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(Li2Br)2O2 crystallizes in the tetragonal P4/mmm space group. The structure is two-dimensional and consists of one water molecule and one Li2Br sheet oriented in the (0, 0, 1) direction. In the Li2Br sheet, Li is bonded in a linear geometry to two equivalent Br atoms. Both Li–Br bond lengths are 2.36 Å. Br is bonded in a square co-planar geometry to four equivalent Li atoms.
Li2OBr crystallizes in the tetragonal P4/mmm space group. The structure is three-dimensional. Li is bonded in a distorted linear geometry to two equivalent O and four equivalent Br atoms. Both Li–O bond lengths are 2.01 Å. All Li–Br bond lengths are 2.80 Å. O is bonded in a square co-planar geometry to four equivalent Li atoms. Br is bonded in a body-centered cubic geometry to eight equivalent Li atoms.