LiTi2O4 crystallizes in the orthorhombic Imm2 space group. Li(1) is bonded to one O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO5 trigonal bipyramids that share  a cornercorner with one Ti(2)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with four equivalent Li(1)O5 trigonal bipyramids, edges with two equivalent Ti(1)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-71°. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form TiO6 octahedra that share corners with four equivalent Ti(1)O6 octahedra, corners with two equivalent Li(1)O5 trigonal bipyramids, edges with four equivalent Ti(2)O6 octahedra, and edges with two equivalent Li(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 3-23°. 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 TiO6 octahedra that share corners with four equivalent Ti(2)O6 octahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid, edges with four equivalent Ti(1)O6 octahedra, and edges with four equivalent Li(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 2-24°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Ti(2) and two equivalent Ti(1) atoms. In the second O site, O(2) is bonded in a square co-planar geometry to one Li(1), one Ti(2), and two equivalent Ti(1) atoms. 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 a mixture of corner and edge-sharing OLi2Ti3 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 a mixture of corner and edge-sharing OLi2Ti3 trigonal bipyramids.
LiTi2O4 crystallizes in the orthorhombic Imm2 space group. Li(1) is bonded to one O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO5 trigonal bipyramids that share  a cornercorner with one Ti(2)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with four equivalent Li(1)O5 trigonal bipyramids, edges with two equivalent Ti(1)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-71°. The Li(1)-O(2) bond length is 1.98 Å. Both Li(1)-O(3) bond lengths are 2.03 Å. Both Li(1)-O(4) bond lengths are 2.04 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form TiO6 octahedra that share corners with four equivalent Ti(1)O6 octahedra, corners with two equivalent Li(1)O5 trigonal bipyramids, edges with four equivalent Ti(2)O6 octahedra, and edges with two equivalent Li(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 3-23°. The Ti(1)-O(3) bond length is 1.98 Å. The Ti(1)-O(4) bond length is 2.14 Å. Both Ti(1)-O(1) bond lengths are 1.96 Å. Both Ti(1)-O(2) bond lengths are 2.03 Å. 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 TiO6 octahedra that share corners with four equivalent Ti(2)O6 octahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid, edges with four equivalent Ti(1)O6 octahedra, and edges with four equivalent Li(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 2-24°. The Ti(2)-O(1) bond length is 2.15 Å. The Ti(2)-O(2) bond length is 1.96 Å. Both Ti(2)-O(3) bond lengths are 2.03 Å. Both Ti(2)-O(4) bond lengths are 1.96 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Ti(2) and two equivalent Ti(1) atoms. In the second O site, O(2) is bonded in a square co-planar geometry to one Li(1), one Ti(2), and two equivalent Ti(1) atoms. 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 a mixture of corner and edge-sharing OLi2Ti3 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 a mixture of corner and edge-sharing OLi2Ti3 trigonal bipyramids.