Li3Ti4O8 crystallizes in the trigonal R-3m space group. Li(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with six equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-7°. 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 corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-7°. In the second Ti site, Ti(2) is bonded to six equivalent O(1) atoms to form TiO6 octahedra that share edges with six equivalent Li(1)O6 octahedra and edges with six equivalent Ti(1)O6 octahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Ti(2), and two equivalent Ti(1) atoms to form OLi2Ti3 square pyramids that share corners with nine equivalent O(1)Li2Ti3 square pyramids, edges with four equivalent O(2)Li3Ti3 octahedra, and edges with four equivalent O(1)Li2Ti3 square pyramids. In the second O site, O(2) is bonded to three equivalent Li(1) and three equivalent Ti(1) atoms to form OLi3Ti3 octahedra that share corners with six equivalent O(2)Li3Ti3 octahedra and edges with twelve equivalent O(1)Li2Ti3 square pyramids. The corner-sharing octahedra are not tilted.
Li3Ti4O8 crystallizes in the trigonal R-3m space group. Li(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with six equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-7°. Both Li(1)-O(2) bond lengths are 2.16 Å. All Li(1)-O(1) bond lengths are 2.18 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 corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-7°. Both Ti(1)-O(2) bond lengths are 2.06 Å. All Ti(1)-O(1) bond lengths are 2.05 Å. In the second Ti site, Ti(2) is bonded to six equivalent O(1) atoms to form TiO6 octahedra that share edges with six equivalent Li(1)O6 octahedra and edges with six equivalent Ti(1)O6 octahedra. All Ti(2)-O(1) bond lengths are 2.01 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Ti(2), and two equivalent Ti(1) atoms to form OLi2Ti3 square pyramids that share corners with nine equivalent O(1)Li2Ti3 square pyramids, edges with four equivalent O(2)Li3Ti3 octahedra, and edges with four equivalent O(1)Li2Ti3 square pyramids. In the second O site, O(2) is bonded to three equivalent Li(1) and three equivalent Ti(1) atoms to form OLi3Ti3 octahedra that share corners with six equivalent O(2)Li3Ti3 octahedra and edges with twelve equivalent O(1)Li2Ti3 square pyramids. The corner-sharing octahedra are not tilted.