synthesis of Sulfidobismuth spiro ‐Dicubane Cations

Bi 2 S 3 was dissolved in the presence of NaCl in the ionic liquid [BMIm]Cl ⋅ 4AlCl 3 (BMIm=1‐ n ‐butyl‐3‐methylimidazolium) through annealing the mixture at 180 °C. Upon cooling to room temperature, orange, air‐sensitive crystals of Na(Bi 7 S 8 )[S(AlCl 3 ) 3 ] 2 [AlCl 4 ] 2 ( 1 ) precipitated. X‐ray diffraction on single‐crystals of 1 revealed a triclinic crystal structure that contains (Bi 7 S 8 ) 5+ spiro ‐dicubanes, [S(AlCl 3 ) 3 ] 2− tetrahedra triples, isolated [AlCl 4 ] − tetrahedra, and sodium cations.