Li7Ti7O16 crystallizes in the trigonal R3m space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(5), one O(6), two equivalent O(1), and two equivalent O(7) atoms to form LiO6 octahedra that share corners with three equivalent Ti(1)O6 octahedra, corners with three equivalent Ti(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-9°. In the second Li site, Li(2) is bonded to three equivalent O(1) and three equivalent O(7) atoms to form LiO6 octahedra that share edges with three equivalent Ti(1)O6 octahedra, edges with three equivalent Ti(2)O6 octahedra, and edges with six equivalent Li(1)O6 octahedra. In the third Li site, Li(3) is bonded to one O(2) and three equivalent O(4) atoms to form LiO4 tetrahedra that share corners with three equivalent Ti(1)O6 octahedra, corners with three equivalent Ti(3)O6 octahedra, and corners with six equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-65°. In the fourth Li site, Li(4) is bonded to one O(8) and three equivalent O(3) atoms to form LiO4 tetrahedra that share corners with three 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 56-62°. In the fifth Li site, Li(5) is bonded in a distorted trigonal non-coplanar geometry to three equivalent O(4) and three equivalent O(7) atoms. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(2), one O(5), two equivalent O(1), and two equivalent O(3) atoms to form TiO6 octahedra that share corners with three equivalent Li(1)O6 octahedra,  a cornercorner with one Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Ti(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-7°. In the second Ti site, Ti(2) is bonded to one O(6), one O(8), two equivalent O(4), and two equivalent O(7) atoms to form TiO6 octahedra that share corners with three equivalent Li(1)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Ti(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. In the third Ti site, Ti(3) is bonded to three equivalent O(3) and three equivalent O(4) atoms to form TiO6 octahedra that share corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent Li(4)O4 tetrahedra, edges with three equivalent Ti(1)O6 octahedra, and edges with three equivalent Ti(2)O6 octahedra. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), and two equivalent Ti(1) atoms to form OLi3Ti2 square pyramids that share corners with three equivalent O(7)Li4Ti2 octahedra, corners with two equivalent O(1)Li3Ti2 square pyramids, corners with four equivalent O(3)LiTi3 tetrahedra,  an edgeedge with one O(6)Li3Ti3 octahedra, edges with two equivalent O(5)Li3Ti3 octahedra, edges with two equivalent O(7)Li4Ti2 octahedra, edges with two equivalent O(1)Li3Ti2 square pyramids, and  an edgeedge with one O(2)LiTi3 trigonal pyramid. The corner-sharing octahedral tilt angles range from 0-7°. In the second O site, O(2) is bonded to one Li(3) and three equivalent Ti(1) atoms to form distorted OLiTi3 trigonal pyramids that share corners with three equivalent O(5)Li3Ti3 octahedra, corners with six equivalent O(3)LiTi3 tetrahedra, corners with three equivalent O(4)Li2Ti3 trigonal bipyramids, and edges with three equivalent O(1)Li3Ti2 square pyramids. The corner-sharing octahedral tilt angles are 1°. In the third O site, O(3) is bonded to one Li(4), one Ti(3), and two equivalent Ti(1) atoms to form distorted OLiTi3 tetrahedra that share corners with four equivalent O(1)Li3Ti2 square pyramids, corners with two equivalent O(3)LiTi3 tetrahedra, corners with three equivalent O(4)Li2Ti3 trigonal bipyramids,  a cornercorner with one O(8)LiTi3 trigonal pyramid, corners with two equivalent O(2)LiTi3 trigonal pyramids,  an edgeedge with one O(5)Li3Ti3 octahedra, and edges with two equivalent O(3)LiTi3 tetrahedra. In the fourth O site, O(4) is bonded to one Li(3), one Li(5), one Ti(3), and two equivalent Ti(2) atoms to form distorted OLi2Ti3 trigonal bipyramids that share corners with three equivalent O(7)Li4Ti2 octahedra, corners with three equivalent O(3)LiTi3 tetrahedra,  a cornercorner with one O(2)LiTi3 trigonal pyramid, corners with two equivalent O(8)LiTi3 trigonal pyramids,  an edgeedge with one O(6)Li3Ti3 octahedra, edges with two equivalent O(7)Li4Ti2 octahedra, and edges with four equivalent O(4)Li2Ti3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 4-20°. In the fifth O site, O(5) is bonded to three equivalent Li(1) and three equivalent Ti(1) atoms to form OLi3Ti3 octahedra that share corners with three equivalent O(6)Li3Ti3 octahedra, corners with three equivalent O(2)LiTi3 trigonal pyramids, edges with three equivalent O(7)Li4Ti2 octahedra, edges with six equivalent O(1)Li3Ti2 square pyramids, and edges with three equivalent O(3)LiTi3 tetrahedra. The corner-sharing octahedral tilt angles are 9°. In the sixth O site, O(6) is bonded to three equivalent Li(1) and three equivalent Ti(2) atoms to form OLi3Ti3 octahedra that share corners with three equivalent O(5)Li3Ti3 octahedra, corners with three equivalent O(8)LiTi3 trigonal pyramids, edges with six equivalent O(7)Li4Ti2 octahedra, edges with three equivalent O(1)Li3Ti2 square pyramids, and edges with three equivalent O(4)Li2Ti3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 9°. In the seventh O site, O(7) is bonded to one Li(2), one Li(5), two equivalent Li(1), and two equivalent Ti(2) atoms to form OLi4Ti2 octahedra that share corners with three equivalent O(1)Li3Ti2 square pyramids, corners with three equivalent O(4)Li2Ti3 trigonal bipyramids,  an edgeedge with one O(5)Li3Ti3 octahedra, edges with two equivalent O(6)Li3Ti3 octahedra, edges with four equivalent O(7)Li4Ti2 octahedra, edges with two equivalent O(1)Li3Ti2 square pyramids, edges with two equivalent O(4)Li2Ti3 trigonal bipyramids, and  an edgeedge with one O(8)LiTi3 trigonal pyramid. In the eighth O site, O(8) is bonded to one Li(4) and three equivalent Ti(2) atoms to form distorted OLiTi3 trigonal pyramids that share corners with three equivalent O(6)Li3Ti3 octahedra, corners with three equivalent O(3)LiTi3 tetrahedra, corners with six equivalent O(4)Li2Ti3 trigonal bipyramids, and edges with three equivalent O(7)Li4Ti2 octahedra. The corner-sharing octahedra are not tilted.
Li7Ti7O16 crystallizes in the trigonal R3m space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(5), one O(6), two equivalent O(1), and two equivalent O(7) atoms to form LiO6 octahedra that share corners with three equivalent Ti(1)O6 octahedra, corners with three equivalent Ti(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-9°. The Li(1)-O(5) bond length is 2.18 Å. The Li(1)-O(6) bond length is 2.14 Å. Both Li(1)-O(1) bond lengths are 2.10 Å. Both Li(1)-O(7) bond lengths are 2.32 Å. In the second Li site, Li(2) is bonded to three equivalent O(1) and three equivalent O(7) atoms to form LiO6 octahedra that share edges with three equivalent Ti(1)O6 octahedra, edges with three equivalent Ti(2)O6 octahedra, and edges with six equivalent Li(1)O6 octahedra. All Li(2)-O(1) bond lengths are 2.08 Å. All Li(2)-O(7) bond lengths are 2.10 Å. In the third Li site, Li(3) is bonded to one O(2) and three equivalent O(4) atoms to form LiO4 tetrahedra that share corners with three equivalent Ti(1)O6 octahedra, corners with three equivalent Ti(3)O6 octahedra, and corners with six equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-65°. The Li(3)-O(2) bond length is 1.89 Å. All Li(3)-O(4) bond lengths are 2.04 Å. In the fourth Li site, Li(4) is bonded to one O(8) and three equivalent O(3) atoms to form LiO4 tetrahedra that share corners with three 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 56-62°. The Li(4)-O(8) bond length is 2.09 Å. All Li(4)-O(3) bond lengths are 1.99 Å. In the fifth Li site, Li(5) is bonded in a distorted trigonal non-coplanar geometry to three equivalent O(4) and three equivalent O(7) atoms. All Li(5)-O(4) bond lengths are 2.45 Å. All Li(5)-O(7) bond lengths are 1.92 Å. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(2), one O(5), two equivalent O(1), and two equivalent O(3) atoms to form TiO6 octahedra that share corners with three equivalent Li(1)O6 octahedra,  a cornercorner with one Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Ti(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-7°. The Ti(1)-O(2) bond length is 1.99 Å. The Ti(1)-O(5) bond length is 2.07 Å. Both Ti(1)-O(1) bond lengths are 1.96 Å. Both Ti(1)-O(3) bond lengths are 2.05 Å. In the second Ti site, Ti(2) is bonded to one O(6), one O(8), two equivalent O(4), and two equivalent O(7) atoms to form TiO6 octahedra that share corners with three equivalent Li(1)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Ti(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. The Ti(2)-O(6) bond length is 2.08 Å. The Ti(2)-O(8) bond length is 1.99 Å. Both Ti(2)-O(4) bond lengths are 2.03 Å. Both Ti(2)-O(7) bond lengths are 1.99 Å. In the third Ti site, Ti(3) is bonded to three equivalent O(3) and three equivalent O(4) atoms to form TiO6 octahedra that share corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent Li(4)O4 tetrahedra, edges with three equivalent Ti(1)O6 octahedra, and edges with three equivalent Ti(2)O6 octahedra. All Ti(3)-O(3) bond lengths are 1.97 Å. All Ti(3)-O(4) bond lengths are 2.06 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), and two equivalent Ti(1) atoms to form OLi3Ti2 square pyramids that share corners with three equivalent O(7)Li4Ti2 octahedra, corners with two equivalent O(1)Li3Ti2 square pyramids, corners with four equivalent O(3)LiTi3 tetrahedra,  an edgeedge with one O(6)Li3Ti3 octahedra, edges with two equivalent O(5)Li3Ti3 octahedra, edges with two equivalent O(7)Li4Ti2 octahedra, edges with two equivalent O(1)Li3Ti2 square pyramids, and  an edgeedge with one O(2)LiTi3 trigonal pyramid. The corner-sharing octahedral tilt angles range from 0-7°. In the second O site, O(2) is bonded to one Li(3) and three equivalent Ti(1) atoms to form distorted OLiTi3 trigonal pyramids that share corners with three equivalent O(5)Li3Ti3 octahedra, corners with six equivalent O(3)LiTi3 tetrahedra, corners with three equivalent O(4)Li2Ti3 trigonal bipyramids, and edges with three equivalent O(1)Li3Ti2 square pyramids. The corner-sharing octahedral tilt angles are 1°. In the third O site, O(3) is bonded to one Li(4), one Ti(3), and two equivalent Ti(1) atoms to form distorted OLiTi3 tetrahedra that share corners with four equivalent O(1)Li3Ti2 square pyramids, corners with two equivalent O(3)LiTi3 tetrahedra, corners with three equivalent O(4)Li2Ti3 trigonal bipyramids,  a cornercorner with one O(8)LiTi3 trigonal pyramid, corners with two equivalent O(2)LiTi3 trigonal pyramids,  an edgeedge with one O(5)Li3Ti3 octahedra, and edges with two equivalent O(3)LiTi3 tetrahedra. In the fourth O site, O(4) is bonded to one Li(3), one Li(5), one Ti(3), and two equivalent Ti(2) atoms to form distorted OLi2Ti3 trigonal bipyramids that share corners with three equivalent O(7)Li4Ti2 octahedra, corners with three equivalent O(3)LiTi3 tetrahedra,  a cornercorner with one O(2)LiTi3 trigonal pyramid, corners with two equivalent O(8)LiTi3 trigonal pyramids,  an edgeedge with one O(6)Li3Ti3 octahedra, edges with two equivalent O(7)Li4Ti2 octahedra, and edges with four equivalent O(4)Li2Ti3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 4-20°. In the fifth O site, O(5) is bonded to three equivalent Li(1) and three equivalent Ti(1) atoms to form OLi3Ti3 octahedra that share corners with three equivalent O(6)Li3Ti3 octahedra, corners with three equivalent O(2)LiTi3 trigonal pyramids, edges with three equivalent O(7)Li4Ti2 octahedra, edges with six equivalent O(1)Li3Ti2 square pyramids, and edges with three equivalent O(3)LiTi3 tetrahedra. The corner-sharing octahedral tilt angles are 9°. In the sixth O site, O(6) is bonded to three equivalent Li(1) and three equivalent Ti(2) atoms to form OLi3Ti3 octahedra that share corners with three equivalent O(5)Li3Ti3 octahedra, corners with three equivalent O(8)LiTi3 trigonal pyramids, edges with six equivalent O(7)Li4Ti2 octahedra, edges with three equivalent O(1)Li3Ti2 square pyramids, and edges with three equivalent O(4)Li2Ti3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 9°. In the seventh O site, O(7) is bonded to one Li(2), one Li(5), two equivalent Li(1), and two equivalent Ti(2) atoms to form OLi4Ti2 octahedra that share corners with three equivalent O(1)Li3Ti2 square pyramids, corners with three equivalent O(4)Li2Ti3 trigonal bipyramids,  an edgeedge with one O(5)Li3Ti3 octahedra, edges with two equivalent O(6)Li3Ti3 octahedra, edges with four equivalent O(7)Li4Ti2 octahedra, edges with two equivalent O(1)Li3Ti2 square pyramids, edges with two equivalent O(4)Li2Ti3 trigonal bipyramids, and  an edgeedge with one O(8)LiTi3 trigonal pyramid. In the eighth O site, O(8) is bonded to one Li(4) and three equivalent Ti(2) atoms to form distorted OLiTi3 trigonal pyramids that share corners with three equivalent O(6)Li3Ti3 octahedra, corners with three equivalent O(3)LiTi3 tetrahedra, corners with six equivalent O(4)Li2Ti3 trigonal bipyramids, and edges with three equivalent O(7)Li4Ti2 octahedra. The corner-sharing octahedra are not tilted.