Li3Ti3VO8 crystallizes in the monoclinic P2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(4) and four 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 four equivalent Li(3)O6 octahedra, and edges with four equivalent Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. In the second Li site, Li(2) is bonded to two equivalent O(3) and four equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with four equivalent V(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. In the third Li site, Li(3) 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 LiO6 octahedra that share corners with six equivalent Ti(3)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,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, and edges with two equivalent Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(1) and four equivalent O(6) atoms to form TiO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Ti(3)O6 octahedra. In the second Ti site, Ti(2) is bonded to two equivalent O(2) and four equivalent O(5) atoms to form TiO6 octahedra that share edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Ti(3)O6 octahedra. In the third Ti site, Ti(3) 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 six equivalent Li(3)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,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, and edges with two equivalent Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(4) and four equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. In the second V site, V(2) is bonded to two equivalent O(3) and four equivalent O(6) 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 Ti(1)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. There are six inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(3), one Ti(1), and two equivalent Ti(3) atoms to form OLi2Ti3 square pyramids that share  a cornercorner with one O(1)Li2Ti3 square pyramid, corners with four equivalent O(5)Li2Ti2V square pyramids, corners with four equivalent O(2)Li2Ti3 square pyramids, edges with two equivalent O(3)Li3Ti2V octahedra, edges with two equivalent O(4)Li3Ti2V octahedra, and edges with four equivalent O(6)Li2Ti2V square pyramids. In the second O site, O(2) is bonded to two equivalent Li(3), one Ti(2), and two equivalent Ti(3) atoms to form OLi2Ti3 square pyramids that share  a cornercorner with one O(2)Li2Ti3 square pyramid, corners with four equivalent O(6)Li2Ti2V square pyramids, corners with four equivalent O(1)Li2Ti3 square pyramids, edges with two equivalent O(3)Li3Ti2V octahedra, edges with two equivalent O(4)Li3Ti2V octahedra, and edges with four equivalent O(5)Li2Ti2V square pyramids. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(3), two equivalent Ti(3), and one V(2) atom to form OLi3Ti2V octahedra that share corners with two equivalent O(3)Li3Ti2V octahedra, corners with four equivalent O(4)Li3Ti2V octahedra, edges with two equivalent O(1)Li2Ti3 square pyramids, edges with two equivalent O(2)Li2Ti3 square pyramids, edges with four equivalent O(5)Li2Ti2V square pyramids, and edges with four equivalent O(6)Li2Ti2V square pyramids. The corner-sharing octahedral tilt angles range from 0-1°. In the fourth O site, O(4) is bonded to one Li(1), two equivalent Li(3), two equivalent Ti(3), and one V(1) atom to form OLi3Ti2V octahedra that share corners with two equivalent O(4)Li3Ti2V octahedra, corners with four equivalent O(3)Li3Ti2V octahedra, edges with two equivalent O(1)Li2Ti3 square pyramids, edges with two equivalent O(2)Li2Ti3 square pyramids, edges with four equivalent O(5)Li2Ti2V square pyramids, and edges with four equivalent O(6)Li2Ti2V square pyramids. The corner-sharing octahedral tilt angles range from 0-1°. In the fifth O site, O(5) is bonded to one Li(2), one Li(3), one Ti(2), one Ti(3), and one V(1) atom to form OLi2Ti2V square pyramids that share corners with two equivalent O(6)Li2Ti2V square pyramids, corners with two equivalent O(1)Li2Ti3 square pyramids, corners with five equivalent O(5)Li2Ti2V square pyramids, edges with two equivalent O(3)Li3Ti2V octahedra, edges with two equivalent O(4)Li3Ti2V octahedra, edges with two equivalent O(5)Li2Ti2V square pyramids, and edges with two equivalent O(2)Li2Ti3 square pyramids. In the sixth O site, O(6) is bonded to one Li(1), one Li(3), one Ti(1), one Ti(3), and one V(2) atom to form OLi2Ti2V square pyramids that share corners with two equivalent O(5)Li2Ti2V square pyramids, corners with two equivalent O(2)Li2Ti3 square pyramids, corners with five equivalent O(6)Li2Ti2V square pyramids, edges with two equivalent O(3)Li3Ti2V octahedra, edges with two equivalent O(4)Li3Ti2V octahedra, edges with two equivalent O(6)Li2Ti2V square pyramids, and edges with two equivalent O(1)Li2Ti3 square pyramids.
Li3Ti3VO8 crystallizes in the monoclinic P2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(4) and four 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 four equivalent Li(3)O6 octahedra, and edges with four equivalent Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. Both Li(1)-O(4) bond lengths are 2.10 Å. All Li(1)-O(6) bond lengths are 2.15 Å. In the second Li site, Li(2) is bonded to two equivalent O(3) and four equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with four equivalent V(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. Both Li(2)-O(3) bond lengths are 2.12 Å. All Li(2)-O(5) bond lengths are 2.14 Å. In the third Li site, Li(3) 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 LiO6 octahedra that share corners with six equivalent Ti(3)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,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, and edges with two equivalent Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. The Li(3)-O(1) bond length is 2.20 Å. The Li(3)-O(2) bond length is 2.20 Å. The Li(3)-O(3) bond length is 2.21 Å. The Li(3)-O(4) bond length is 2.20 Å. The Li(3)-O(5) bond length is 2.22 Å. The Li(3)-O(6) bond length is 2.23 Å. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(1) and four equivalent O(6) atoms to form TiO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Ti(3)O6 octahedra. Both Ti(1)-O(1) bond lengths are 2.00 Å. All Ti(1)-O(6) bond lengths are 1.98 Å. In the second Ti site, Ti(2) is bonded to two equivalent O(2) and four equivalent O(5) atoms to form TiO6 octahedra that share edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Ti(3)O6 octahedra. Both Ti(2)-O(2) bond lengths are 2.00 Å. All Ti(2)-O(5) bond lengths are 1.98 Å. In the third Ti site, Ti(3) 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 six equivalent Li(3)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,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, and edges with two equivalent Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. The Ti(3)-O(1) bond length is 2.05 Å. The Ti(3)-O(2) bond length is 2.06 Å. The Ti(3)-O(3) bond length is 2.05 Å. The Ti(3)-O(4) bond length is 2.05 Å. The Ti(3)-O(5) bond length is 2.00 Å. The Ti(3)-O(6) bond length is 2.01 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(4) and four equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. Both V(1)-O(4) bond lengths are 2.12 Å. All V(1)-O(5) bond lengths are 2.12 Å. In the second V site, V(2) is bonded to two equivalent O(3) and four equivalent O(6) 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 Ti(1)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. Both V(2)-O(3) bond lengths are 2.11 Å. All V(2)-O(6) bond lengths are 2.12 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(3), one Ti(1), and two equivalent Ti(3) atoms to form OLi2Ti3 square pyramids that share  a cornercorner with one O(1)Li2Ti3 square pyramid, corners with four equivalent O(5)Li2Ti2V square pyramids, corners with four equivalent O(2)Li2Ti3 square pyramids, edges with two equivalent O(3)Li3Ti2V octahedra, edges with two equivalent O(4)Li3Ti2V octahedra, and edges with four equivalent O(6)Li2Ti2V square pyramids. In the second O site, O(2) is bonded to two equivalent Li(3), one Ti(2), and two equivalent Ti(3) atoms to form OLi2Ti3 square pyramids that share  a cornercorner with one O(2)Li2Ti3 square pyramid, corners with four equivalent O(6)Li2Ti2V square pyramids, corners with four equivalent O(1)Li2Ti3 square pyramids, edges with two equivalent O(3)Li3Ti2V octahedra, edges with two equivalent O(4)Li3Ti2V octahedra, and edges with four equivalent O(5)Li2Ti2V square pyramids. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(3), two equivalent Ti(3), and one V(2) atom to form OLi3Ti2V octahedra that share corners with two equivalent O(3)Li3Ti2V octahedra, corners with four equivalent O(4)Li3Ti2V octahedra, edges with two equivalent O(1)Li2Ti3 square pyramids, edges with two equivalent O(2)Li2Ti3 square pyramids, edges with four equivalent O(5)Li2Ti2V square pyramids, and edges with four equivalent O(6)Li2Ti2V square pyramids. The corner-sharing octahedral tilt angles range from 0-1°. In the fourth O site, O(4) is bonded to one Li(1), two equivalent Li(3), two equivalent Ti(3), and one V(1) atom to form OLi3Ti2V octahedra that share corners with two equivalent O(4)Li3Ti2V octahedra, corners with four equivalent O(3)Li3Ti2V octahedra, edges with two equivalent O(1)Li2Ti3 square pyramids, edges with two equivalent O(2)Li2Ti3 square pyramids, edges with four equivalent O(5)Li2Ti2V square pyramids, and edges with four equivalent O(6)Li2Ti2V square pyramids. The corner-sharing octahedral tilt angles range from 0-1°. In the fifth O site, O(5) is bonded to one Li(2), one Li(3), one Ti(2), one Ti(3), and one V(1) atom to form OLi2Ti2V square pyramids that share corners with two equivalent O(6)Li2Ti2V square pyramids, corners with two equivalent O(1)Li2Ti3 square pyramids, corners with five equivalent O(5)Li2Ti2V square pyramids, edges with two equivalent O(3)Li3Ti2V octahedra, edges with two equivalent O(4)Li3Ti2V octahedra, edges with two equivalent O(5)Li2Ti2V square pyramids, and edges with two equivalent O(2)Li2Ti3 square pyramids. In the sixth O site, O(6) is bonded to one Li(1), one Li(3), one Ti(1), one Ti(3), and one V(2) atom to form OLi2Ti2V square pyramids that share corners with two equivalent O(5)Li2Ti2V square pyramids, corners with two equivalent O(2)Li2Ti3 square pyramids, corners with five equivalent O(6)Li2Ti2V square pyramids, edges with two equivalent O(3)Li3Ti2V octahedra, edges with two equivalent O(4)Li3Ti2V octahedra, edges with two equivalent O(6)Li2Ti2V square pyramids, and edges with two equivalent O(1)Li2Ti3 square pyramids.