Li2Ti3VO8 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-13°. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Ti(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles are 9°. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form TiO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles are 9°. In the second Ti site, Ti(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form TiO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. V(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-13°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(2), one Ti(1), and two equivalent Ti(2) atoms. In the second O site, O(2) is bonded in a see-saw-like geometry to one Li(1), two equivalent Ti(2), and one V(1) atom. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Ti(1), one Ti(2), and one V(1) atom to form a mixture of corner and edge-sharing OLi2Ti2V square pyramids.
Li2Ti3VO8 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-13°. Both Li(1)-O(2) bond lengths are 2.18 Å. All Li(1)-O(3) bond lengths are 2.15 Å. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Ti(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles are 9°. Both Li(2)-O(1) bond lengths are 2.26 Å. All Li(2)-O(3) bond lengths are 2.25 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form TiO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles are 9°. Both Ti(1)-O(1) bond lengths are 2.03 Å. All Ti(1)-O(3) bond lengths are 2.01 Å. In the second Ti site, Ti(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form TiO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. Both Ti(2)-O(1) bond lengths are 2.01 Å. Both Ti(2)-O(2) bond lengths are 1.96 Å. Both Ti(2)-O(3) bond lengths are 1.98 Å. V(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-13°. Both V(1)-O(2) bond lengths are 2.12 Å. All V(1)-O(3) bond lengths are 2.12 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(2), one Ti(1), and two equivalent Ti(2) atoms. In the second O site, O(2) is bonded in a see-saw-like geometry to one Li(1), two equivalent Ti(2), and one V(1) atom. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Ti(1), one Ti(2), and one V(1) atom to form a mixture of corner and edge-sharing OLi2Ti2V square pyramids.