LiV4Al2O8 crystallizes in the monoclinic Cm space group. Li(1) is bonded in a distorted body-centered cubic geometry to one V(1), one V(3), two equivalent V(2), one O(3), one O(5), and two equivalent O(4) atoms. There are three inequivalent V sites. In the first V site, V(1) is bonded in a 7-coordinate geometry to one Li(1), one O(2), one O(5), two equivalent O(1), and two equivalent O(4) atoms. In the second V site, V(2) is bonded in a 7-coordinate geometry to one Li(1), one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. In the third V site, V(3) is bonded in a 7-coordinate geometry to one Li(1), one O(3), one O(6), two equivalent O(1), and two equivalent O(4) atoms. Al(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form edge-sharing AlO6 octahedra. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted see-saw-like geometry to one V(1), one V(2), one V(3), and one Al(1) atom. In the second O site, O(2) is bonded to one V(1), two equivalent V(2), and two equivalent Al(1) atoms to form OAl2V3 square pyramids that share corners with five equivalent O(5)LiAl2V3 octahedra, edges with two equivalent O(3)LiAl2V3 octahedra, and edges with two equivalent O(6)Al2V3 square pyramids. The corner-sharing octahedral tilt angles range from 3-10°. In the third O site, O(3) is bonded to one Li(1), one V(3), two equivalent V(2), and two equivalent Al(1) atoms to form distorted OLiAl2V3 octahedra that share corners with five equivalent O(6)Al2V3 square pyramids,  an edgeedge with one O(5)LiAl2V3 octahedra, edges with two equivalent O(2)Al2V3 square pyramids, and  a faceface with one O(5)LiAl2V3 octahedra. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Li(1), one V(1), one V(2), one V(3), and one Al(1) atom. In the fifth O site, O(5) is bonded to one Li(1), one V(1), two equivalent V(2), and two equivalent Al(1) atoms to form distorted OLiAl2V3 octahedra that share corners with five equivalent O(2)Al2V3 square pyramids,  an edgeedge with one O(3)LiAl2V3 octahedra, edges with two equivalent O(6)Al2V3 square pyramids, and  a faceface with one O(3)LiAl2V3 octahedra. In the sixth O site, O(6) 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 five equivalent O(3)LiAl2V3 octahedra, edges with two equivalent O(5)LiAl2V3 octahedra, and edges with two equivalent O(2)Al2V3 square pyramids. The corner-sharing octahedral tilt angles range from 3-10°.
LiV4Al2O8 crystallizes in the monoclinic Cm space group. Li(1) is bonded in a distorted body-centered cubic geometry to one V(1), one V(3), two equivalent V(2), one O(3), one O(5), and two equivalent O(4) atoms. The Li(1)-V(1) bond length is 2.04 Å. The Li(1)-V(3) bond length is 2.03 Å. Both Li(1)-V(2) bond lengths are 2.02 Å. The Li(1)-O(3) bond length is 1.93 Å. The Li(1)-O(5) bond length is 1.92 Å. Both Li(1)-O(4) bond lengths are 1.81 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded in a 7-coordinate geometry to one Li(1), one O(2), one O(5), two equivalent O(1), and two equivalent O(4) atoms. The V(1)-O(2) bond length is 2.07 Å. The V(1)-O(5) bond length is 2.09 Å. Both V(1)-O(1) bond lengths are 2.00 Å. Both V(1)-O(4) bond lengths are 2.15 Å. In the second V site, V(2) is bonded in a 7-coordinate geometry to one Li(1), one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. The V(2)-O(1) bond length is 2.22 Å. The V(2)-O(2) bond length is 2.20 Å. The V(2)-O(3) bond length is 2.37 Å. The V(2)-O(4) bond length is 2.37 Å. The V(2)-O(5) bond length is 2.37 Å. The V(2)-O(6) bond length is 2.21 Å. In the third V site, V(3) is bonded in a 7-coordinate geometry to one Li(1), one O(3), one O(6), two equivalent O(1), and two equivalent O(4) atoms. The V(3)-O(3) bond length is 2.10 Å. The V(3)-O(6) bond length is 2.07 Å. Both V(3)-O(1) bond lengths are 2.04 Å. Both V(3)-O(4) bond lengths are 2.17 Å. Al(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form edge-sharing AlO6 octahedra. The Al(1)-O(1) bond length is 1.93 Å. The Al(1)-O(2) bond length is 2.07 Å. The Al(1)-O(3) bond length is 2.14 Å. The Al(1)-O(4) bond length is 1.91 Å. The Al(1)-O(5) bond length is 2.14 Å. The Al(1)-O(6) bond length is 2.07 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted see-saw-like geometry to one V(1), one V(2), one V(3), and one Al(1) atom. In the second O site, O(2) is bonded to one V(1), two equivalent V(2), and two equivalent Al(1) atoms to form OAl2V3 square pyramids that share corners with five equivalent O(5)LiAl2V3 octahedra, edges with two equivalent O(3)LiAl2V3 octahedra, and edges with two equivalent O(6)Al2V3 square pyramids. The corner-sharing octahedral tilt angles range from 3-10°. In the third O site, O(3) is bonded to one Li(1), one V(3), two equivalent V(2), and two equivalent Al(1) atoms to form distorted OLiAl2V3 octahedra that share corners with five equivalent O(6)Al2V3 square pyramids,  an edgeedge with one O(5)LiAl2V3 octahedra, edges with two equivalent O(2)Al2V3 square pyramids, and  a faceface with one O(5)LiAl2V3 octahedra. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Li(1), one V(1), one V(2), one V(3), and one Al(1) atom. In the fifth O site, O(5) is bonded to one Li(1), one V(1), two equivalent V(2), and two equivalent Al(1) atoms to form distorted OLiAl2V3 octahedra that share corners with five equivalent O(2)Al2V3 square pyramids,  an edgeedge with one O(3)LiAl2V3 octahedra, edges with two equivalent O(6)Al2V3 square pyramids, and  a faceface with one O(3)LiAl2V3 octahedra. In the sixth O site, O(6) 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 five equivalent O(3)LiAl2V3 octahedra, edges with two equivalent O(5)LiAl2V3 octahedra, and edges with two equivalent O(2)Al2V3 square pyramids. The corner-sharing octahedral tilt angles range from 3-10°.