LiTi4O8 crystallizes in the trigonal R-3m space group. Li(1) is bonded to six equivalent O(1) atoms to form LiO6 octahedra that share corners with six equivalent Ti(2)O6 octahedra and edges with six equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles are 10°. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form TiO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. In the second Ti site, Ti(2) is bonded to six equivalent O(1) atoms to form TiO6 octahedra that share corners with six equivalent Li(1)O6 octahedra and edges with six equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles are 10°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Ti(2), and two equivalent Ti(1) atoms. In the second O site, O(2) is bonded in a distorted T-shaped geometry to three equivalent Ti(1) atoms.
LiTi4O8 crystallizes in the trigonal R-3m space group. Li(1) is bonded to six equivalent O(1) atoms to form LiO6 octahedra that share corners with six equivalent Ti(2)O6 octahedra and edges with six equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles are 10°. All Li(1)-O(1) bond lengths are 2.20 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form TiO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. Both Ti(1)-O(2) bond lengths are 1.99 Å. All Ti(1)-O(1) bond lengths are 1.99 Å. In the second Ti site, Ti(2) is bonded to six equivalent O(1) atoms to form TiO6 octahedra that share corners with six equivalent Li(1)O6 octahedra and edges with six equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles are 10°. All Ti(2)-O(1) bond lengths are 2.03 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Ti(2), and two equivalent Ti(1) atoms. In the second O site, O(2) is bonded in a distorted T-shaped geometry to three equivalent Ti(1) atoms.