LiTi4O6 crystallizes in the monoclinic Pm space group. Li(1) is bonded in a 5-coordinate geometry to one O(2), two equivalent O(3), and two equivalent O(5) atoms. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(3), one O(5), two equivalent O(1), and two equivalent O(2) atoms to form a mixture of corner, face, and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 46-52°. In the second Ti site, Ti(2) is bonded to one O(3), one O(6), two equivalent O(1), and two equivalent O(4) atoms to form a mixture of corner, face, and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 46-52°. In the third Ti site, Ti(3) is bonded to one O(1), one O(4), two equivalent O(3), and two equivalent O(6) atoms to form a mixture of corner, face, and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 45-52°. In the fourth Ti site, Ti(4) is bonded to one O(2), one O(4), two equivalent O(5), and two equivalent O(6) atoms to form a mixture of corner, face, and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 45-52°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Ti(3), two equivalent Ti(1), and two equivalent Ti(2) atoms. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Ti(4), and two equivalent Ti(1) atoms. In the third O site, O(3) is bonded to two equivalent Li(1), one Ti(1), one Ti(2), and two equivalent Ti(3) atoms to form distorted OLi2Ti4 pentagonal pyramids that share corners with three equivalent O(5)Li2Ti3 square pyramids, corners with three equivalent O(6)Ti5 trigonal bipyramids, edges with two equivalent O(3)Li2Ti4 pentagonal pyramids,  an edgeedge with one O(5)Li2Ti3 square pyramid, and  an edgeedge with one O(6)Ti5 trigonal bipyramid. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Ti(3), one Ti(4), and two equivalent Ti(2) atoms. In the fifth O site, O(5) is bonded to two equivalent Li(1), one Ti(1), and two equivalent Ti(4) atoms to form OLi2Ti3 square pyramids that share corners with three equivalent O(3)Li2Ti4 pentagonal pyramids, corners with two equivalent O(6)Ti5 trigonal bipyramids,  an edgeedge with one O(3)Li2Ti4 pentagonal pyramid, edges with two equivalent O(5)Li2Ti3 square pyramids, and  an edgeedge with one O(6)Ti5 trigonal bipyramid. In the sixth O site, O(6) is bonded to one Ti(2), two equivalent Ti(3), and two equivalent Ti(4) atoms to form distorted OTi5 trigonal bipyramids that share corners with three equivalent O(3)Li2Ti4 pentagonal pyramids, corners with two equivalent O(5)Li2Ti3 square pyramids,  an edgeedge with one O(3)Li2Ti4 pentagonal pyramid,  an edgeedge with one O(5)Li2Ti3 square pyramid, and edges with two equivalent O(6)Ti5 trigonal bipyramids.
LiTi4O6 crystallizes in the monoclinic Pm space group. Li(1) is bonded in a 5-coordinate geometry to one O(2), two equivalent O(3), and two equivalent O(5) atoms. The Li(1)-O(2) bond length is 1.88 Å. Both Li(1)-O(3) bond lengths are 2.37 Å. Both Li(1)-O(5) bond lengths are 1.98 Å. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(3), one O(5), two equivalent O(1), and two equivalent O(2) atoms to form a mixture of corner, face, and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 46-52°. The Ti(1)-O(3) bond length is 2.07 Å. The Ti(1)-O(5) bond length is 2.01 Å. Both Ti(1)-O(1) bond lengths are 2.13 Å. Both Ti(1)-O(2) bond lengths are 1.98 Å. In the second Ti site, Ti(2) is bonded to one O(3), one O(6), two equivalent O(1), and two equivalent O(4) atoms to form a mixture of corner, face, and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 46-52°. The Ti(2)-O(3) bond length is 2.13 Å. The Ti(2)-O(6) bond length is 2.18 Å. Both Ti(2)-O(1) bond lengths are 2.16 Å. Both Ti(2)-O(4) bond lengths are 2.04 Å. In the third Ti site, Ti(3) is bonded to one O(1), one O(4), two equivalent O(3), and two equivalent O(6) atoms to form a mixture of corner, face, and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 45-52°. The Ti(3)-O(1) bond length is 2.14 Å. The Ti(3)-O(4) bond length is 2.06 Å. Both Ti(3)-O(3) bond lengths are 2.09 Å. Both Ti(3)-O(6) bond lengths are 2.13 Å. In the fourth Ti site, Ti(4) is bonded to one O(2), one O(4), two equivalent O(5), and two equivalent O(6) atoms to form a mixture of corner, face, and edge-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 45-52°. The Ti(4)-O(2) bond length is 2.01 Å. The Ti(4)-O(4) bond length is 2.03 Å. Both Ti(4)-O(5) bond lengths are 2.08 Å. Both Ti(4)-O(6) bond lengths are 2.14 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Ti(3), two equivalent Ti(1), and two equivalent Ti(2) atoms. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Ti(4), and two equivalent Ti(1) atoms. In the third O site, O(3) is bonded to two equivalent Li(1), one Ti(1), one Ti(2), and two equivalent Ti(3) atoms to form distorted OLi2Ti4 pentagonal pyramids that share corners with three equivalent O(5)Li2Ti3 square pyramids, corners with three equivalent O(6)Ti5 trigonal bipyramids, edges with two equivalent O(3)Li2Ti4 pentagonal pyramids,  an edgeedge with one O(5)Li2Ti3 square pyramid, and  an edgeedge with one O(6)Ti5 trigonal bipyramid. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Ti(3), one Ti(4), and two equivalent Ti(2) atoms. In the fifth O site, O(5) is bonded to two equivalent Li(1), one Ti(1), and two equivalent Ti(4) atoms to form OLi2Ti3 square pyramids that share corners with three equivalent O(3)Li2Ti4 pentagonal pyramids, corners with two equivalent O(6)Ti5 trigonal bipyramids,  an edgeedge with one O(3)Li2Ti4 pentagonal pyramid, edges with two equivalent O(5)Li2Ti3 square pyramids, and  an edgeedge with one O(6)Ti5 trigonal bipyramid. In the sixth O site, O(6) is bonded to one Ti(2), two equivalent Ti(3), and two equivalent Ti(4) atoms to form distorted OTi5 trigonal bipyramids that share corners with three equivalent O(3)Li2Ti4 pentagonal pyramids, corners with two equivalent O(5)Li2Ti3 square pyramids,  an edgeedge with one O(3)Li2Ti4 pentagonal pyramid,  an edgeedge with one O(5)Li2Ti3 square pyramid, and edges with two equivalent O(6)Ti5 trigonal bipyramids.