LiV4O8 crystallizes in the monoclinic Pm space group. Li(1) is bonded to one O(2), one O(4), and two equivalent O(6) atoms to form distorted LiO4 tetrahedra that share corners with six equivalent V(1)O6 octahedra, corners with two equivalent V(3)O4 tetrahedra, and  an edgeedge with one V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 67°. There are three inequivalent V sites. In the first V site, V(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 VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent V(2)O4 tetrahedra, corners with three equivalent V(3)O4 tetrahedra, and edges with two equivalent V(1)O6 octahedra. In the second V site, V(2) is bonded to one O(2), one O(4), and two equivalent O(1) atoms to form VO4 tetrahedra that share corners with six equivalent V(1)O6 octahedra and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-56°. In the third V site, V(3) is bonded to one O(3), one O(5), and two equivalent O(6) atoms to form VO4 tetrahedra that share corners with six equivalent V(1)O6 octahedra and corners with two equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-53°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(2) atom. In the second O site, O(2) is bonded to one Li(1), one V(2), and two equivalent V(1) atoms to form distorted edge-sharing OLiV3 tetrahedra. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(3) and two equivalent V(1) atoms. In the fourth O site, O(4) is bonded to one Li(1), one V(2), and two equivalent V(1) atoms to form distorted edge-sharing OLiV3 tetrahedra. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(3) and two equivalent V(1) atoms. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one V(3) atom.
LiV4O8 crystallizes in the monoclinic Pm space group. Li(1) is bonded to one O(2), one O(4), and two equivalent O(6) atoms to form distorted LiO4 tetrahedra that share corners with six equivalent V(1)O6 octahedra, corners with two equivalent V(3)O4 tetrahedra, and  an edgeedge with one V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 67°. The Li(1)-O(2) bond length is 2.15 Å. The Li(1)-O(4) bond length is 2.19 Å. Both Li(1)-O(6) bond lengths are 1.94 Å. There are three inequivalent V sites. In the first V site, V(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 VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent V(2)O4 tetrahedra, corners with three equivalent V(3)O4 tetrahedra, and edges with two equivalent V(1)O6 octahedra. The V(1)-O(1) bond length is 2.04 Å. The V(1)-O(2) bond length is 2.17 Å. The V(1)-O(3) bond length is 2.05 Å. The V(1)-O(4) bond length is 2.17 Å. The V(1)-O(5) bond length is 2.05 Å. The V(1)-O(6) bond length is 1.95 Å. In the second V site, V(2) is bonded to one O(2), one O(4), and two equivalent O(1) atoms to form VO4 tetrahedra that share corners with six equivalent V(1)O6 octahedra and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-56°. The V(2)-O(2) bond length is 1.82 Å. The V(2)-O(4) bond length is 1.82 Å. Both V(2)-O(1) bond lengths are 1.69 Å. In the third V site, V(3) is bonded to one O(3), one O(5), and two equivalent O(6) atoms to form VO4 tetrahedra that share corners with six equivalent V(1)O6 octahedra and corners with two equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-53°. The V(3)-O(3) bond length is 1.84 Å. The V(3)-O(5) bond length is 1.84 Å. Both V(3)-O(6) bond lengths are 1.80 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(2) atom. In the second O site, O(2) is bonded to one Li(1), one V(2), and two equivalent V(1) atoms to form distorted edge-sharing OLiV3 tetrahedra. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(3) and two equivalent V(1) atoms. In the fourth O site, O(4) is bonded to one Li(1), one V(2), and two equivalent V(1) atoms to form distorted edge-sharing OLiV3 tetrahedra. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(3) and two equivalent V(1) atoms. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one V(3) atom.