Li4Ti7O16 crystallizes in the monoclinic Cm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one O(5), one O(9), and two equivalent O(10) atoms. In the second Li site, Li(2) is bonded to one O(4), one O(9), two equivalent O(1), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with four equivalent Ti(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with two equivalent Ti(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-52°. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(1), one O(12), one O(3), and one O(4) atom. There are five inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(1), one O(11), one O(12), one O(2), one O(4), and one O(7) atom to form TiO6 octahedra that share corners with two equivalent Ti(3)O6 octahedra, corners with two equivalent Ti(4)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Ti(5)O6 octahedra, and edges with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-53°. In the second Ti site, Ti(2) is bonded to one O(10), one O(3), one O(5), one O(6), one O(8), and one O(9) atom to form distorted TiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Ti(5)O6 octahedra,  an edgeedge with one Ti(3)O6 octahedra,  an edgeedge with one Ti(4)O6 octahedra, and edges with two equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-52°. In the third Ti site, Ti(3) is bonded to one O(2), one O(6), two equivalent O(10), and two equivalent O(7) atoms to form a mixture of edge and corner-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. In the fourth Ti site, Ti(4) is bonded to one O(11), one O(5), two equivalent O(10), and two equivalent O(7) atoms to form a mixture of edge and corner-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 45-50°. In the fifth Ti site, Ti(5) is bonded to one O(12), one O(8), two equivalent O(1), and two equivalent O(3) atoms to form distorted TiO6 octahedra that share corners with four equivalent Ti(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, and edges with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-48°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), one Ti(1), and one Ti(5) atom to form OLi2Ti2 tetrahedra that share  a cornercorner with one O(12)Li2Ti3 square pyramid,  a cornercorner with one O(4)Li3Ti2 square pyramid, corners with two equivalent O(1)Li2Ti2 tetrahedra,  a cornercorner with one O(9)Li2Ti2 trigonal pyramid,  an edgeedge with one O(12)Li2Ti3 square pyramid, and  an edgeedge with one O(4)Li3Ti2 square pyramid. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Ti(3) and two equivalent Ti(1) atoms. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Ti(2), and one Ti(5) atom. In the fourth O site, O(4) is bonded to one Li(2), two equivalent Li(3), and two equivalent Ti(1) atoms to form OLi3Ti2 square pyramids that share corners with two equivalent O(1)Li2Ti2 tetrahedra,  a cornercorner with one O(9)Li2Ti2 trigonal pyramid, edges with two equivalent O(12)Li2Ti3 square pyramids, and edges with two equivalent O(1)Li2Ti2 tetrahedra. In the fifth O site, O(5) is bonded to one Li(1), one Ti(4), and two equivalent Ti(2) atoms to form distorted corner-sharing OLiTi3 tetrahedra. In the sixth O site, O(6) is bonded in a trigonal non-coplanar geometry to one Ti(3) and two equivalent Ti(2) atoms. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Ti(1), one Ti(3), and one Ti(4) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Ti(5) and two equivalent Ti(2) atoms. In the ninth O site, O(9) is bonded to one Li(1), one Li(2), and two equivalent Ti(2) atoms to form OLi2Ti2 trigonal pyramids that share  a cornercorner with one O(4)Li3Ti2 square pyramid, corners with two equivalent O(1)Li2Ti2 tetrahedra, and corners with three equivalent O(5)LiTi3 tetrahedra. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(1), one Ti(2), one Ti(3), and one Ti(4) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Ti(4) and two equivalent Ti(1) atoms. In the twelfth O site, O(12) is bonded to two equivalent Li(3), one Ti(5), and two equivalent Ti(1) atoms to form OLi2Ti3 square pyramids that share corners with two equivalent O(1)Li2Ti2 tetrahedra, edges with two equivalent O(4)Li3Ti2 square pyramids, and edges with two equivalent O(1)Li2Ti2 tetrahedra.
Li4Ti7O16 crystallizes in the monoclinic Cm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one O(5), one O(9), and two equivalent O(10) atoms. The Li(1)-O(5) bond length is 1.90 Å. The Li(1)-O(9) bond length is 2.03 Å. Both Li(1)-O(10) bond lengths are 2.01 Å. In the second Li site, Li(2) is bonded to one O(4), one O(9), two equivalent O(1), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with four equivalent Ti(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with two equivalent Ti(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-52°. The Li(2)-O(4) bond length is 2.22 Å. The Li(2)-O(9) bond length is 2.04 Å. Both Li(2)-O(1) bond lengths are 2.08 Å. Both Li(2)-O(3) bond lengths are 2.13 Å. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(1), one O(12), one O(3), and one O(4) atom. The Li(3)-O(1) bond length is 1.87 Å. The Li(3)-O(12) bond length is 2.02 Å. The Li(3)-O(3) bond length is 2.05 Å. The Li(3)-O(4) bond length is 2.03 Å. There are five inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(1), one O(11), one O(12), one O(2), one O(4), and one O(7) atom to form TiO6 octahedra that share corners with two equivalent Ti(3)O6 octahedra, corners with two equivalent Ti(4)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Ti(5)O6 octahedra, and edges with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-53°. The Ti(1)-O(1) bond length is 1.91 Å. The Ti(1)-O(11) bond length is 2.00 Å. The Ti(1)-O(12) bond length is 2.06 Å. The Ti(1)-O(2) bond length is 1.95 Å. The Ti(1)-O(4) bond length is 1.95 Å. The Ti(1)-O(7) bond length is 2.09 Å. In the second Ti site, Ti(2) is bonded to one O(10), one O(3), one O(5), one O(6), one O(8), and one O(9) atom to form distorted TiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Ti(5)O6 octahedra,  an edgeedge with one Ti(3)O6 octahedra,  an edgeedge with one Ti(4)O6 octahedra, and edges with two equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-52°. The Ti(2)-O(10) bond length is 2.14 Å. The Ti(2)-O(3) bond length is 1.85 Å. The Ti(2)-O(5) bond length is 1.99 Å. The Ti(2)-O(6) bond length is 2.00 Å. The Ti(2)-O(8) bond length is 2.05 Å. The Ti(2)-O(9) bond length is 1.93 Å. In the third Ti site, Ti(3) is bonded to one O(2), one O(6), two equivalent O(10), and two equivalent O(7) atoms to form a mixture of edge and corner-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. The Ti(3)-O(2) bond length is 2.12 Å. The Ti(3)-O(6) bond length is 1.97 Å. Both Ti(3)-O(10) bond lengths are 2.07 Å. Both Ti(3)-O(7) bond lengths are 1.88 Å. In the fourth Ti site, Ti(4) is bonded to one O(11), one O(5), two equivalent O(10), and two equivalent O(7) atoms to form a mixture of edge and corner-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles range from 45-50°. The Ti(4)-O(11) bond length is 1.94 Å. The Ti(4)-O(5) bond length is 2.08 Å. Both Ti(4)-O(10) bond lengths are 1.91 Å. Both Ti(4)-O(7) bond lengths are 2.07 Å. In the fifth Ti site, Ti(5) is bonded to one O(12), one O(8), two equivalent O(1), and two equivalent O(3) atoms to form distorted TiO6 octahedra that share corners with four equivalent Ti(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, and edges with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-48°. The Ti(5)-O(12) bond length is 2.14 Å. The Ti(5)-O(8) bond length is 1.92 Å. Both Ti(5)-O(1) bond lengths are 1.94 Å. Both Ti(5)-O(3) bond lengths are 2.00 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), one Ti(1), and one Ti(5) atom to form OLi2Ti2 tetrahedra that share  a cornercorner with one O(12)Li2Ti3 square pyramid,  a cornercorner with one O(4)Li3Ti2 square pyramid, corners with two equivalent O(1)Li2Ti2 tetrahedra,  a cornercorner with one O(9)Li2Ti2 trigonal pyramid,  an edgeedge with one O(12)Li2Ti3 square pyramid, and  an edgeedge with one O(4)Li3Ti2 square pyramid. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Ti(3) and two equivalent Ti(1) atoms. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Ti(2), and one Ti(5) atom. In the fourth O site, O(4) is bonded to one Li(2), two equivalent Li(3), and two equivalent Ti(1) atoms to form OLi3Ti2 square pyramids that share corners with two equivalent O(1)Li2Ti2 tetrahedra,  a cornercorner with one O(9)Li2Ti2 trigonal pyramid, edges with two equivalent O(12)Li2Ti3 square pyramids, and edges with two equivalent O(1)Li2Ti2 tetrahedra. In the fifth O site, O(5) is bonded to one Li(1), one Ti(4), and two equivalent Ti(2) atoms to form distorted corner-sharing OLiTi3 tetrahedra. In the sixth O site, O(6) is bonded in a trigonal non-coplanar geometry to one Ti(3) and two equivalent Ti(2) atoms. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Ti(1), one Ti(3), and one Ti(4) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Ti(5) and two equivalent Ti(2) atoms. In the ninth O site, O(9) is bonded to one Li(1), one Li(2), and two equivalent Ti(2) atoms to form OLi2Ti2 trigonal pyramids that share  a cornercorner with one O(4)Li3Ti2 square pyramid, corners with two equivalent O(1)Li2Ti2 tetrahedra, and corners with three equivalent O(5)LiTi3 tetrahedra. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(1), one Ti(2), one Ti(3), and one Ti(4) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Ti(4) and two equivalent Ti(1) atoms. In the twelfth O site, O(12) is bonded to two equivalent Li(3), one Ti(5), and two equivalent Ti(1) atoms to form OLi2Ti3 square pyramids that share corners with two equivalent O(1)Li2Ti2 tetrahedra, edges with two equivalent O(4)Li3Ti2 square pyramids, and edges with two equivalent O(1)Li2Ti2 tetrahedra.