Li2Ti3O7 crystallizes in the monoclinic C2/c space group. Li(1) is bonded to one O(2), one O(3), one O(4), and two equivalent O(1) atoms to form distorted LiO5 trigonal bipyramids that share corners with two equivalent Ti(1)O6 octahedra, corners with three equivalent Li(1)O5 trigonal bipyramids, corners with five equivalent Ti(2)O5 trigonal bipyramids,  an edgeedge with one Ti(1)O6 octahedra, and  an edgeedge with one Ti(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 59-65°. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form TiO6 octahedra that share corners with four equivalent Li(1)O5 trigonal bipyramids, corners with four equivalent Ti(2)O5 trigonal bipyramids, edges with two equivalent Li(1)O5 trigonal bipyramids, and edges with two equivalent Ti(2)O5 trigonal bipyramids. In the second Ti site, Ti(2) is bonded to one O(1), one O(3), one O(4), and two equivalent O(2) atoms to form distorted TiO5 trigonal bipyramids that share corners with two equivalent Ti(1)O6 octahedra,  a cornercorner with one Ti(2)O5 trigonal bipyramid, corners with five equivalent Li(1)O5 trigonal bipyramids,  an edgeedge with one Ti(1)O6 octahedra,  an edgeedge with one Li(1)O5 trigonal bipyramid, and  an edgeedge with one Ti(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 27-58°. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Ti(1), and one Ti(2) atom to form OLi2Ti2 tetrahedra that share corners with three equivalent O(1)Li2Ti2 tetrahedra, corners with three equivalent O(4)Li2Ti2 tetrahedra, corners with four equivalent O(2)LiTi3 trigonal pyramids, and  an edgeedge with one O(2)LiTi3 trigonal pyramid. In the second O site, O(2) is bonded to one Li(1), one Ti(1), and two equivalent Ti(2) atoms to form OLiTi3 trigonal pyramids that share corners with three equivalent O(4)Li2Ti2 tetrahedra, corners with four equivalent O(1)Li2Ti2 tetrahedra,  a cornercorner with one O(2)LiTi3 trigonal pyramid,  an edgeedge with one O(1)Li2Ti2 tetrahedra, and  an edgeedge with one O(2)LiTi3 trigonal pyramid. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Li(1), one Ti(1), and one Ti(2) atom. In the fourth O site, O(4) is bonded to two equivalent Li(1) and two equivalent Ti(2) atoms to form OLi2Ti2 tetrahedra that share corners with six equivalent O(1)Li2Ti2 tetrahedra and corners with six equivalent O(2)LiTi3 trigonal pyramids.
Li2Ti3O7 crystallizes in the monoclinic C2/c space group. Li(1) is bonded to one O(2), one O(3), one O(4), and two equivalent O(1) atoms to form distorted LiO5 trigonal bipyramids that share corners with two equivalent Ti(1)O6 octahedra, corners with three equivalent Li(1)O5 trigonal bipyramids, corners with five equivalent Ti(2)O5 trigonal bipyramids,  an edgeedge with one Ti(1)O6 octahedra, and  an edgeedge with one Ti(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 59-65°. The Li(1)-O(2) bond length is 2.13 Å. The Li(1)-O(3) bond length is 2.23 Å. The Li(1)-O(4) bond length is 2.27 Å. There is one shorter (2.09 Å) and one longer (2.14 Å) Li(1)-O(1) bond length. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form TiO6 octahedra that share corners with four equivalent Li(1)O5 trigonal bipyramids, corners with four equivalent Ti(2)O5 trigonal bipyramids, edges with two equivalent Li(1)O5 trigonal bipyramids, and edges with two equivalent Ti(2)O5 trigonal bipyramids. Both Ti(1)-O(1) bond lengths are 2.05 Å. Both Ti(1)-O(2) bond lengths are 2.02 Å. Both Ti(1)-O(3) bond lengths are 1.87 Å. In the second Ti site, Ti(2) is bonded to one O(1), one O(3), one O(4), and two equivalent O(2) atoms to form distorted TiO5 trigonal bipyramids that share corners with two equivalent Ti(1)O6 octahedra,  a cornercorner with one Ti(2)O5 trigonal bipyramid, corners with five equivalent Li(1)O5 trigonal bipyramids,  an edgeedge with one Ti(1)O6 octahedra,  an edgeedge with one Li(1)O5 trigonal bipyramid, and  an edgeedge with one Ti(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 27-58°. The Ti(2)-O(1) bond length is 1.86 Å. The Ti(2)-O(3) bond length is 1.82 Å. The Ti(2)-O(4) bond length is 1.91 Å. There is one shorter (1.89 Å) and one longer (2.16 Å) Ti(2)-O(2) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Ti(1), and one Ti(2) atom to form OLi2Ti2 tetrahedra that share corners with three equivalent O(1)Li2Ti2 tetrahedra, corners with three equivalent O(4)Li2Ti2 tetrahedra, corners with four equivalent O(2)LiTi3 trigonal pyramids, and  an edgeedge with one O(2)LiTi3 trigonal pyramid. In the second O site, O(2) is bonded to one Li(1), one Ti(1), and two equivalent Ti(2) atoms to form OLiTi3 trigonal pyramids that share corners with three equivalent O(4)Li2Ti2 tetrahedra, corners with four equivalent O(1)Li2Ti2 tetrahedra,  a cornercorner with one O(2)LiTi3 trigonal pyramid,  an edgeedge with one O(1)Li2Ti2 tetrahedra, and  an edgeedge with one O(2)LiTi3 trigonal pyramid. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Li(1), one Ti(1), and one Ti(2) atom. In the fourth O site, O(4) is bonded to two equivalent Li(1) and two equivalent Ti(2) atoms to form OLi2Ti2 tetrahedra that share corners with six equivalent O(1)Li2Ti2 tetrahedra and corners with six equivalent O(2)LiTi3 trigonal pyramids.