LiTi2O4 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to one O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO5 square pyramids that share  a cornercorner with one Ti(2)O6 octahedra, corners with two equivalent Li(1)O5 square pyramids, edges with four equivalent Ti(2)O6 octahedra, and  an edgeedge with one Li(1)O5 square pyramid. The corner-sharing octahedral tilt angles are 8°. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(4), and three equivalent O(2) atoms. In the second Ti site, Ti(2) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form distorted TiO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra,  a cornercorner with one Li(1)O5 square pyramid,  an edgeedge with one Ti(2)O6 octahedra, and edges with four equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles are 13°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to one Ti(1) and one Ti(2) atom. In the second O site, O(2) is bonded to one Li(1), one Ti(2), and three equivalent Ti(1) atoms to form OLiTi4 trigonal bipyramids that share  a cornercorner with one O(3)Li2Ti3 square pyramid,  a cornercorner with one O(4)Li2Ti3 trigonal bipyramid, corners with two equivalent O(2)LiTi4 trigonal bipyramids, edges with three equivalent O(3)Li2Ti3 square pyramids, edges with two equivalent O(2)LiTi4 trigonal bipyramids, and edges with three equivalent O(4)Li2Ti3 trigonal bipyramids. In the third O site, O(3) is bonded to two equivalent Li(1), one Ti(1), and two equivalent Ti(2) atoms to form OLi2Ti3 square pyramids that share corners with two equivalent O(3)Li2Ti3 square pyramids,  a cornercorner with one O(4)Li2Ti3 trigonal bipyramid,  a cornercorner with one O(2)LiTi4 trigonal bipyramid,  an edgeedge with one O(3)Li2Ti3 square pyramid, edges with three equivalent O(2)LiTi4 trigonal bipyramids, and edges with four equivalent O(4)Li2Ti3 trigonal bipyramids. In the fourth O site, O(4) is bonded to two equivalent Li(1), one Ti(1), and two equivalent Ti(2) atoms to form OLi2Ti3 trigonal bipyramids that share  a cornercorner with one O(3)Li2Ti3 square pyramid,  a cornercorner with one O(2)LiTi4 trigonal bipyramid, corners with two equivalent O(4)Li2Ti3 trigonal bipyramids, edges with four equivalent O(3)Li2Ti3 square pyramids,  an edgeedge with one O(4)Li2Ti3 trigonal bipyramid, and edges with three equivalent O(2)LiTi4 trigonal bipyramids.
LiTi2O4 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to one O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO5 square pyramids that share  a cornercorner with one Ti(2)O6 octahedra, corners with two equivalent Li(1)O5 square pyramids, edges with four equivalent Ti(2)O6 octahedra, and  an edgeedge with one Li(1)O5 square pyramid. The corner-sharing octahedral tilt angles are 8°. The Li(1)-O(2) bond length is 2.05 Å. There is one shorter (2.03 Å) and one longer (2.05 Å) Li(1)-O(3) bond length. Both Li(1)-O(4) bond lengths are 2.01 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(4), and three equivalent O(2) atoms. The Ti(1)-O(1) bond length is 1.80 Å. The Ti(1)-O(3) bond length is 2.04 Å. The Ti(1)-O(4) bond length is 2.00 Å. There are two shorter (2.04 Å) and one longer (2.34 Å) Ti(1)-O(2) bond length. In the second Ti site, Ti(2) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form distorted TiO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra,  a cornercorner with one Li(1)O5 square pyramid,  an edgeedge with one Ti(2)O6 octahedra, and edges with four equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles are 13°. The Ti(2)-O(1) bond length is 1.85 Å. The Ti(2)-O(2) bond length is 2.05 Å. Both Ti(2)-O(3) bond lengths are 2.02 Å. There is one shorter (2.01 Å) and one longer (2.21 Å) Ti(2)-O(4) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to one Ti(1) and one Ti(2) atom. In the second O site, O(2) is bonded to one Li(1), one Ti(2), and three equivalent Ti(1) atoms to form OLiTi4 trigonal bipyramids that share  a cornercorner with one O(3)Li2Ti3 square pyramid,  a cornercorner with one O(4)Li2Ti3 trigonal bipyramid, corners with two equivalent O(2)LiTi4 trigonal bipyramids, edges with three equivalent O(3)Li2Ti3 square pyramids, edges with two equivalent O(2)LiTi4 trigonal bipyramids, and edges with three equivalent O(4)Li2Ti3 trigonal bipyramids. In the third O site, O(3) is bonded to two equivalent Li(1), one Ti(1), and two equivalent Ti(2) atoms to form OLi2Ti3 square pyramids that share corners with two equivalent O(3)Li2Ti3 square pyramids,  a cornercorner with one O(4)Li2Ti3 trigonal bipyramid,  a cornercorner with one O(2)LiTi4 trigonal bipyramid,  an edgeedge with one O(3)Li2Ti3 square pyramid, edges with three equivalent O(2)LiTi4 trigonal bipyramids, and edges with four equivalent O(4)Li2Ti3 trigonal bipyramids. In the fourth O site, O(4) is bonded to two equivalent Li(1), one Ti(1), and two equivalent Ti(2) atoms to form OLi2Ti3 trigonal bipyramids that share  a cornercorner with one O(3)Li2Ti3 square pyramid,  a cornercorner with one O(2)LiTi4 trigonal bipyramid, corners with two equivalent O(4)Li2Ti3 trigonal bipyramids, edges with four equivalent O(3)Li2Ti3 square pyramids,  an edgeedge with one O(4)Li2Ti3 trigonal bipyramid, and edges with three equivalent O(2)LiTi4 trigonal bipyramids.