LiV4Al2O8 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with four equivalent V(2)O6 octahedra, and edges with four equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-11°. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with four equivalent V(2)O6 octahedra, and edges with four equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-11°. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent Al(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-7°. In the third V site, V(3) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form VO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent V(2)O6 octahedra, and edges with four equivalent Al(1)O6 octahedra. Al(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form AlO6 octahedra that share corners with six equivalent V(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-7°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one V(1), one V(2), one V(3), and one Al(1) atom to form OLiAlV3 square pyramids that share corners with two equivalent O(3)Al2V3 square pyramids, corners with seven equivalent O(1)LiAlV3 square pyramids, edges with four equivalent O(2)LiAl2V3 octahedra, edges with two equivalent O(3)Al2V3 square pyramids, and edges with two equivalent O(1)LiAlV3 square pyramids. In the second O site, O(2) is bonded to one Li(1), one V(1), two equivalent V(2), and two equivalent Al(1) atoms to form OLiAl2V3 octahedra that share corners with six equivalent O(2)LiAl2V3 octahedra, edges with four equivalent O(3)Al2V3 square pyramids, and edges with eight equivalent O(1)LiAlV3 square pyramids. The corner-sharing octahedra are not tilted. In the third O site, O(3) is bonded to one V(3), two equivalent V(2), and two equivalent Al(1) atoms to form OAl2V3 square pyramids that share corners with four equivalent O(1)LiAlV3 square pyramids, corners with five equivalent O(3)Al2V3 square pyramids, edges with four equivalent O(2)LiAl2V3 octahedra, and edges with four equivalent O(1)LiAlV3 square pyramids.
LiV4Al2O8 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with four equivalent V(2)O6 octahedra, and edges with four equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-11°. Both Li(1)-O(2) bond lengths are 2.06 Å. All Li(1)-O(1) bond lengths are 2.13 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with four equivalent V(2)O6 octahedra, and edges with four equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-11°. Both V(1)-O(2) bond lengths are 2.13 Å. All V(1)-O(1) bond lengths are 2.15 Å. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent Al(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-7°. Both V(2)-O(1) bond lengths are 2.26 Å. Both V(2)-O(2) bond lengths are 2.25 Å. Both V(2)-O(3) bond lengths are 2.25 Å. In the third V site, V(3) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form VO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent V(2)O6 octahedra, and edges with four equivalent Al(1)O6 octahedra. Both V(3)-O(3) bond lengths are 2.06 Å. All V(3)-O(1) bond lengths are 2.01 Å. Al(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form AlO6 octahedra that share corners with six equivalent V(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent Al(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-7°. Both Al(1)-O(1) bond lengths are 1.93 Å. Both Al(1)-O(2) bond lengths are 2.01 Å. Both Al(1)-O(3) bond lengths are 2.01 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one V(1), one V(2), one V(3), and one Al(1) atom to form OLiAlV3 square pyramids that share corners with two equivalent O(3)Al2V3 square pyramids, corners with seven equivalent O(1)LiAlV3 square pyramids, edges with four equivalent O(2)LiAl2V3 octahedra, edges with two equivalent O(3)Al2V3 square pyramids, and edges with two equivalent O(1)LiAlV3 square pyramids. In the second O site, O(2) is bonded to one Li(1), one V(1), two equivalent V(2), and two equivalent Al(1) atoms to form OLiAl2V3 octahedra that share corners with six equivalent O(2)LiAl2V3 octahedra, edges with four equivalent O(3)Al2V3 square pyramids, and edges with eight equivalent O(1)LiAlV3 square pyramids. The corner-sharing octahedra are not tilted. In the third O site, O(3) is bonded to one V(3), two equivalent V(2), and two equivalent Al(1) atoms to form OAl2V3 square pyramids that share corners with four equivalent O(1)LiAlV3 square pyramids, corners with five equivalent O(3)Al2V3 square pyramids, edges with four equivalent O(2)LiAl2V3 octahedra, and edges with four equivalent O(1)LiAlV3 square pyramids.