Li3Ti8O16 is beta indium sulfide-derived structured and crystallizes in the orthorhombic Pmmn space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(5) and two equivalent O(7) atoms to form LiO4 tetrahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Ti(3)O6 octahedra, corners with four equivalent Ti(1)O6 octahedra, and corners with four equivalent Ti(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-60°. In the second Li site, Li(2) is bonded to one O(1), one O(4), and two equivalent O(3) atoms to form LiO4 tetrahedra that share corners with two equivalent Ti(4)O6 octahedra, corners with three equivalent Ti(1)O6 octahedra, corners with three equivalent Ti(3)O6 octahedra, and corners with four equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-60°. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(1), one O(6), two equivalent O(3), and two equivalent O(7) atoms to form TiO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Ti(1)O6 octahedra,  an edgeedge with one Ti(3)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with two equivalent Ti(4)O6 octahedra. In the second Ti site, Ti(2) is bonded to one O(2), one O(7), two equivalent O(1), and two equivalent O(4) atoms to form TiO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with two equivalent Ti(3)O6 octahedra. In the third Ti site, Ti(3) is bonded to one O(4), one O(5), two equivalent O(2), and two equivalent O(3) atoms to form TiO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Ti(1)O6 octahedra,  an edgeedge with one Ti(3)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with two equivalent Ti(4)O6 octahedra. In the fourth Ti site, Ti(4) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(6) atoms to form TiO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, and edges with two equivalent Ti(4)O6 octahedra. There are seven inequivalent O sites. In the first O site, O(7) is bonded to one Li(1), one Ti(2), and two equivalent Ti(1) atoms to form a mixture of distorted corner and edge-sharing OLiTi3 trigonal pyramids. In the second O site, O(1) is bonded to one Li(2), one Ti(1), and two equivalent Ti(2) atoms to form a mixture of distorted corner and edge-sharing OLiTi3 trigonal pyramids. In the third O site, O(2) is bonded in a distorted T-shaped geometry to one Ti(2) and two equivalent Ti(3) atoms. In the fourth O site, O(3) is bonded to one Li(2), one Ti(1), one Ti(3), and one Ti(4) atom to form a mixture of distorted corner and edge-sharing OLiTi3 trigonal pyramids. In the fifth O site, O(4) is bonded to one Li(2), one Ti(3), and two equivalent Ti(2) atoms to form a mixture of distorted corner and edge-sharing OLiTi3 trigonal pyramids. In the sixth O site, O(5) is bonded to one Li(1), one Ti(3), and two equivalent Ti(4) atoms to form a mixture of distorted corner and edge-sharing OLiTi3 trigonal pyramids. In the seventh O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Ti(1) and two equivalent Ti(4) atoms.
Li3Ti8O16 is beta indium sulfide-derived structured and crystallizes in the orthorhombic Pmmn space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(5) and two equivalent O(7) atoms to form LiO4 tetrahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Ti(3)O6 octahedra, corners with four equivalent Ti(1)O6 octahedra, and corners with four equivalent Ti(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-60°. Both Li(1)-O(5) bond lengths are 2.01 Å. Both Li(1)-O(7) bond lengths are 2.03 Å. In the second Li site, Li(2) is bonded to one O(1), one O(4), and two equivalent O(3) atoms to form LiO4 tetrahedra that share corners with two equivalent Ti(4)O6 octahedra, corners with three equivalent Ti(1)O6 octahedra, corners with three equivalent Ti(3)O6 octahedra, and corners with four equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-60°. The Li(2)-O(1) bond length is 2.02 Å. The Li(2)-O(4) bond length is 2.03 Å. Both Li(2)-O(3) bond lengths are 2.02 Å. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(1), one O(6), two equivalent O(3), and two equivalent O(7) atoms to form TiO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Ti(1)O6 octahedra,  an edgeedge with one Ti(3)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with two equivalent Ti(4)O6 octahedra. The Ti(1)-O(1) bond length is 2.05 Å. The Ti(1)-O(6) bond length is 1.95 Å. Both Ti(1)-O(3) bond lengths are 2.01 Å. Both Ti(1)-O(7) bond lengths are 2.01 Å. In the second Ti site, Ti(2) is bonded to one O(2), one O(7), two equivalent O(1), and two equivalent O(4) atoms to form TiO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with two equivalent Ti(3)O6 octahedra. The Ti(2)-O(2) bond length is 1.95 Å. The Ti(2)-O(7) bond length is 2.04 Å. Both Ti(2)-O(1) bond lengths are 2.01 Å. Both Ti(2)-O(4) bond lengths are 2.02 Å. In the third Ti site, Ti(3) is bonded to one O(4), one O(5), two equivalent O(2), and two equivalent O(3) atoms to form TiO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Ti(1)O6 octahedra,  an edgeedge with one Ti(3)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with two equivalent Ti(4)O6 octahedra. The Ti(3)-O(4) bond length is 2.02 Å. The Ti(3)-O(5) bond length is 2.01 Å. Both Ti(3)-O(2) bond lengths are 1.98 Å. Both Ti(3)-O(3) bond lengths are 2.03 Å. In the fourth Ti site, Ti(4) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(6) atoms to form TiO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, and edges with two equivalent Ti(4)O6 octahedra. Both Ti(4)-O(3) bond lengths are 2.02 Å. Both Ti(4)-O(5) bond lengths are 2.02 Å. Both Ti(4)-O(6) bond lengths are 1.99 Å. There are seven inequivalent O sites. In the first O site, O(7) is bonded to one Li(1), one Ti(2), and two equivalent Ti(1) atoms to form a mixture of distorted corner and edge-sharing OLiTi3 trigonal pyramids. In the second O site, O(1) is bonded to one Li(2), one Ti(1), and two equivalent Ti(2) atoms to form a mixture of distorted corner and edge-sharing OLiTi3 trigonal pyramids. In the third O site, O(2) is bonded in a distorted T-shaped geometry to one Ti(2) and two equivalent Ti(3) atoms. In the fourth O site, O(3) is bonded to one Li(2), one Ti(1), one Ti(3), and one Ti(4) atom to form a mixture of distorted corner and edge-sharing OLiTi3 trigonal pyramids. In the fifth O site, O(4) is bonded to one Li(2), one Ti(3), and two equivalent Ti(2) atoms to form a mixture of distorted corner and edge-sharing OLiTi3 trigonal pyramids. In the sixth O site, O(5) is bonded to one Li(1), one Ti(3), and two equivalent Ti(4) atoms to form a mixture of distorted corner and edge-sharing OLiTi3 trigonal pyramids. In the seventh O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Ti(1) and two equivalent Ti(4) atoms.