Li3Ti2VO6 is alpha Po-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 two equivalent O(2) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with four equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. In the second Li site, Li(2) is bonded to one O(3), two equivalent O(2), and three equivalent O(1) atoms to form LiO6 octahedra that share  a cornercorner with one V(1)O6 octahedra, corners with five equivalent Ti(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. Ti(1) is bonded to one O(3), two equivalent O(1), and three equivalent O(2) atoms to form TiO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with five equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. V(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. There are three inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(2), two equivalent Ti(1), and one V(1) atom to form OLi3Ti2V octahedra that share  a cornercorner with one O(1)Li3Ti2V octahedra,  a cornercorner with one O(3)Li3TiV2 octahedra, corners with four equivalent O(2)Li3Ti3 octahedra, edges with four equivalent O(1)Li3Ti2V octahedra, edges with four equivalent O(2)Li3Ti3 octahedra, and edges with four equivalent O(3)Li3TiV2 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), and three equivalent Ti(1) atoms to form OLi3Ti3 octahedra that share  a cornercorner with one O(2)Li3Ti3 octahedra,  a cornercorner with one O(3)Li3TiV2 octahedra, corners with four equivalent O(1)Li3Ti2V octahedra, edges with four equivalent O(1)Li3Ti2V octahedra, edges with four equivalent O(2)Li3Ti3 octahedra, and edges with four equivalent O(3)Li3TiV2 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), one Ti(1), and two equivalent V(1) atoms to form OLi3TiV2 octahedra that share  a cornercorner with one O(1)Li3Ti2V octahedra,  a cornercorner with one O(2)Li3Ti3 octahedra, corners with four equivalent O(3)Li3TiV2 octahedra, edges with four equivalent O(1)Li3Ti2V octahedra, edges with four equivalent O(2)Li3Ti3 octahedra, and edges with four equivalent O(3)Li3TiV2 octahedra. The corner-sharing octahedral tilt angles range from 0-7°.
Li3Ti2VO6 is alpha Po-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 two equivalent O(2) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with four equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. Both Li(1)-O(2) bond lengths are 2.20 Å. All Li(1)-O(3) bond lengths are 2.12 Å. In the second Li site, Li(2) is bonded to one O(3), two equivalent O(2), and three equivalent O(1) atoms to form LiO6 octahedra that share  a cornercorner with one V(1)O6 octahedra, corners with five equivalent Ti(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. The Li(2)-O(3) bond length is 2.13 Å. Both Li(2)-O(2) bond lengths are 2.19 Å. There is one shorter (2.10 Å) and two longer (2.16 Å) Li(2)-O(1) bond lengths. Ti(1) is bonded to one O(3), two equivalent O(1), and three equivalent O(2) atoms to form TiO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with five equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. The Ti(1)-O(3) bond length is 1.99 Å. Both Ti(1)-O(1) bond lengths are 2.03 Å. There are two shorter (2.05 Å) and one longer (2.12 Å) Ti(1)-O(2) bond length. V(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. Both V(1)-O(1) bond lengths are 2.12 Å. All V(1)-O(3) bond lengths are 2.09 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(2), two equivalent Ti(1), and one V(1) atom to form OLi3Ti2V octahedra that share  a cornercorner with one O(1)Li3Ti2V octahedra,  a cornercorner with one O(3)Li3TiV2 octahedra, corners with four equivalent O(2)Li3Ti3 octahedra, edges with four equivalent O(1)Li3Ti2V octahedra, edges with four equivalent O(2)Li3Ti3 octahedra, and edges with four equivalent O(3)Li3TiV2 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), and three equivalent Ti(1) atoms to form OLi3Ti3 octahedra that share  a cornercorner with one O(2)Li3Ti3 octahedra,  a cornercorner with one O(3)Li3TiV2 octahedra, corners with four equivalent O(1)Li3Ti2V octahedra, edges with four equivalent O(1)Li3Ti2V octahedra, edges with four equivalent O(2)Li3Ti3 octahedra, and edges with four equivalent O(3)Li3TiV2 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), one Ti(1), and two equivalent V(1) atoms to form OLi3TiV2 octahedra that share  a cornercorner with one O(1)Li3Ti2V octahedra,  a cornercorner with one O(2)Li3Ti3 octahedra, corners with four equivalent O(3)Li3TiV2 octahedra, edges with four equivalent O(1)Li3Ti2V octahedra, edges with four equivalent O(2)Li3Ti3 octahedra, and edges with four equivalent O(3)Li3TiV2 octahedra. The corner-sharing octahedral tilt angles range from 0-7°.