The crystal and molecular structures of compounds (Cat>2[Cd 4^-SPh) 6 Cl 4 ] (Cat = Et^N^.l; Pr^N 4 ". 2; Bu^N", 3) have been determined by single crystal X-ray (Effraction techniques to study the influence of the cations on the stereochemistry and configurational isomerism of the [Cd 4^-SPh) 6 Cl 4 ] 2 " anions. The results of our investigation show that the cations have profound effect on the crystal and molecular structures including the orientation of phenyl rings along the S-C axes, but do not change the configuration of the substituents, i.e., the phenyl rings of the thiolate ligands. In each anion, the configuration (axial or equatorial) of the phenyl groups in the four six-membered rings is [aae, aae, aee, aee], corresponding to isomer III.
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