Li4Ti7O16 crystallizes in the orthorhombic Pnnm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(4), and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with three equivalent Ti(3)O6 octahedra, and corners with six equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-64°. In the second Li site, Li(2) is bonded to one O(3), one O(6), and two equivalent O(5) atoms to form LiO4 tetrahedra that share  a cornercorner with one Ti(2)O6 octahedra, corners with three equivalent Ti(3)O6 octahedra, and corners with six equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-63°. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form TiO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Ti(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with two equivalent Ti(3)O6 octahedra. In the second Ti site, Ti(2) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form TiO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, edges with two equivalent Ti(3)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. In the third Ti site, Ti(3) is bonded to one O(4), one O(6), two equivalent O(2), and two equivalent O(5) atoms to form TiO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Ti(2)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. There are six inequivalent O sites. In the first O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(2), one Ti(3), and two equivalent Ti(1) atoms. In the second O site, O(1) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Ti(1) atoms. In the third O site, O(2) is bonded to one Li(1), one Ti(1), one Ti(2), and one Ti(3) atom to form a mixture of distorted corner and edge-sharing OLiTi3 trigonal pyramids. In the fourth O site, O(3) is bonded to one Li(2), one Ti(2), and two equivalent Ti(1) atoms to form a mixture of corner and edge-sharing OLiTi3 tetrahedra. In the fifth O site, O(4) is bonded to one Li(1), one Ti(3), and two equivalent Ti(1) atoms to form a mixture of distorted corner and edge-sharing OLiTi3 tetrahedra. In the sixth O site, O(5) is bonded in a trigonal planar geometry to one Li(2), one Ti(1), and one Ti(3) atom.
Li4Ti7O16 crystallizes in the orthorhombic Pnnm space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(4), and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with three equivalent Ti(3)O6 octahedra, and corners with six equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-64°. The Li(1)-O(1) bond length is 2.00 Å. The Li(1)-O(4) bond length is 2.02 Å. Both Li(1)-O(2) bond lengths are 2.02 Å. In the second Li site, Li(2) is bonded to one O(3), one O(6), and two equivalent O(5) atoms to form LiO4 tetrahedra that share  a cornercorner with one Ti(2)O6 octahedra, corners with three equivalent Ti(3)O6 octahedra, and corners with six equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-63°. The Li(2)-O(3) bond length is 2.02 Å. The Li(2)-O(6) bond length is 1.99 Å. Both Li(2)-O(5) bond lengths are 1.97 Å. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form TiO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Ti(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with two equivalent Ti(3)O6 octahedra. The Ti(1)-O(1) bond length is 1.88 Å. The Ti(1)-O(2) bond length is 2.12 Å. The Ti(1)-O(3) bond length is 2.02 Å. The Ti(1)-O(4) bond length is 2.14 Å. The Ti(1)-O(5) bond length is 1.86 Å. The Ti(1)-O(6) bond length is 1.98 Å. In the second Ti site, Ti(2) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form TiO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, edges with two equivalent Ti(3)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. Both Ti(2)-O(3) bond lengths are 2.03 Å. All Ti(2)-O(2) bond lengths are 1.96 Å. In the third Ti site, Ti(3) is bonded to one O(4), one O(6), two equivalent O(2), and two equivalent O(5) atoms to form TiO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Ti(2)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The Ti(3)-O(4) bond length is 1.88 Å. The Ti(3)-O(6) bond length is 2.15 Å. Both Ti(3)-O(2) bond lengths are 2.06 Å. Both Ti(3)-O(5) bond lengths are 1.91 Å. There are six inequivalent O sites. In the first O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(2), one Ti(3), and two equivalent Ti(1) atoms. In the second O site, O(1) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Ti(1) atoms. In the third O site, O(2) is bonded to one Li(1), one Ti(1), one Ti(2), and one Ti(3) atom to form a mixture of distorted corner and edge-sharing OLiTi3 trigonal pyramids. In the fourth O site, O(3) is bonded to one Li(2), one Ti(2), and two equivalent Ti(1) atoms to form a mixture of corner and edge-sharing OLiTi3 tetrahedra. In the fifth O site, O(4) is bonded to one Li(1), one Ti(3), and two equivalent Ti(1) atoms to form a mixture of distorted corner and edge-sharing OLiTi3 tetrahedra. In the sixth O site, O(5) is bonded in a trigonal planar geometry to one Li(2), one Ti(1), and one Ti(3) atom.