LiTi2O4 crystallizes in the monoclinic P2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(8), two equivalent O(4), and two equivalent O(6) atoms to form distorted LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra,  an edgeedge with one Ti(4)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-17°. In the second Li site, Li(2) is bonded to one O(2), one O(6), two equivalent O(1), and two equivalent O(8) atoms to form distorted LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Ti(2)O6 octahedra,  an edgeedge with one Ti(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Ti(4)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-18°. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(4), one O(7), two equivalent O(1), and two equivalent O(8) atoms to form distorted TiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(4)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra,  an edgeedge with one Ti(4)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-20°. In the second Ti site, Ti(2) is bonded to one O(1), one O(5), two equivalent O(4), and two equivalent O(6) atoms to form TiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Ti(3)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Ti(2)O6 octahedra,  an edgeedge with one Ti(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-21°. In the third Ti site, Ti(3) is bonded to one O(2), one O(6), two equivalent O(3), and two equivalent O(5) atoms to form TiO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Ti(3)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Ti(2)O6 octahedra,  an edgeedge with one Ti(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, and edges with two equivalent Ti(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-21°. In the fourth Ti site, Ti(4) is bonded to one O(3), one O(8), two equivalent O(2), and two equivalent O(7) atoms to form TiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(4)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra,  an edgeedge with one Ti(4)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, and edges with two equivalent Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-21°. There are eight inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(2), one Ti(2), and two equivalent Ti(1) atoms to form distorted OLi2Ti3 square pyramids that share corners with two equivalent O(6)Li3Ti3 octahedra, corners with two equivalent O(1)Li2Ti3 square pyramids, corners with two equivalent O(2)LiTi3 trigonal pyramids,  an edgeedge with one O(6)Li3Ti3 octahedra, edges with four equivalent O(8)Li3Ti3 octahedra,  an edgeedge with one O(1)Li2Ti3 square pyramid, and edges with two equivalent O(4)Li2Ti3 square pyramids. The corner-sharing octahedral tilt angles range from 2-12°. In the second O site, O(2) is bonded to one Li(2), one Ti(3), and two equivalent Ti(4) atoms to form OLiTi3 trigonal pyramids that share corners with two equivalent O(1)Li2Ti3 square pyramids, corners with two equivalent O(2)LiTi3 trigonal pyramids,  an edgeedge with one O(6)Li3Ti3 octahedra, edges with two equivalent O(8)Li3Ti3 octahedra, and edges with two equivalent O(3)LiTi3 trigonal pyramids. In the third O site, O(3) is bonded to one Li(1), one Ti(4), and two equivalent Ti(3) atoms to form OLiTi3 trigonal pyramids that share corners with two equivalent O(4)Li2Ti3 square pyramids, corners with two equivalent O(3)LiTi3 trigonal pyramids,  an edgeedge with one O(8)Li3Ti3 octahedra, edges with two equivalent O(6)Li3Ti3 octahedra, and edges with two equivalent O(2)LiTi3 trigonal pyramids. 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 distorted OLi2Ti3 square pyramids that share corners with two equivalent O(8)Li3Ti3 octahedra, corners with two equivalent O(4)Li2Ti3 square pyramids, corners with two equivalent O(3)LiTi3 trigonal pyramids,  an edgeedge with one O(8)Li3Ti3 octahedra, edges with four equivalent O(6)Li3Ti3 octahedra,  an edgeedge with one O(4)Li2Ti3 square pyramid, and edges with two equivalent O(1)Li2Ti3 square pyramids. The corner-sharing octahedral tilt angles range from 2-11°. In the fifth O site, O(5) is bonded in a T-shaped geometry to one Ti(2) and two equivalent Ti(3) atoms. In the sixth O site, O(6) is bonded to one Li(2), two equivalent Li(1), one Ti(3), and two equivalent Ti(2) atoms to form OLi3Ti3 octahedra that share corners with two equivalent O(6)Li3Ti3 octahedra, corners with two equivalent O(1)Li2Ti3 square pyramids,  an edgeedge with one O(6)Li3Ti3 octahedra, edges with two equivalent O(8)Li3Ti3 octahedra,  an edgeedge with one O(1)Li2Ti3 square pyramid, edges with four equivalent O(4)Li2Ti3 square pyramids,  an edgeedge with one O(2)LiTi3 trigonal pyramid, and edges with two equivalent O(3)LiTi3 trigonal pyramids. The corner-sharing octahedral tilt angles are 17°. In the seventh O site, O(7) is bonded in a T-shaped geometry to one Ti(1) and two equivalent Ti(4) atoms. In the eighth O site, O(8) is bonded to one Li(1), two equivalent Li(2), one Ti(4), and two equivalent Ti(1) atoms to form distorted OLi3Ti3 octahedra that share corners with two equivalent O(8)Li3Ti3 octahedra, corners with two equivalent O(4)Li2Ti3 square pyramids,  an edgeedge with one O(8)Li3Ti3 octahedra, edges with two equivalent O(6)Li3Ti3 octahedra,  an edgeedge with one O(4)Li2Ti3 square pyramid, edges with four equivalent O(1)Li2Ti3 square pyramids,  an edgeedge with one O(3)LiTi3 trigonal pyramid, and edges with two equivalent O(2)LiTi3 trigonal pyramids. The corner-sharing octahedral tilt angles are 18°.
LiTi2O4 crystallizes in the monoclinic P2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(8), two equivalent O(4), and two equivalent O(6) atoms to form distorted LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra,  an edgeedge with one Ti(4)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-17°. The Li(1)-O(3) bond length is 1.99 Å. The Li(1)-O(8) bond length is 2.41 Å. There is one shorter (2.00 Å) and one longer (2.46 Å) Li(1)-O(4) bond length. Both Li(1)-O(6) bond lengths are 1.98 Å. In the second Li site, Li(2) is bonded to one O(2), one O(6), two equivalent O(1), and two equivalent O(8) atoms to form distorted LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Ti(2)O6 octahedra,  an edgeedge with one Ti(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Ti(4)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-18°. The Li(2)-O(2) bond length is 2.00 Å. The Li(2)-O(6) bond length is 2.39 Å. There is one shorter (2.01 Å) and one longer (2.53 Å) Li(2)-O(1) bond length. Both Li(2)-O(8) bond lengths are 1.98 Å. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(4), one O(7), two equivalent O(1), and two equivalent O(8) atoms to form distorted TiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(4)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra,  an edgeedge with one Ti(4)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-20°. The Ti(1)-O(4) bond length is 2.09 Å. The Ti(1)-O(7) bond length is 1.89 Å. Both Ti(1)-O(1) bond lengths are 1.99 Å. There is one shorter (1.97 Å) and one longer (2.23 Å) Ti(1)-O(8) bond length. In the second Ti site, Ti(2) is bonded to one O(1), one O(5), two equivalent O(4), and two equivalent O(6) atoms to form TiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Ti(3)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Ti(2)O6 octahedra,  an edgeedge with one Ti(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-21°. The Ti(2)-O(1) bond length is 2.10 Å. The Ti(2)-O(5) bond length is 1.88 Å. Both Ti(2)-O(4) bond lengths are 1.99 Å. There is one shorter (1.91 Å) and one longer (2.23 Å) Ti(2)-O(6) bond length. In the third Ti site, Ti(3) is bonded to one O(2), one O(6), two equivalent O(3), and two equivalent O(5) atoms to form TiO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Ti(3)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Ti(2)O6 octahedra,  an edgeedge with one Ti(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, and edges with two equivalent Ti(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-21°. The Ti(3)-O(2) bond length is 2.10 Å. The Ti(3)-O(6) bond length is 2.17 Å. Both Ti(3)-O(3) bond lengths are 1.99 Å. There is one shorter (1.94 Å) and one longer (1.97 Å) Ti(3)-O(5) bond length. In the fourth Ti site, Ti(4) is bonded to one O(3), one O(8), two equivalent O(2), and two equivalent O(7) atoms to form TiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(4)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra,  an edgeedge with one Ti(4)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, and edges with two equivalent Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-21°. The Ti(4)-O(3) bond length is 2.10 Å. The Ti(4)-O(8) bond length is 2.16 Å. Both Ti(4)-O(2) bond lengths are 1.99 Å. There is one shorter (1.95 Å) and one longer (1.96 Å) Ti(4)-O(7) bond length. There are eight inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(2), one Ti(2), and two equivalent Ti(1) atoms to form distorted OLi2Ti3 square pyramids that share corners with two equivalent O(6)Li3Ti3 octahedra, corners with two equivalent O(1)Li2Ti3 square pyramids, corners with two equivalent O(2)LiTi3 trigonal pyramids,  an edgeedge with one O(6)Li3Ti3 octahedra, edges with four equivalent O(8)Li3Ti3 octahedra,  an edgeedge with one O(1)Li2Ti3 square pyramid, and edges with two equivalent O(4)Li2Ti3 square pyramids. The corner-sharing octahedral tilt angles range from 2-12°. In the second O site, O(2) is bonded to one Li(2), one Ti(3), and two equivalent Ti(4) atoms to form OLiTi3 trigonal pyramids that share corners with two equivalent O(1)Li2Ti3 square pyramids, corners with two equivalent O(2)LiTi3 trigonal pyramids,  an edgeedge with one O(6)Li3Ti3 octahedra, edges with two equivalent O(8)Li3Ti3 octahedra, and edges with two equivalent O(3)LiTi3 trigonal pyramids. In the third O site, O(3) is bonded to one Li(1), one Ti(4), and two equivalent Ti(3) atoms to form OLiTi3 trigonal pyramids that share corners with two equivalent O(4)Li2Ti3 square pyramids, corners with two equivalent O(3)LiTi3 trigonal pyramids,  an edgeedge with one O(8)Li3Ti3 octahedra, edges with two equivalent O(6)Li3Ti3 octahedra, and edges with two equivalent O(2)LiTi3 trigonal pyramids. 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 distorted OLi2Ti3 square pyramids that share corners with two equivalent O(8)Li3Ti3 octahedra, corners with two equivalent O(4)Li2Ti3 square pyramids, corners with two equivalent O(3)LiTi3 trigonal pyramids,  an edgeedge with one O(8)Li3Ti3 octahedra, edges with four equivalent O(6)Li3Ti3 octahedra,  an edgeedge with one O(4)Li2Ti3 square pyramid, and edges with two equivalent O(1)Li2Ti3 square pyramids. The corner-sharing octahedral tilt angles range from 2-11°. In the fifth O site, O(5) is bonded in a T-shaped geometry to one Ti(2) and two equivalent Ti(3) atoms. In the sixth O site, O(6) is bonded to one Li(2), two equivalent Li(1), one Ti(3), and two equivalent Ti(2) atoms to form OLi3Ti3 octahedra that share corners with two equivalent O(6)Li3Ti3 octahedra, corners with two equivalent O(1)Li2Ti3 square pyramids,  an edgeedge with one O(6)Li3Ti3 octahedra, edges with two equivalent O(8)Li3Ti3 octahedra,  an edgeedge with one O(1)Li2Ti3 square pyramid, edges with four equivalent O(4)Li2Ti3 square pyramids,  an edgeedge with one O(2)LiTi3 trigonal pyramid, and edges with two equivalent O(3)LiTi3 trigonal pyramids. The corner-sharing octahedral tilt angles are 17°. In the seventh O site, O(7) is bonded in a T-shaped geometry to one Ti(1) and two equivalent Ti(4) atoms. In the eighth O site, O(8) is bonded to one Li(1), two equivalent Li(2), one Ti(4), and two equivalent Ti(1) atoms to form distorted OLi3Ti3 octahedra that share corners with two equivalent O(8)Li3Ti3 octahedra, corners with two equivalent O(4)Li2Ti3 square pyramids,  an edgeedge with one O(8)Li3Ti3 octahedra, edges with two equivalent O(6)Li3Ti3 octahedra,  an edgeedge with one O(4)Li2Ti3 square pyramid, edges with four equivalent O(1)Li2Ti3 square pyramids,  an edgeedge with one O(3)LiTi3 trigonal pyramid, and edges with two equivalent O(2)LiTi3 trigonal pyramids. The corner-sharing octahedral tilt angles are 18°.