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SBr crystallizes in the orthorhombic Aea2 space group. The structure is zero-dimensional and consists of four disulphur dibromide molecules. S is bonded in a water-like geometry to one S and one Br atom. The S–S bond length is 1.93 Å. The S–Br bond length is 2.29 Å. Br is bonded in a single-bond geometry to one S atom.
(S)2SBr crystallizes in the tetragonal I4/mmm space group. The structure is two-dimensional and consists of two S sheets oriented in the (0, 0, 1) direction and two SBr sheets oriented in the (0, 0, 1) direction. In each S sheet, S+1.67- is bonded in a square co-planar geometry to four equivalent S+1.67- atoms. All S–S bond lengths are 2.50 Å. In each SBr sheet, S+1.67- is bonded in a square co-planar geometry to four equivalent Br5+ atoms. All S–Br bond lengths are 2.50 Å. Br5+ is bonded in a square co-planar geometry to four equivalent S+1.67- atoms.