Li2Ti3O7 crystallizes in the monoclinic P2_1/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(4), and two equivalent O(1) atoms to form LiO4 trigonal pyramids that share corners with three equivalent Ti(1)O6 octahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid, corners with two equivalent Li(1)O4 trigonal pyramids,  an edgeedge with one Ti(2)O6 octahedra, and edges with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 17-81°. In the second Li site, Li(2) is bonded to one O(1), one O(2), and three equivalent O(3) atoms to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Li(2)O5 trigonal bipyramids,  a cornercorner with one Li(1)O4 trigonal pyramid,  an edgeedge with one Ti(2)O6 octahedra, edges with two equivalent Li(2)O5 trigonal bipyramids, and edges with two equivalent Li(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 9-70°. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(1), one O(4), one O(5), and three equivalent O(7) atoms to form distorted TiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid, corners with three equivalent Li(1)O4 trigonal pyramids,  an edgeedge with one Ti(2)O6 octahedra, and edges with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles are 32°. In the second Ti site, Ti(2) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(6) atoms to form distorted TiO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Li(2)O5 trigonal bipyramids,  an edgeedge with one Ti(1)O6 octahedra,  an edgeedge with one Li(2)O5 trigonal bipyramid, and  an edgeedge with one Li(1)O4 trigonal pyramid. The corner-sharing octahedral tilt angles are 32°. In the third Ti site, Ti(3) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(6), one O(7), and two equivalent O(5) atoms. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Li(2), two equivalent Li(1), one Ti(1), and one Ti(3) atom. In the second O site, O(2) is bonded in a T-shaped geometry to one Li(2), one Ti(2), and one Ti(3) atom. In the third O site, O(3) is bonded to one Li(1), three equivalent Li(2), and one Ti(2) atom to form OLi4Ti trigonal bipyramids that share corners with two equivalent O(3)Li4Ti trigonal bipyramids,  a cornercorner with one O(5)Ti4 trigonal pyramid, and edges with two equivalent O(3)Li4Ti trigonal bipyramids. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(1), one Ti(1), and one Ti(2) atom. In the fifth O site, O(5) is bonded to one Ti(1), one Ti(2), and two equivalent Ti(3) atoms to form distorted OTi4 trigonal pyramids that share  a cornercorner with one O(3)Li4Ti trigonal bipyramid,  a cornercorner with one O(7)Ti4 trigonal pyramid, corners with two equivalent O(5)Ti4 trigonal pyramids, and edges with two equivalent O(7)Ti4 trigonal pyramids. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Ti(3) and two equivalent Ti(2) atoms. In the seventh O site, O(7) is bonded to one Ti(3) and three equivalent Ti(1) atoms to form a mixture of distorted corner and edge-sharing OTi4 trigonal pyramids.
Li2Ti3O7 crystallizes in the monoclinic P2_1/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(4), and two equivalent O(1) atoms to form LiO4 trigonal pyramids that share corners with three equivalent Ti(1)O6 octahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid, corners with two equivalent Li(1)O4 trigonal pyramids,  an edgeedge with one Ti(2)O6 octahedra, and edges with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 17-81°. The Li(1)-O(3) bond length is 1.95 Å. The Li(1)-O(4) bond length is 1.95 Å. Both Li(1)-O(1) bond lengths are 2.15 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), and three equivalent O(3) atoms to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Li(2)O5 trigonal bipyramids,  a cornercorner with one Li(1)O4 trigonal pyramid,  an edgeedge with one Ti(2)O6 octahedra, edges with two equivalent Li(2)O5 trigonal bipyramids, and edges with two equivalent Li(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 9-70°. The Li(2)-O(1) bond length is 2.44 Å. The Li(2)-O(2) bond length is 1.95 Å. There are two shorter (2.00 Å) and one longer (2.05 Å) Li(2)-O(3) bond length. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(1), one O(4), one O(5), and three equivalent O(7) atoms to form distorted TiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid, corners with three equivalent Li(1)O4 trigonal pyramids,  an edgeedge with one Ti(2)O6 octahedra, and edges with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles are 32°. The Ti(1)-O(1) bond length is 1.88 Å. The Ti(1)-O(4) bond length is 1.79 Å. The Ti(1)-O(5) bond length is 2.16 Å. There are two shorter (1.94 Å) and one longer (2.19 Å) Ti(1)-O(7) bond length. In the second Ti site, Ti(2) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(6) atoms to form distorted TiO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Li(2)O5 trigonal bipyramids,  an edgeedge with one Ti(1)O6 octahedra,  an edgeedge with one Li(2)O5 trigonal bipyramid, and  an edgeedge with one Li(1)O4 trigonal pyramid. The corner-sharing octahedral tilt angles are 32°. The Ti(2)-O(2) bond length is 1.98 Å. The Ti(2)-O(3) bond length is 1.78 Å. The Ti(2)-O(4) bond length is 2.02 Å. The Ti(2)-O(5) bond length is 2.26 Å. Both Ti(2)-O(6) bond lengths are 1.94 Å. In the third Ti site, Ti(3) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(6), one O(7), and two equivalent O(5) atoms. The Ti(3)-O(1) bond length is 1.99 Å. The Ti(3)-O(2) bond length is 1.76 Å. The Ti(3)-O(6) bond length is 2.01 Å. The Ti(3)-O(7) bond length is 2.28 Å. Both Ti(3)-O(5) bond lengths are 1.94 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Li(2), two equivalent Li(1), one Ti(1), and one Ti(3) atom. In the second O site, O(2) is bonded in a T-shaped geometry to one Li(2), one Ti(2), and one Ti(3) atom. In the third O site, O(3) is bonded to one Li(1), three equivalent Li(2), and one Ti(2) atom to form OLi4Ti trigonal bipyramids that share corners with two equivalent O(3)Li4Ti trigonal bipyramids,  a cornercorner with one O(5)Ti4 trigonal pyramid, and edges with two equivalent O(3)Li4Ti trigonal bipyramids. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(1), one Ti(1), and one Ti(2) atom. In the fifth O site, O(5) is bonded to one Ti(1), one Ti(2), and two equivalent Ti(3) atoms to form distorted OTi4 trigonal pyramids that share  a cornercorner with one O(3)Li4Ti trigonal bipyramid,  a cornercorner with one O(7)Ti4 trigonal pyramid, corners with two equivalent O(5)Ti4 trigonal pyramids, and edges with two equivalent O(7)Ti4 trigonal pyramids. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Ti(3) and two equivalent Ti(2) atoms. In the seventh O site, O(7) is bonded to one Ti(3) and three equivalent Ti(1) atoms to form a mixture of distorted corner and edge-sharing OTi4 trigonal pyramids.