Li2Ti3V3O12 is Corundum-derived structured and crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent V(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(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), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with four equivalent Ti(2)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-11°. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms to form TiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 10°. In the second Ti site, Ti(2) is bonded to one O(1), one O(2), one O(3), one O(6), and two equivalent O(4) atoms to form TiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra,  an edgeedge with one Ti(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-11°. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles are 11°. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(6), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with two equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles are 13°. There are six 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(2), one V(1), and one V(2) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(2), one Ti(1), one Ti(2), and one V(2) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Ti(1), one Ti(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(2), two equivalent Ti(2), and one V(1) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(1), one Ti(1), and two equivalent V(2) atoms. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(1), one Ti(2), one V(1), and one V(2) atom.
Li2Ti3V3O12 is Corundum-derived structured and crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent V(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(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-13°. Both Li(1)-O(3) bond lengths are 2.19 Å. Both Li(1)-O(5) bond lengths are 2.23 Å. Both Li(1)-O(6) bond lengths are 2.34 Å. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with four equivalent Ti(2)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-11°. Both Li(2)-O(1) bond lengths are 2.30 Å. Both Li(2)-O(2) bond lengths are 2.22 Å. Both Li(2)-O(4) 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(2), two equivalent O(3), and two equivalent O(5) atoms to form TiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 10°. Both Ti(1)-O(2) bond lengths are 2.04 Å. Both Ti(1)-O(3) bond lengths are 1.97 Å. Both Ti(1)-O(5) bond lengths are 1.96 Å. In the second Ti site, Ti(2) is bonded to one O(1), one O(2), one O(3), one O(6), and two equivalent O(4) atoms to form TiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra,  an edgeedge with one Ti(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-11°. The Ti(2)-O(1) bond length is 1.95 Å. The Ti(2)-O(2) bond length is 1.92 Å. The Ti(2)-O(3) bond length is 1.96 Å. The Ti(2)-O(6) bond length is 2.06 Å. There is one shorter (1.95 Å) and one longer (2.09 Å) Ti(2)-O(4) bond length. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles are 11°. Both V(1)-O(1) bond lengths are 1.99 Å. Both V(1)-O(4) bond lengths are 1.99 Å. Both V(1)-O(6) bond lengths are 1.92 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(6), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with two equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles are 13°. The V(2)-O(1) bond length is 2.02 Å. The V(2)-O(2) bond length is 2.09 Å. The V(2)-O(3) bond length is 2.10 Å. The V(2)-O(6) bond length is 2.05 Å. There is one shorter (2.00 Å) and one longer (2.04 Å) V(2)-O(5) bond length. There are six 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(2), one V(1), and one V(2) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(2), one Ti(1), one Ti(2), and one V(2) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Ti(1), one Ti(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(2), two equivalent Ti(2), and one V(1) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(1), one Ti(1), and two equivalent V(2) atoms. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(1), one Ti(2), one V(1), and one V(2) atom.