Li4Ti15O32 crystallizes in the trigonal R-3m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3) and three equivalent O(1) atoms to form LiO4 tetrahedra that share corners with nine equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-62°. In the second Li site, Li(2) is bonded to one O(5) and three equivalent O(6) 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 55-62°. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to three equivalent O(6) and three equivalent O(7) atoms to form TiO6 octahedra that share corners with three equivalent Li(2)O4 tetrahedra, edges with three equivalent Ti(2)O6 octahedra, and edges with three equivalent Ti(3)O6 octahedra. In the second Ti site, Ti(2) is bonded to one O(3), one O(8), two equivalent O(1), and two equivalent O(6) atoms to form TiO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ti(1)O6 octahedra, and edges with four equivalent Ti(2)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(7) atoms to form TiO6 octahedra that share  a cornercorner with one Li(2)O4 tetrahedra,  an edgeedge with one Ti(1)O6 octahedra,  an edgeedge with one Ti(4)O6 octahedra, and edges with four equivalent Ti(3)O6 octahedra. In the fourth Ti site, Ti(4) is bonded to six equivalent O(2) atoms to form edge-sharing TiO6 octahedra. There are eight inequivalent O sites. In the first O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Ti(1), and two equivalent Ti(2) atoms. In the second O site, O(7) is bonded in a distorted T-shaped geometry to one Ti(1) and two equivalent Ti(3) atoms. In the third O site, O(8) is bonded in a distorted T-shaped geometry to three equivalent Ti(2) atoms. In the fourth O site, O(1) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Ti(2) atoms. In the fifth O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Ti(4) and two equivalent Ti(3) atoms. In the sixth O site, O(3) is bonded in a tetrahedral geometry to one Li(1) and three equivalent Ti(2) atoms. In the seventh O site, O(4) is bonded in a distorted T-shaped geometry to three equivalent Ti(3) atoms. In the eighth O site, O(5) is bonded in a distorted trigonal pyramidal geometry to one Li(2) and three equivalent Ti(3) atoms.
Li4Ti15O32 crystallizes in the trigonal R-3m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3) and three equivalent O(1) atoms to form LiO4 tetrahedra that share corners with nine equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-62°. The Li(1)-O(3) bond length is 2.00 Å. All Li(1)-O(1) bond lengths are 1.96 Å. In the second Li site, Li(2) is bonded to one O(5) and three equivalent O(6) 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 55-62°. The Li(2)-O(5) bond length is 2.00 Å. All Li(2)-O(6) bond lengths are 2.02 Å. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to three equivalent O(6) and three equivalent O(7) atoms to form TiO6 octahedra that share corners with three equivalent Li(2)O4 tetrahedra, edges with three equivalent Ti(2)O6 octahedra, and edges with three equivalent Ti(3)O6 octahedra. All Ti(1)-O(6) bond lengths are 1.92 Å. All Ti(1)-O(7) bond lengths are 2.05 Å. In the second Ti site, Ti(2) is bonded to one O(3), one O(8), two equivalent O(1), and two equivalent O(6) atoms to form TiO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ti(1)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. The Ti(2)-O(3) bond length is 2.03 Å. The Ti(2)-O(8) bond length is 1.97 Å. Both Ti(2)-O(1) bond lengths are 1.88 Å. Both Ti(2)-O(6) bond lengths are 2.10 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(7) atoms to form TiO6 octahedra that share  a cornercorner with one Li(2)O4 tetrahedra,  an edgeedge with one Ti(1)O6 octahedra,  an edgeedge with one Ti(4)O6 octahedra, and edges with four equivalent Ti(3)O6 octahedra. The Ti(3)-O(4) bond length is 1.98 Å. The Ti(3)-O(5) bond length is 2.04 Å. Both Ti(3)-O(2) bond lengths are 1.99 Å. Both Ti(3)-O(7) bond lengths are 1.97 Å. In the fourth Ti site, Ti(4) is bonded to six equivalent O(2) atoms to form edge-sharing TiO6 octahedra. All Ti(4)-O(2) bond lengths are 1.99 Å. There are eight inequivalent O sites. In the first O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Ti(1), and two equivalent Ti(2) atoms. In the second O site, O(7) is bonded in a distorted T-shaped geometry to one Ti(1) and two equivalent Ti(3) atoms. In the third O site, O(8) is bonded in a distorted T-shaped geometry to three equivalent Ti(2) atoms. In the fourth O site, O(1) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Ti(2) atoms. In the fifth O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Ti(4) and two equivalent Ti(3) atoms. In the sixth O site, O(3) is bonded in a tetrahedral geometry to one Li(1) and three equivalent Ti(2) atoms. In the seventh O site, O(4) is bonded in a distorted T-shaped geometry to three equivalent Ti(3) atoms. In the eighth O site, O(5) is bonded in a distorted trigonal pyramidal geometry to one Li(2) and three equivalent Ti(3) atoms.