Reactions of [BiBr₆]³⁻ and bromide salts of various substituted pyridinium cations in excess of HBr result in a series of bromobismuthate anionic complexes of various geometry and nuclearity: [{BiBr₄}_n]ⁿ⁻, [Bi₂Br₉]³⁻ and [Bi₂Br₁₀]⁴⁻. Hirshfeld surface analysis for 19 crystal structure was performed; impact of various X-Br contacts on the crystal structures is discussed.