Synthesis and molecular structure of the adduct trichlorobismuth–1,4,7,10,13,16-hexathiacyclooctadecane (1/1)

Abstract

The reaction (1:1) of BiCl3 and [18]aneS6 in acetonitrile provides colourless crystals of the adduct BiCl3·[18]aneS6. An X-ray crystal structure determination has revealed a BiCl3 pyramidal unit bonded to all six sulfur atoms of the macrocyclic ring which adopts an unusual S-shaped conformation. The bismuth atom sits on a crystallographically imposed three-fold axis in a nine-co-ordinate [3:3:3] geometrical arrangement involving two sets of three sulfur atoms and the three chlorine atoms respectively. Crystals are cubic, space group Pa3 with Z= 8 and a= 16.381(5)A 1312 independent reflections were measured of which 825 with [I/σ(I) 2.0] were used in the final refinement, R= 0.044 (R′= 0.067), Bi–S 3.146(4) and 3.225(4)A, Bi–Cl 2.607(4)A and Cl–Bi–Cl 89.0(1)°.