Li3V3O8 is Spinel-like structured and crystallizes in the orthorhombic Imm2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(3) and two equivalent O(4) atoms to form LiO4 tetrahedra that share corners with six equivalent Li(2)O6 octahedra and corners with six equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-64°. In the second Li site, Li(2) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent V(1)O4 tetrahedra, edges with two equivalent Li(2)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form VO4 tetrahedra that share corners with six equivalent Li(2)O6 octahedra and corners with six equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-59°. In the second V site, V(2) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form distorted VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent V(1)O4 tetrahedra, edges with two equivalent V(2)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to two equivalent Li(2), one V(1), and one V(2) atom. In the second O site, O(2) is bonded to one Li(2), one V(1), and two equivalent V(2) atoms to form a mixture of distorted corner and edge-sharing OLiV3 trigonal pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Li(2), and one V(2) atom. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), and two equivalent V(2) atoms.
Li3V3O8 is Spinel-like structured and crystallizes in the orthorhombic Imm2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(3) and two equivalent O(4) atoms to form LiO4 tetrahedra that share corners with six equivalent Li(2)O6 octahedra and corners with six equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-64°. Both Li(1)-O(3) bond lengths are 1.96 Å. Both Li(1)-O(4) bond lengths are 1.95 Å. In the second Li site, Li(2) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent V(1)O4 tetrahedra, edges with two equivalent Li(2)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The Li(2)-O(2) bond length is 2.12 Å. The Li(2)-O(4) bond length is 2.06 Å. Both Li(2)-O(1) bond lengths are 2.17 Å. Both Li(2)-O(3) bond lengths are 2.08 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form VO4 tetrahedra that share corners with six equivalent Li(2)O6 octahedra and corners with six equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-59°. Both V(1)-O(1) bond lengths are 1.72 Å. Both V(1)-O(2) bond lengths are 1.83 Å. In the second V site, V(2) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form distorted VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent V(1)O4 tetrahedra, edges with two equivalent V(2)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The V(2)-O(1) bond length is 2.30 Å. The V(2)-O(3) bond length is 1.70 Å. Both V(2)-O(2) bond lengths are 2.16 Å. Both V(2)-O(4) bond lengths are 1.91 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to two equivalent Li(2), one V(1), and one V(2) atom. In the second O site, O(2) is bonded to one Li(2), one V(1), and two equivalent V(2) atoms to form a mixture of distorted corner and edge-sharing OLiV3 trigonal pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Li(2), and one V(2) atom. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), and two equivalent V(2) atoms.