Li4Ti5VO12 crystallizes in the monoclinic C2/m space group. Li(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(2) atoms. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form edge-sharing TiO6 octahedra. In the second Ti site, Ti(2) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form TiO6 octahedra that share edges with three equivalent Ti(2)O6 octahedra and edges with three equivalent V(1)O6 octahedra. In the third Ti site, Ti(3) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form edge-sharing TiO6 octahedra. V(1) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form VO6 octahedra that share edges with six equivalent Ti(2)O6 octahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent Ti(2), and one V(1) atom to form OLi2Ti2V trigonal bipyramids that share corners with two equivalent O(2)Li2Ti3 trigonal bipyramids, corners with three equivalent O(1)Li2Ti2V trigonal bipyramids,  an edgeedge with one O(2)Li2Ti3 trigonal bipyramid, and edges with four equivalent O(1)Li2Ti2V trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Li(1), one Ti(3), and two equivalent Ti(1) atoms to form OLi2Ti3 trigonal bipyramids that share corners with two equivalent O(1)Li2Ti2V trigonal bipyramids, corners with three equivalent O(2)Li2Ti3 trigonal bipyramids,  an edgeedge with one O(1)Li2Ti2V trigonal bipyramid, and edges with four equivalent O(2)Li2Ti3 trigonal bipyramids. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Ti(3) and two equivalent Ti(1) atoms. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to two equivalent Ti(2) and one V(1) atom.
Li4Ti5VO12 crystallizes in the monoclinic C2/m space group. Li(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(2) atoms. There is one shorter (1.99 Å) and one longer (2.06 Å) Li(1)-O(1) bond length. There is one shorter (1.98 Å) and one longer (2.10 Å) Li(1)-O(2) bond length. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form edge-sharing TiO6 octahedra. Both Ti(1)-O(3) bond lengths are 1.96 Å. There are two shorter (2.02 Å) and two longer (2.03 Å) Ti(1)-O(2) bond lengths. In the second Ti site, Ti(2) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form TiO6 octahedra that share edges with three equivalent Ti(2)O6 octahedra and edges with three equivalent V(1)O6 octahedra. Both Ti(2)-O(4) bond lengths are 1.94 Å. There are two shorter (2.00 Å) and two longer (2.01 Å) Ti(2)-O(1) bond lengths. In the third Ti site, Ti(3) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form edge-sharing TiO6 octahedra. Both Ti(3)-O(3) bond lengths are 2.03 Å. All Ti(3)-O(2) bond lengths are 2.09 Å. V(1) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form VO6 octahedra that share edges with six equivalent Ti(2)O6 octahedra. Both V(1)-O(4) bond lengths are 2.05 Å. All V(1)-O(1) bond lengths are 2.13 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent Ti(2), and one V(1) atom to form OLi2Ti2V trigonal bipyramids that share corners with two equivalent O(2)Li2Ti3 trigonal bipyramids, corners with three equivalent O(1)Li2Ti2V trigonal bipyramids,  an edgeedge with one O(2)Li2Ti3 trigonal bipyramid, and edges with four equivalent O(1)Li2Ti2V trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Li(1), one Ti(3), and two equivalent Ti(1) atoms to form OLi2Ti3 trigonal bipyramids that share corners with two equivalent O(1)Li2Ti2V trigonal bipyramids, corners with three equivalent O(2)Li2Ti3 trigonal bipyramids,  an edgeedge with one O(1)Li2Ti2V trigonal bipyramid, and edges with four equivalent O(2)Li2Ti3 trigonal bipyramids. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Ti(3) and two equivalent Ti(1) atoms. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to two equivalent Ti(2) and one V(1) atom.