Li5SbO5 crystallizes in the monoclinic C2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), and three equivalent O(3) atoms to form distorted LiO5 square pyramids that share corners with two equivalent Sb(1)O6 octahedra, corners with two equivalent Li(3)O5 square pyramids, corners with three equivalent Li(1)O5 square pyramids, edges with two equivalent Sb(1)O6 octahedra, edges with two equivalent Li(1)O5 square pyramids, and edges with three equivalent Li(3)O5 square pyramids. The corner-sharing octahedral tilt angles range from 0-9°. In the second Li site, Li(2) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(3) atoms. In the third Li site, Li(3) is bonded to one O(2), one O(3), and three equivalent O(1) atoms to form LiO5 square pyramids that share corners with two equivalent Li(1)O5 square pyramids, corners with three equivalent Li(3)O5 square pyramids, edges with three equivalent Sb(1)O6 octahedra, edges with two equivalent Li(3)O5 square pyramids, and edges with three equivalent Li(1)O5 square pyramids. Sb(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form SbO6 octahedra that share corners with two equivalent Sb(1)O6 octahedra, corners with four equivalent Li(1)O5 square pyramids, edges with four equivalent Li(1)O5 square pyramids, and edges with six equivalent Li(3)O5 square pyramids. The corner-sharing octahedra are not tilted. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), three equivalent Li(3), and one Sb(1) atom to form OLi5Sb octahedra that share corners with four equivalent O(1)Li5Sb octahedra, edges with two equivalent O(1)Li5Sb octahedra, edges with three equivalent O(2)Li4Sb2 octahedra, and edges with five equivalent O(3)Li5Sb octahedra. The corner-sharing octahedral tilt angles range from 0-23°. In the second O site, O(2) is bonded to two equivalent Li(1), two equivalent Li(3), and two equivalent Sb(1) atoms to form OLi4Sb2 octahedra that share corners with two equivalent O(2)Li4Sb2 octahedra, corners with four equivalent O(3)Li5Sb octahedra, edges with four equivalent O(3)Li5Sb octahedra, and edges with six equivalent O(1)Li5Sb octahedra. The corner-sharing octahedral tilt angles range from 0-18°. In the third O site, O(3) is bonded to one Li(2), one Li(3), three equivalent Li(1), and one Sb(1) atom to form OLi5Sb octahedra that share corners with two equivalent O(2)Li4Sb2 octahedra, corners with four equivalent O(3)Li5Sb octahedra, edges with two equivalent O(2)Li4Sb2 octahedra, edges with two equivalent O(3)Li5Sb octahedra, and edges with five equivalent O(1)Li5Sb octahedra. The corner-sharing octahedral tilt angles range from 0-28°.
Li5SbO5 crystallizes in the monoclinic C2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), and three equivalent O(3) atoms to form distorted LiO5 square pyramids that share corners with two equivalent Sb(1)O6 octahedra, corners with two equivalent Li(3)O5 square pyramids, corners with three equivalent Li(1)O5 square pyramids, edges with two equivalent Sb(1)O6 octahedra, edges with two equivalent Li(1)O5 square pyramids, and edges with three equivalent Li(3)O5 square pyramids. The corner-sharing octahedral tilt angles range from 0-9°. The Li(1)-O(1) bond length is 1.93 Å. The Li(1)-O(2) bond length is 2.35 Å. There is one shorter (1.95 Å) and two longer (2.07 Å) Li(1)-O(3) bond lengths. In the second Li site, Li(2) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(3) atoms. Both Li(2)-O(1) bond lengths are 1.95 Å. Both Li(2)-O(3) bond lengths are 2.11 Å. In the third Li site, Li(3) is bonded to one O(2), one O(3), and three equivalent O(1) atoms to form LiO5 square pyramids that share corners with two equivalent Li(1)O5 square pyramids, corners with three equivalent Li(3)O5 square pyramids, edges with three equivalent Sb(1)O6 octahedra, edges with two equivalent Li(3)O5 square pyramids, and edges with three equivalent Li(1)O5 square pyramids. The Li(3)-O(2) bond length is 2.22 Å. The Li(3)-O(3) bond length is 2.06 Å. There is one shorter (2.00 Å) and two longer (2.04 Å) Li(3)-O(1) bond lengths. Sb(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form SbO6 octahedra that share corners with two equivalent Sb(1)O6 octahedra, corners with four equivalent Li(1)O5 square pyramids, edges with four equivalent Li(1)O5 square pyramids, and edges with six equivalent Li(3)O5 square pyramids. The corner-sharing octahedra are not tilted. Both Sb(1)-O(1) bond lengths are 1.97 Å. Both Sb(1)-O(2) bond lengths are 2.00 Å. Both Sb(1)-O(3) bond lengths are 1.97 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), three equivalent Li(3), and one Sb(1) atom to form OLi5Sb octahedra that share corners with four equivalent O(1)Li5Sb octahedra, edges with two equivalent O(1)Li5Sb octahedra, edges with three equivalent O(2)Li4Sb2 octahedra, and edges with five equivalent O(3)Li5Sb octahedra. The corner-sharing octahedral tilt angles range from 0-23°. In the second O site, O(2) is bonded to two equivalent Li(1), two equivalent Li(3), and two equivalent Sb(1) atoms to form OLi4Sb2 octahedra that share corners with two equivalent O(2)Li4Sb2 octahedra, corners with four equivalent O(3)Li5Sb octahedra, edges with four equivalent O(3)Li5Sb octahedra, and edges with six equivalent O(1)Li5Sb octahedra. The corner-sharing octahedral tilt angles range from 0-18°. In the third O site, O(3) is bonded to one Li(2), one Li(3), three equivalent Li(1), and one Sb(1) atom to form OLi5Sb octahedra that share corners with two equivalent O(2)Li4Sb2 octahedra, corners with four equivalent O(3)Li5Sb octahedra, edges with two equivalent O(2)Li4Sb2 octahedra, edges with two equivalent O(3)Li5Sb octahedra, and edges with five equivalent O(1)Li5Sb octahedra. The corner-sharing octahedral tilt angles range from 0-28°.