Li2Ti3VO8 is Spinel-derived structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(4), and two equivalent O(5) atoms to form LiO4 tetrahedra that share corners with three equivalent Ti(2)O6 octahedra, corners with three equivalent V(1)O6 octahedra, and corners with six equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-62°. In the second Li site, Li(2) is bonded to one O(2), one O(3), and two equivalent O(6) atoms to form LiO4 tetrahedra that share corners with three equivalent Ti(3)O6 octahedra, corners with three equivalent V(1)O6 octahedra, and corners with six equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-62°. There are three inequivalent Ti sites. In the first Ti site, Ti(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 TiO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Ti(2)O6 octahedra,  an edgeedge with one Ti(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. In the second Ti site, Ti(2) is bonded to two equivalent O(1) and four equivalent O(5) atoms to form TiO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. In the third Ti site, Ti(3) is bonded to two equivalent O(2) and four equivalent O(6) atoms to form TiO6 octahedra that share corners with six equivalent Li(2)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. V(1) is bonded to one O(3), one O(4), two equivalent O(5), and two equivalent O(6) atoms to form VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Ti(2)O6 octahedra,  an edgeedge with one Ti(3)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Ti(2), and two equivalent Ti(1) atoms to form distorted corner-sharing OLiTi3 trigonal pyramids. In the second O site, O(2) is bonded to one Li(2), one Ti(3), and two equivalent Ti(1) atoms to form distorted corner-sharing OLiTi3 trigonal pyramids. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), two equivalent Ti(1), and one V(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent Ti(1), and one V(1) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Ti(1), one Ti(2), and one V(1) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Ti(1), one Ti(3), and one V(1) atom.
Li2Ti3VO8 is Spinel-derived structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(4), and two equivalent O(5) atoms to form LiO4 tetrahedra that share corners with three equivalent Ti(2)O6 octahedra, corners with three equivalent V(1)O6 octahedra, and corners with six equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-62°. The Li(1)-O(1) bond length is 2.07 Å. The Li(1)-O(4) bond length is 2.01 Å. Both Li(1)-O(5) bond lengths are 2.01 Å. In the second Li site, Li(2) is bonded to one O(2), one O(3), and two equivalent O(6) atoms to form LiO4 tetrahedra that share corners with three equivalent Ti(3)O6 octahedra, corners with three equivalent V(1)O6 octahedra, and corners with six equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-62°. The Li(2)-O(2) bond length is 2.07 Å. The Li(2)-O(3) bond length is 2.01 Å. Both Li(2)-O(6) bond lengths are 2.01 Å. There are three inequivalent Ti sites. In the first Ti site, Ti(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 TiO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Ti(2)O6 octahedra,  an edgeedge with one Ti(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The Ti(1)-O(1) bond length is 2.03 Å. The Ti(1)-O(2) bond length is 2.02 Å. The Ti(1)-O(3) bond length is 1.98 Å. The Ti(1)-O(4) bond length is 1.98 Å. The Ti(1)-O(5) bond length is 1.98 Å. The Ti(1)-O(6) bond length is 1.98 Å. In the second Ti site, Ti(2) is bonded to two equivalent O(1) and four equivalent O(5) atoms to form TiO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. Both Ti(2)-O(1) bond lengths are 2.03 Å. All Ti(2)-O(5) bond lengths are 1.98 Å. In the third Ti site, Ti(3) is bonded to two equivalent O(2) and four equivalent O(6) atoms to form TiO6 octahedra that share corners with six equivalent Li(2)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. Both Ti(3)-O(2) bond lengths are 2.03 Å. All Ti(3)-O(6) bond lengths are 1.98 Å. V(1) is bonded to one O(3), one O(4), two equivalent O(5), and two equivalent O(6) atoms to form VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Ti(2)O6 octahedra,  an edgeedge with one Ti(3)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The V(1)-O(3) bond length is 2.09 Å. The V(1)-O(4) bond length is 2.09 Å. Both V(1)-O(5) bond lengths are 2.09 Å. Both V(1)-O(6) bond lengths are 2.10 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Ti(2), and two equivalent Ti(1) atoms to form distorted corner-sharing OLiTi3 trigonal pyramids. In the second O site, O(2) is bonded to one Li(2), one Ti(3), and two equivalent Ti(1) atoms to form distorted corner-sharing OLiTi3 trigonal pyramids. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), two equivalent Ti(1), and one V(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent Ti(1), and one V(1) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Ti(1), one Ti(2), and one V(1) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Ti(1), one Ti(3), and one V(1) atom.