Effect of the counter-ion on the structures of tetraphenylantimony(V)–stibonium compounds: crystal and molecular structures of tetraphenylantimony(V) bromide, perchlorate, and tetraphenylborate

Abstract
Crystals of Ph4SbBr are monoclinic, a= 16.293(3), b= 10.616(3), c= 12.507(2)Å, β= 105.60(1)°, space group P21/n. The structure consists of trigonal bipyramidal molecules in which the apical Sb–Br bond is very long [2.965(1)Å]: the apical and mean equatorial Sb–C distances are 2.151(9) and 2.102(9)Å, respectively. The perchlorate [tetragonal, a= 12.670(2), c= 6.711(2)Å, space group /] crystallises with isolated ions of almost perfect tetrahedral local symmetry; in the cation, the Sb–C distance is 2.095(2)Å. The structures of a range of tetraphenylantimony(V) derivatives Ph4SbX are discussed in terms of the basicity/nucleophilicity of X. Crystals of Ph4SbBPh4 are tetragonal, a= 16.272(3), c= 13.703(3)Å, with an I lattice: structure solution was attempted, without success, in all possible space groups. The SbPh4 + and BPh4 ions are scrambled.

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