Li6PO5Br crystallizes in the cubic F-43m space group. Li(1) is bonded in a trigonal planar geometry to one O(2), two equivalent O(1), and two equivalent Br(1) atoms. P(1) is bonded in a tetrahedral geometry to four equivalent O(1) atoms. There are two inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(1) and one P(1) atom to form OLi3P tetrahedra that share corners with three equivalent O(2)Li6 octahedra, corners with six equivalent O(1)Li3P tetrahedra, and edges with three equivalent Br(1)Li12 cuboctahedra. The corner-sharing octahedral tilt angles are 58°. In the second O site, O(2) is bonded to six equivalent Li(1) atoms to form OLi6 octahedra that share corners with twelve equivalent O(1)Li3P tetrahedra and faces with four equivalent Br(1)Li12 cuboctahedra. Br(1) is bonded to twelve equivalent Li(1) atoms to form BrLi12 cuboctahedra that share corners with twelve equivalent Br(1)Li12 cuboctahedra, edges with twelve equivalent O(1)Li3P tetrahedra, and faces with four equivalent O(2)Li6 octahedra.
Li6PO5Br crystallizes in the cubic F-43m space group. Li(1) is bonded in a trigonal planar geometry to one O(2), two equivalent O(1), and two equivalent Br(1) atoms. The Li(1)-O(2) bond length is 1.95 Å. Both Li(1)-O(1) bond lengths are 2.00 Å. Both Li(1)-Br(1) bond lengths are 2.97 Å. P(1) is bonded in a tetrahedral geometry to four equivalent O(1) atoms. All P(1)-O(1) bond lengths are 1.56 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(1) and one P(1) atom to form OLi3P tetrahedra that share corners with three equivalent O(2)Li6 octahedra, corners with six equivalent O(1)Li3P tetrahedra, and edges with three equivalent Br(1)Li12 cuboctahedra. The corner-sharing octahedral tilt angles are 58°. In the second O site, O(2) is bonded to six equivalent Li(1) atoms to form OLi6 octahedra that share corners with twelve equivalent O(1)Li3P tetrahedra and faces with four equivalent Br(1)Li12 cuboctahedra. Br(1) is bonded to twelve equivalent Li(1) atoms to form BrLi12 cuboctahedra that share corners with twelve equivalent Br(1)Li12 cuboctahedra, edges with twelve equivalent O(1)Li3P tetrahedra, and faces with four equivalent O(2)Li6 octahedra.