In the reactions between the mononuclear [SbBr ₆ ] ^3- species, Br ₂ and various {cationBr} salts, Sb(iii) is commonly oxidized to Sb(v), and the cations play a key role in the formation of the particular bromoantimonate or polybromide-bromoantimonate frameworks of different dimensionalities (1D, 2D or even 3D). Screening this system yielded eleven novel compounds belonging to both the known and the novel structural types. The role of Br⋯Br halogen bonding was studied by DFT calculations, resulting in the estimation of its bond energy (1.1-2.9 kcal mol ^-1 ).