Structures of Bromine Oxygen Compounds

The crystal structures of Br 2 O, BrO 2 F, and O 2 BrOTeF 5 are reported. Br 2 O is prepared in a novel manner from BrOTeF 5 and H 2 O, and obtained pure as a yellow brown crystalline solid. The single crystal structure determination a = 390.4(1), b = 686.2(1), c = 1062.2(2) pm, space group Pc2 1 n (No. 33), Z = 4) reveals bent 114.2(2)° BrOBr molecules that have strong Br … Br interactions in the solid state resulting in a chain. BrO 2 F is prepared in the known manner from KBrO 3 and BrF 5 . It is extremely sensitive towards reduction. Crystals obtained by sublimation are rhomboedric with a sixfold disorder making oxygen and fluorine atoms undistinguishable (a = 051.1(2) pm, α = 47.05(2)°, space group R3c, Z = 2). The BrO 2 F molecular shape is pyramidal with an averaged bond angle of 103.8(3)°. O 2 BrOTeF 5 is prepared by ozonisation of BrOTeF 5 as a colorless solid, mp −20°C. It is fully characterized by vibrational and nmr spetroscopy and a single crystal structure determination (a = 517.40(1), b = 614.00(1), c = 1950.70(1) pm, β= 90.6(1)°, space group P2 1 /c, Z = 4). The molecule has the expected pyramidal geometry at the BrO 3 group.