Li3Ti4O8 crystallizes in the monoclinic Pm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(7), and two equivalent O(2) atoms. In the second Li site, Li(2) is bonded to one O(2), one O(8), two equivalent O(4), and two equivalent O(7) atoms to form distorted LiO6 octahedra that share corners with two equivalent Ti(3)O6 octahedra, corners with three equivalent Ti(4)O6 octahedra,  an edgeedge with one Ti(4)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with four equivalent Ti(1)O6 octahedra, and  a faceface with one Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-53°. In the third Li site, Li(3) is bonded in a distorted rectangular see-saw-like geometry to one O(3), one O(5), and two equivalent O(6) atoms. 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(2), and two equivalent O(8) atoms to form TiO6 octahedra that share corners with four equivalent Ti(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(4)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-48°. In the second Ti site, Ti(2) is bonded to one O(1), one O(6), two equivalent O(3), and two equivalent O(5) atoms to form a mixture of edge and corner-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 45-47°. In the third Ti site, Ti(3) is bonded to one O(3), one O(8), 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 four equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, and  a faceface with one Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. In the fourth Ti site, Ti(4) is bonded to one O(2), one O(5), two equivalent O(1), and two equivalent O(7) atoms to form TiO6 octahedra that share corners with three equivalent Li(2)O6 octahedra, corners with four equivalent Ti(2)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with two equivalent Ti(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-47°. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Ti(2), and two equivalent Ti(4) atoms to form OLiTi3 trigonal pyramids that share corners with three equivalent O(7)Li3Ti3 octahedra,  a cornercorner with one O(6)Li2Ti3 square pyramid, corners with two equivalent O(3)LiTi3 tetrahedra, corners with two equivalent O(1)LiTi3 trigonal pyramids,  an edgeedge with one O(7)Li3Ti3 octahedra, and edges with two equivalent O(2)Li3Ti3 octahedra. The corner-sharing octahedral tilt angles range from 12-25°. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(1), one Ti(4), and two equivalent Ti(1) atoms to form OLi3Ti3 octahedra that share corners with three equivalent O(8)LiTi3 trigonal pyramids, edges with two equivalent O(2)Li3Ti3 octahedra, edges with four equivalent O(7)Li3Ti3 octahedra,  an edgeedge with one O(8)LiTi3 trigonal pyramid, and edges with two equivalent O(1)LiTi3 trigonal pyramids. In the third O site, O(3) is bonded to one Li(3), one Ti(3), and two equivalent Ti(2) atoms to form distorted OLiTi3 tetrahedra that share corners with two equivalent O(6)Li2Ti3 square pyramids, corners with two equivalent O(3)LiTi3 tetrahedra,  a cornercorner with one O(8)LiTi3 trigonal pyramid, corners with two equivalent O(1)LiTi3 trigonal pyramids, and edges with two equivalent O(6)Li2Ti3 square pyramids. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to two equivalent Li(2), one Ti(1), and two equivalent Ti(3) atoms. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Ti(4), and two equivalent Ti(2) atoms. In the sixth O site, O(6) is bonded to two equivalent Li(3), one Ti(2), and two equivalent Ti(3) atoms to form OLi2Ti3 square pyramids that share corners with two equivalent O(3)LiTi3 tetrahedra,  a cornercorner with one O(1)LiTi3 trigonal pyramid, corners with two equivalent O(8)LiTi3 trigonal pyramids, edges with two equivalent O(6)Li2Ti3 square pyramids, and edges with two equivalent O(3)LiTi3 tetrahedra. In the seventh O site, O(7) is bonded to one Li(1), two equivalent Li(2), one Ti(1), and two equivalent Ti(4) atoms to form OLi3Ti3 octahedra that share corners with three equivalent O(1)LiTi3 trigonal pyramids, edges with two equivalent O(7)Li3Ti3 octahedra, edges with four equivalent O(2)Li3Ti3 octahedra,  an edgeedge with one O(1)LiTi3 trigonal pyramid, and edges with two equivalent O(8)LiTi3 trigonal pyramids. In the eighth O site, O(8) is bonded to one Li(2), one Ti(3), and two equivalent Ti(1) atoms to form OLiTi3 trigonal pyramids that share corners with three equivalent O(2)Li3Ti3 octahedra, corners with two equivalent O(6)Li2Ti3 square pyramids,  a cornercorner with one O(3)LiTi3 tetrahedra, corners with two equivalent O(8)LiTi3 trigonal pyramids,  an edgeedge with one O(2)Li3Ti3 octahedra, and edges with two equivalent O(7)Li3Ti3 octahedra. The corner-sharing octahedral tilt angles range from 14-19°.
Li3Ti4O8 crystallizes in the monoclinic Pm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(7), and two equivalent O(2) atoms. The Li(1)-O(1) bond length is 1.95 Å. The Li(1)-O(7) bond length is 1.97 Å. Both Li(1)-O(2) bond lengths are 2.02 Å. In the second Li site, Li(2) is bonded to one O(2), one O(8), two equivalent O(4), and two equivalent O(7) atoms to form distorted LiO6 octahedra that share corners with two equivalent Ti(3)O6 octahedra, corners with three equivalent Ti(4)O6 octahedra,  an edgeedge with one Ti(4)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with four equivalent Ti(1)O6 octahedra, and  a faceface with one Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-53°. The Li(2)-O(2) bond length is 1.99 Å. The Li(2)-O(8) bond length is 1.95 Å. Both Li(2)-O(4) bond lengths are 2.38 Å. Both Li(2)-O(7) bond lengths are 2.08 Å. In the third Li site, Li(3) is bonded in a distorted rectangular see-saw-like geometry to one O(3), one O(5), and two equivalent O(6) atoms. The Li(3)-O(3) bond length is 1.85 Å. The Li(3)-O(5) bond length is 2.25 Å. Both Li(3)-O(6) bond lengths are 1.96 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(2), and two equivalent O(8) atoms to form TiO6 octahedra that share corners with four equivalent Ti(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(4)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-48°. The Ti(1)-O(4) bond length is 1.95 Å. The Ti(1)-O(7) bond length is 2.23 Å. Both Ti(1)-O(2) bond lengths are 2.10 Å. Both Ti(1)-O(8) bond lengths are 2.00 Å. In the second Ti site, Ti(2) is bonded to one O(1), one O(6), two equivalent O(3), and two equivalent O(5) atoms to form a mixture of edge and corner-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 45-47°. The Ti(2)-O(1) bond length is 2.00 Å. The Ti(2)-O(6) bond length is 2.05 Å. Both Ti(2)-O(3) bond lengths are 2.02 Å. Both Ti(2)-O(5) bond lengths are 2.07 Å. In the third Ti site, Ti(3) is bonded to one O(3), one O(8), 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 four equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, and  a faceface with one Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. The Ti(3)-O(3) bond length is 1.99 Å. The Ti(3)-O(8) bond length is 2.03 Å. Both Ti(3)-O(4) bond lengths are 2.07 Å. Both Ti(3)-O(6) bond lengths are 2.06 Å. In the fourth Ti site, Ti(4) is bonded to one O(2), one O(5), two equivalent O(1), and two equivalent O(7) atoms to form TiO6 octahedra that share corners with three equivalent Li(2)O6 octahedra, corners with four equivalent Ti(2)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with two equivalent Ti(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-47°. The Ti(4)-O(2) bond length is 2.16 Å. The Ti(4)-O(5) bond length is 1.99 Å. Both Ti(4)-O(1) bond lengths are 2.03 Å. Both Ti(4)-O(7) bond lengths are 2.08 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Ti(2), and two equivalent Ti(4) atoms to form OLiTi3 trigonal pyramids that share corners with three equivalent O(7)Li3Ti3 octahedra,  a cornercorner with one O(6)Li2Ti3 square pyramid, corners with two equivalent O(3)LiTi3 tetrahedra, corners with two equivalent O(1)LiTi3 trigonal pyramids,  an edgeedge with one O(7)Li3Ti3 octahedra, and edges with two equivalent O(2)Li3Ti3 octahedra. The corner-sharing octahedral tilt angles range from 12-25°. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(1), one Ti(4), and two equivalent Ti(1) atoms to form OLi3Ti3 octahedra that share corners with three equivalent O(8)LiTi3 trigonal pyramids, edges with two equivalent O(2)Li3Ti3 octahedra, edges with four equivalent O(7)Li3Ti3 octahedra,  an edgeedge with one O(8)LiTi3 trigonal pyramid, and edges with two equivalent O(1)LiTi3 trigonal pyramids. In the third O site, O(3) is bonded to one Li(3), one Ti(3), and two equivalent Ti(2) atoms to form distorted OLiTi3 tetrahedra that share corners with two equivalent O(6)Li2Ti3 square pyramids, corners with two equivalent O(3)LiTi3 tetrahedra,  a cornercorner with one O(8)LiTi3 trigonal pyramid, corners with two equivalent O(1)LiTi3 trigonal pyramids, and edges with two equivalent O(6)Li2Ti3 square pyramids. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to two equivalent Li(2), one Ti(1), and two equivalent Ti(3) atoms. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Ti(4), and two equivalent Ti(2) atoms. In the sixth O site, O(6) is bonded to two equivalent Li(3), one Ti(2), and two equivalent Ti(3) atoms to form OLi2Ti3 square pyramids that share corners with two equivalent O(3)LiTi3 tetrahedra,  a cornercorner with one O(1)LiTi3 trigonal pyramid, corners with two equivalent O(8)LiTi3 trigonal pyramids, edges with two equivalent O(6)Li2Ti3 square pyramids, and edges with two equivalent O(3)LiTi3 tetrahedra. In the seventh O site, O(7) is bonded to one Li(1), two equivalent Li(2), one Ti(1), and two equivalent Ti(4) atoms to form OLi3Ti3 octahedra that share corners with three equivalent O(1)LiTi3 trigonal pyramids, edges with two equivalent O(7)Li3Ti3 octahedra, edges with four equivalent O(2)Li3Ti3 octahedra,  an edgeedge with one O(1)LiTi3 trigonal pyramid, and edges with two equivalent O(8)LiTi3 trigonal pyramids. In the eighth O site, O(8) is bonded to one Li(2), one Ti(3), and two equivalent Ti(1) atoms to form OLiTi3 trigonal pyramids that share corners with three equivalent O(2)Li3Ti3 octahedra, corners with two equivalent O(6)Li2Ti3 square pyramids,  a cornercorner with one O(3)LiTi3 tetrahedra, corners with two equivalent O(8)LiTi3 trigonal pyramids,  an edgeedge with one O(2)Li3Ti3 octahedra, and edges with two equivalent O(7)Li3Ti3 octahedra. The corner-sharing octahedral tilt angles range from 14-19°.