Li5O2Br3 crystallizes in the tetragonal I-4m2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted linear geometry to two equivalent O(1) and four equivalent Br(1) atoms. In the second Li site, Li(2) is bonded to one O(1) and five equivalent Br(2) atoms to form a mixture of distorted corner and edge-sharing LiBr5O octahedra. The corner-sharing octahedral tilt angles are 2°. In the third Li site, Li(3) is bonded in a distorted linear geometry to two equivalent O(1), two equivalent Br(1), and two equivalent Br(2) atoms. O(1) is bonded in a square co-planar geometry to one Li(1), one Li(2), and two equivalent Li(3) atoms. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded to four equivalent Li(1) and four equivalent Li(3) atoms to form distorted BrLi8 hexagonal bipyramids that share corners with four equivalent Br(1)Li8 hexagonal bipyramids, corners with four equivalent Br(2)Li7 pentagonal bipyramids, edges with two equivalent Br(2)Li7 pentagonal bipyramids, and faces with four equivalent Br(1)Li8 hexagonal bipyramids. In the second Br site, Br(2) is bonded to two equivalent Li(3) and five equivalent Li(2) atoms to form distorted BrLi7 pentagonal bipyramids that share corners with two equivalent Br(1)Li8 hexagonal bipyramids, corners with four equivalent Br(2)Li7 pentagonal bipyramids,  an edgeedge with one Br(1)Li8 hexagonal bipyramid, edges with six equivalent Br(2)Li7 pentagonal bipyramids, and faces with two equivalent Br(2)Li7 pentagonal bipyramids.
Li5O2Br3 crystallizes in the tetragonal I-4m2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted linear geometry to two equivalent O(1) and four equivalent Br(1) atoms. Both Li(1)-O(1) bond lengths are 2.00 Å. All Li(1)-Br(1) bond lengths are 2.81 Å. In the second Li site, Li(2) is bonded to one O(1) and five equivalent Br(2) atoms to form a mixture of distorted corner and edge-sharing LiBr5O octahedra. The corner-sharing octahedral tilt angles are 2°. The Li(2)-O(1) bond length is 1.97 Å. There is one shorter (2.72 Å) and four longer (2.81 Å) Li(2)-Br(2) bond lengths. In the third Li site, Li(3) is bonded in a distorted linear geometry to two equivalent O(1), two equivalent Br(1), and two equivalent Br(2) atoms. Both Li(3)-O(1) bond lengths are 1.98 Å. Both Li(3)-Br(1) bond lengths are 2.81 Å. Both Li(3)-Br(2) bond lengths are 2.83 Å. O(1) is bonded in a square co-planar geometry to one Li(1), one Li(2), and two equivalent Li(3) atoms. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded to four equivalent Li(1) and four equivalent Li(3) atoms to form distorted BrLi8 hexagonal bipyramids that share corners with four equivalent Br(1)Li8 hexagonal bipyramids, corners with four equivalent Br(2)Li7 pentagonal bipyramids, edges with two equivalent Br(2)Li7 pentagonal bipyramids, and faces with four equivalent Br(1)Li8 hexagonal bipyramids. In the second Br site, Br(2) is bonded to two equivalent Li(3) and five equivalent Li(2) atoms to form distorted BrLi7 pentagonal bipyramids that share corners with two equivalent Br(1)Li8 hexagonal bipyramids, corners with four equivalent Br(2)Li7 pentagonal bipyramids,  an edgeedge with one Br(1)Li8 hexagonal bipyramid, edges with six equivalent Br(2)Li7 pentagonal bipyramids, and faces with two equivalent Br(2)Li7 pentagonal bipyramids.