Li2V3O8 crystallizes in the orthorhombic P2_12_12_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form LiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent V(2)O6 octahedra, and corners with three equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-60°. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(7), and one O(8) atom to form LiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent V(2)O6 octahedra, and corners with three equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-61°. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), one O(4), one O(5), one O(7), and one O(8) atom to form VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(8) atom to form distorted VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. In the third V site, V(3) is bonded to one O(1), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form distorted VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(2), one V(2), and one V(3) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one V(2) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one V(1), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one V(3) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one V(3) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Li(2), one V(1), and one V(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal pyramidal geometry to one Li(2), one V(1), one V(2), and one V(3) atom.
Li2V3O8 crystallizes in the orthorhombic P2_12_12_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form LiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent V(2)O6 octahedra, and corners with three equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-60°. The Li(1)-O(3) bond length is 1.96 Å. The Li(1)-O(4) bond length is 2.00 Å. The Li(1)-O(5) bond length is 2.00 Å. The Li(1)-O(6) bond length is 1.99 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(7), and one O(8) atom to form LiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent V(2)O6 octahedra, and corners with three equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-61°. The Li(2)-O(1) bond length is 2.00 Å. The Li(2)-O(2) bond length is 1.99 Å. The Li(2)-O(7) bond length is 1.99 Å. The Li(2)-O(8) bond length is 1.97 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), one O(4), one O(5), one O(7), and one O(8) atom to form VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The V(1)-O(2) bond length is 2.05 Å. The V(1)-O(3) bond length is 1.96 Å. The V(1)-O(4) bond length is 1.84 Å. The V(1)-O(5) bond length is 2.00 Å. The V(1)-O(7) bond length is 2.00 Å. The V(1)-O(8) bond length is 1.95 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(8) atom to form distorted VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The V(2)-O(1) bond length is 1.95 Å. The V(2)-O(2) bond length is 1.75 Å. The V(2)-O(3) bond length is 2.10 Å. The V(2)-O(4) bond length is 1.94 Å. The V(2)-O(6) bond length is 1.74 Å. The V(2)-O(8) bond length is 2.12 Å. In the third V site, V(3) is bonded to one O(1), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form distorted VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The V(3)-O(1) bond length is 1.81 Å. The V(3)-O(3) bond length is 2.02 Å. The V(3)-O(5) bond length is 1.77 Å. The V(3)-O(6) bond length is 2.13 Å. The V(3)-O(7) bond length is 1.76 Å. The V(3)-O(8) bond length is 2.08 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(2), one V(2), and one V(3) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one V(2) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one V(1), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one V(3) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one V(3) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Li(2), one V(1), and one V(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal pyramidal geometry to one Li(2), one V(1), one V(2), and one V(3) atom.