Li2TiVO4 is alpha Po-derived structured and crystallizes in the tetragonal I-42m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with four equivalent Li(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-3°. In the second Li site, Li(2) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the third Li site, Li(3) is bonded to one O(4), one O(5), and four equivalent O(1) atoms to form LiO6 octahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, edges with four equivalent Ti(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. Ti(1) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent O(3) atoms to form TiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Ti(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-4°. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent V(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the second V site, V(2) is bonded to two equivalent O(4) and four equivalent O(2) atoms to form VO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent V(3)O6 octahedra, edges with four equivalent Li(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°. In the third V site, V(3) is bonded to two equivalent O(5) and four equivalent O(2) atoms to form VO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent V(2)O6 octahedra, edges with four equivalent Li(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°. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(3), one Ti(1), and two equivalent V(1) atoms to form OLi3TiV2 octahedra that share corners with two equivalent O(2)Li3TiV2 octahedra, corners with four equivalent O(1)Li3TiV2 octahedra, edges with two equivalent O(4)Li3Ti2V octahedra, edges with two equivalent O(5)Li3Ti2V octahedra, edges with four equivalent O(3)Li3Ti2V octahedra, and edges with four equivalent O(1)Li3TiV2 octahedra. The corner-sharing octahedral tilt angles range from 1-8°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), one Ti(1), one V(2), and one V(3) atom to form OLi3TiV2 octahedra that share corners with two equivalent O(1)Li3TiV2 octahedra, corners with four equivalent O(2)Li3TiV2 octahedra, edges with two equivalent O(4)Li3Ti2V octahedra, edges with two equivalent O(5)Li3Ti2V octahedra, edges with four equivalent O(3)Li3Ti2V octahedra, and edges with four equivalent O(2)Li3TiV2 octahedra. The corner-sharing octahedral tilt angles range from 1-9°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), two equivalent Ti(1), and one V(1) atom to form OLi3Ti2V octahedra that share corners with six equivalent O(3)Li3Ti2V octahedra, edges with two equivalent O(4)Li3Ti2V octahedra, edges with two equivalent O(5)Li3Ti2V octahedra, edges with four equivalent O(1)Li3TiV2 octahedra, and edges with four equivalent O(2)Li3TiV2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the fourth O site, O(4) is bonded to one Li(3), two equivalent Li(1), two equivalent Ti(1), and one V(2) atom to form OLi3Ti2V octahedra that share  a cornercorner with one O(4)Li3Ti2V octahedra, corners with five equivalent O(5)Li3Ti2V octahedra, edges with four equivalent O(3)Li3Ti2V octahedra, edges with four equivalent O(1)Li3TiV2 octahedra, and edges with four equivalent O(2)Li3TiV2 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the fifth O site, O(5) is bonded to one Li(3), two equivalent Li(1), two equivalent Ti(1), and one V(3) atom to form OLi3Ti2V octahedra that share  a cornercorner with one O(5)Li3Ti2V octahedra, corners with five equivalent O(4)Li3Ti2V octahedra, edges with four equivalent O(3)Li3Ti2V octahedra, edges with four equivalent O(1)Li3TiV2 octahedra, and edges with four equivalent O(2)Li3TiV2 octahedra. The corner-sharing octahedral tilt angles range from 0-4°.
Li2TiVO4 is alpha Po-derived structured and crystallizes in the tetragonal I-42m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with four equivalent Li(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-3°. The Li(1)-O(1) bond length is 2.27 Å. The Li(1)-O(2) bond length is 2.30 Å. The Li(1)-O(4) bond length is 2.06 Å. The Li(1)-O(5) bond length is 2.08 Å. Both Li(1)-O(3) bond lengths are 2.07 Å. In the second Li site, Li(2) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. Both Li(2)-O(3) bond lengths are 2.16 Å. All Li(2)-O(2) bond lengths are 2.07 Å. In the third Li site, Li(3) is bonded to one O(4), one O(5), and four equivalent O(1) atoms to form LiO6 octahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, edges with four equivalent Ti(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. The Li(3)-O(4) bond length is 2.16 Å. The Li(3)-O(5) bond length is 2.17 Å. There are two shorter (2.06 Å) and two longer (2.08 Å) Li(3)-O(1) bond lengths. Ti(1) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent O(3) atoms to form TiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Ti(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-4°. The Ti(1)-O(1) bond length is 1.97 Å. The Ti(1)-O(2) bond length is 2.04 Å. The Ti(1)-O(4) bond length is 2.08 Å. The Ti(1)-O(5) bond length is 2.05 Å. Both Ti(1)-O(3) bond lengths are 2.07 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent V(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. Both V(1)-O(3) bond lengths are 2.12 Å. All V(1)-O(1) bond lengths are 2.07 Å. In the second V site, V(2) is bonded to two equivalent O(4) and four equivalent O(2) atoms to form VO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent V(3)O6 octahedra, edges with four equivalent Li(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°. Both V(2)-O(4) bond lengths are 2.11 Å. All V(2)-O(2) bond lengths are 2.02 Å. In the third V site, V(3) is bonded to two equivalent O(5) and four equivalent O(2) atoms to form VO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent V(2)O6 octahedra, edges with four equivalent Li(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°. Both V(3)-O(5) bond lengths are 2.13 Å. All V(3)-O(2) bond lengths are 2.13 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(3), one Ti(1), and two equivalent V(1) atoms to form OLi3TiV2 octahedra that share corners with two equivalent O(2)Li3TiV2 octahedra, corners with four equivalent O(1)Li3TiV2 octahedra, edges with two equivalent O(4)Li3Ti2V octahedra, edges with two equivalent O(5)Li3Ti2V octahedra, edges with four equivalent O(3)Li3Ti2V octahedra, and edges with four equivalent O(1)Li3TiV2 octahedra. The corner-sharing octahedral tilt angles range from 1-8°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), one Ti(1), one V(2), and one V(3) atom to form OLi3TiV2 octahedra that share corners with two equivalent O(1)Li3TiV2 octahedra, corners with four equivalent O(2)Li3TiV2 octahedra, edges with two equivalent O(4)Li3Ti2V octahedra, edges with two equivalent O(5)Li3Ti2V octahedra, edges with four equivalent O(3)Li3Ti2V octahedra, and edges with four equivalent O(2)Li3TiV2 octahedra. The corner-sharing octahedral tilt angles range from 1-9°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), two equivalent Ti(1), and one V(1) atom to form OLi3Ti2V octahedra that share corners with six equivalent O(3)Li3Ti2V octahedra, edges with two equivalent O(4)Li3Ti2V octahedra, edges with two equivalent O(5)Li3Ti2V octahedra, edges with four equivalent O(1)Li3TiV2 octahedra, and edges with four equivalent O(2)Li3TiV2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the fourth O site, O(4) is bonded to one Li(3), two equivalent Li(1), two equivalent Ti(1), and one V(2) atom to form OLi3Ti2V octahedra that share  a cornercorner with one O(4)Li3Ti2V octahedra, corners with five equivalent O(5)Li3Ti2V octahedra, edges with four equivalent O(3)Li3Ti2V octahedra, edges with four equivalent O(1)Li3TiV2 octahedra, and edges with four equivalent O(2)Li3TiV2 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the fifth O site, O(5) is bonded to one Li(3), two equivalent Li(1), two equivalent Ti(1), and one V(3) atom to form OLi3Ti2V octahedra that share  a cornercorner with one O(5)Li3Ti2V octahedra, corners with five equivalent O(4)Li3Ti2V octahedra, edges with four equivalent O(3)Li3Ti2V octahedra, edges with four equivalent O(1)Li3TiV2 octahedra, and edges with four equivalent O(2)Li3TiV2 octahedra. The corner-sharing octahedral tilt angles range from 0-4°.