Several polyhalide anions containing iodine and bromine have been synthesized with 2,2′- bipyridylium (BPH+) as the cation. The crystal structures of three compounds have been investigated by X-ray crystal structure analyses. BPH+(H3O)+(IBr2)2- (P1̄, a = 780.0(3), b = 815.4(3), c = 1547.9(6) pm, α = 75.59(7), β = 82.28(8), γ = 88.15(8)°, R = 6.5%) contains two independent, nearly linear, asymmetric IBr2- groups. In BPH+I2Br3- (P21/c, a = 1269.1(6), b = 673.0(4), c = 2047.4(8) pm, β = 112.39(9)°, R = 6.3%), the anion is V-shaped like other pentahalide anions. It can be characterized as consisting of two IBr molecules linked to a bromide anion with the longer I-Br bonds at the central atom. The polyhalide anions in [xxx] (P21/m, a = 435.1(2), b = 1710.6(7), c = 1349.0(6) pm, β = 97.56(9)°, R = 15.5%) form infinite zigzag layers. They are built up by IBr2- anions which are connected by iodine molecules. The cations are enclosed in columnar cavities within these layers

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Die Kristallstrukturen der Polyhalogenide (III), (V) und (VII) (keine Ausb.‐Angaben) werden durch Röntgen‐Strukturanalyse aufgeklärt.