LiV3O8 crystallizes in the monoclinic Cm space group. Li(1) is bonded to one O(1), one O(2), one O(6), and two equivalent O(5) atoms to form LiO5 trigonal bipyramids that share corners with two equivalent V(2)O6 octahedra, corners with three equivalent V(3)O4 tetrahedra, and corners with two equivalent Li(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 60°. There are three inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(2), one O(4), one O(7), and two equivalent O(3) atoms. In the second V site, V(2) is bonded to one O(3), one O(5), one O(7), one O(8), and two equivalent O(4) atoms to form distorted VO6 octahedra that share corners with two equivalent V(2)O6 octahedra,  a cornercorner with one V(3)O4 tetrahedra, and corners with two equivalent Li(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 40°. In the third V site, V(3) is bonded to one O(1), one O(8), and two equivalent O(6) atoms to form distorted VO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent V(3)O4 tetrahedra, and corners with three equivalent Li(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 9°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Li(1) and one V(3) atom. In the second O site, O(2) is bonded in a linear geometry to one Li(1) and one V(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(2) and two equivalent V(1) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one V(1) and two equivalent V(2) atoms. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one V(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Li(1) and two equivalent V(3) atoms. In the seventh O site, O(7) is bonded in a linear geometry to one V(1) and one V(2) atom. In the eighth O site, O(8) is bonded in a linear geometry to one V(2) and one V(3) atom.
LiV3O8 crystallizes in the monoclinic Cm space group. Li(1) is bonded to one O(1), one O(2), one O(6), and two equivalent O(5) atoms to form LiO5 trigonal bipyramids that share corners with two equivalent V(2)O6 octahedra, corners with three equivalent V(3)O4 tetrahedra, and corners with two equivalent Li(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 60°. The Li(1)-O(1) bond length is 1.97 Å. The Li(1)-O(2) bond length is 1.98 Å. The Li(1)-O(6) bond length is 2.19 Å. Both Li(1)-O(5) bond lengths are 2.04 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(2), one O(4), one O(7), and two equivalent O(3) atoms. The V(1)-O(2) bond length is 1.62 Å. The V(1)-O(4) bond length is 2.14 Å. The V(1)-O(7) bond length is 1.82 Å. Both V(1)-O(3) bond lengths are 1.85 Å. In the second V site, V(2) is bonded to one O(3), one O(5), one O(7), one O(8), and two equivalent O(4) atoms to form distorted VO6 octahedra that share corners with two equivalent V(2)O6 octahedra,  a cornercorner with one V(3)O4 tetrahedra, and corners with two equivalent Li(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 40°. The V(2)-O(3) bond length is 2.26 Å. The V(2)-O(5) bond length is 1.68 Å. The V(2)-O(7) bond length is 1.80 Å. The V(2)-O(8) bond length is 2.16 Å. Both V(2)-O(4) bond lengths are 1.87 Å. In the third V site, V(3) is bonded to one O(1), one O(8), and two equivalent O(6) atoms to form distorted VO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent V(3)O4 tetrahedra, and corners with three equivalent Li(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 9°. The V(3)-O(1) bond length is 1.67 Å. The V(3)-O(8) bond length is 1.69 Å. Both V(3)-O(6) bond lengths are 1.89 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Li(1) and one V(3) atom. In the second O site, O(2) is bonded in a linear geometry to one Li(1) and one V(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(2) and two equivalent V(1) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one V(1) and two equivalent V(2) atoms. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one V(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Li(1) and two equivalent V(3) atoms. In the seventh O site, O(7) is bonded in a linear geometry to one V(1) and one V(2) atom. In the eighth O site, O(8) is bonded in a linear geometry to one V(2) and one V(3) atom.