The outcome of reactions of triarylantimony (Ar₃Sb) with diiodine in benzene is strongly affected by the identity of the substituents. For R = 4-MePh, 3-MePh and 4-FPh, they form Sb^Vderivatives Ar₃SbI₂, while for (2-MeO-5-BrC₆H₄)₃Sb the reaction results in [(2-MeO-5-BrC₆H₄)₃SbI](I₃) where I is bound to the Sb center. The features of noncovalent interactions in the structure of the latter compound, as well as the electronic structure of the [(2-MeO-5-BrPh)₃SbI]⁺cation, were studied by theoretical methods.