Bromoantimonate(III) species, which can be generated in solution by reaction of Sb₂O₃ and HBr, can be oxidized by Br₂ into mixed-valence complexes or bromoantimonates(V). The outcome of these reactions governs by the nature of cation which salt is used for isolation of solid complexes. Using bromides of three 1,n-bis(pyridinium)alkane cations (PyC_n, where X = 2, 3 and 4), we isolated three complexes: (PyC₂){[SbBr₆](Br₃)} (1), (PyC₃)₂[Sb₂Br₉][SbBr₆] (2) and (PyC₄){[SbBr₆](Br₃)} (3), respectively. Their structures were determined by X-ray diffractometry. For 1 and 3, the energies of non-covalent interactions between tribromide units and [SbBr₆]⁻ were estimated using DFT calculations.