Li3Ti4O8 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form TiO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the second Ti site, Ti(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form TiO6 octahedra that share corners with six equivalent Ti(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the third Ti site, Ti(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form TiO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(2), one Ti(1), and two equivalent Ti(2) atoms to form OLi3Ti3 octahedra that share corners with six equivalent O(1)Li3Ti3 octahedra, edges with four equivalent O(3)Li2Ti3 square pyramids, edges with four equivalent O(4)Li3Ti2 square pyramids, and edges with four equivalent O(2)LiTi4 square pyramids. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), one Ti(1), one Ti(3), and two equivalent Ti(2) atoms to form OLiTi4 square pyramids that share corners with two equivalent O(3)Li2Ti3 square pyramids, corners with two equivalent O(4)Li3Ti2 square pyramids, corners with five equivalent O(2)LiTi4 square pyramids, edges with four equivalent O(1)Li3Ti3 octahedra, edges with two equivalent O(3)Li2Ti3 square pyramids, and edges with two equivalent O(4)Li3Ti2 square pyramids. In the third O site, O(3) is bonded to two equivalent Li(2), one Ti(3), and two equivalent Ti(2) atoms to form OLi2Ti3 square pyramids that share corners with two equivalent O(4)Li3Ti2 square pyramids, corners with two equivalent O(2)LiTi4 square pyramids, corners with five equivalent O(3)Li2Ti3 square pyramids, edges with four equivalent O(1)Li3Ti3 octahedra, edges with two equivalent O(4)Li3Ti2 square pyramids, and edges with two equivalent O(2)LiTi4 square pyramids. In the fourth O site, O(4) is bonded to one Li(1), two equivalent Li(2), one Ti(1), and one Ti(3) atom to form OLi3Ti2 square pyramids that share corners with two equivalent O(3)Li2Ti3 square pyramids, corners with two equivalent O(2)LiTi4 square pyramids, corners with five equivalent O(4)Li3Ti2 square pyramids, edges with four equivalent O(1)Li3Ti3 octahedra, edges with two equivalent O(3)Li2Ti3 square pyramids, and edges with two equivalent O(2)LiTi4 square pyramids.
Li3Ti4O8 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. Both Li(1)-O(1) bond lengths are 2.10 Å. Both Li(1)-O(2) bond lengths are 2.09 Å. Both Li(1)-O(4) bond lengths are 2.16 Å. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. Both Li(2)-O(1) bond lengths are 2.04 Å. Both Li(2)-O(3) bond lengths are 2.09 Å. Both Li(2)-O(4) bond lengths are 2.10 Å. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form TiO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. Both Ti(1)-O(1) bond lengths are 2.09 Å. Both Ti(1)-O(2) bond lengths are 2.09 Å. Both Ti(1)-O(4) bond lengths are 1.94 Å. In the second Ti site, Ti(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form TiO6 octahedra that share corners with six equivalent Ti(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. Both Ti(2)-O(1) bond lengths are 2.09 Å. Both Ti(2)-O(2) bond lengths are 2.09 Å. Both Ti(2)-O(3) bond lengths are 2.04 Å. In the third Ti site, Ti(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form TiO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. Both Ti(3)-O(2) bond lengths are 2.04 Å. Both Ti(3)-O(3) bond lengths are 2.04 Å. Both Ti(3)-O(4) bond lengths are 1.93 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(2), one Ti(1), and two equivalent Ti(2) atoms to form OLi3Ti3 octahedra that share corners with six equivalent O(1)Li3Ti3 octahedra, edges with four equivalent O(3)Li2Ti3 square pyramids, edges with four equivalent O(4)Li3Ti2 square pyramids, and edges with four equivalent O(2)LiTi4 square pyramids. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), one Ti(1), one Ti(3), and two equivalent Ti(2) atoms to form OLiTi4 square pyramids that share corners with two equivalent O(3)Li2Ti3 square pyramids, corners with two equivalent O(4)Li3Ti2 square pyramids, corners with five equivalent O(2)LiTi4 square pyramids, edges with four equivalent O(1)Li3Ti3 octahedra, edges with two equivalent O(3)Li2Ti3 square pyramids, and edges with two equivalent O(4)Li3Ti2 square pyramids. In the third O site, O(3) is bonded to two equivalent Li(2), one Ti(3), and two equivalent Ti(2) atoms to form OLi2Ti3 square pyramids that share corners with two equivalent O(4)Li3Ti2 square pyramids, corners with two equivalent O(2)LiTi4 square pyramids, corners with five equivalent O(3)Li2Ti3 square pyramids, edges with four equivalent O(1)Li3Ti3 octahedra, edges with two equivalent O(4)Li3Ti2 square pyramids, and edges with two equivalent O(2)LiTi4 square pyramids. In the fourth O site, O(4) is bonded to one Li(1), two equivalent Li(2), one Ti(1), and one Ti(3) atom to form OLi3Ti2 square pyramids that share corners with two equivalent O(3)Li2Ti3 square pyramids, corners with two equivalent O(2)LiTi4 square pyramids, corners with five equivalent O(4)Li3Ti2 square pyramids, edges with four equivalent O(1)Li3Ti3 octahedra, edges with two equivalent O(3)Li2Ti3 square pyramids, and edges with two equivalent O(2)LiTi4 square pyramids.