LiTi3O4 is Caswellsilverite-like structured and crystallizes in the orthorhombic Cmmm 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 Li(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with eight equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. 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 Li(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with eight equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second Ti site, Ti(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form TiO6 octahedra that share corners with six equivalent Ti(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, edges with four equivalent Ti(1)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-5°. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent Ti(1), and two equivalent Ti(2) atoms to form OLi2Ti4 octahedra that share corners with six equivalent O(1)Li2Ti4 octahedra, edges with four equivalent O(1)Li2Ti4 octahedra, and edges with eight equivalent O(2)LiTi5 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), one Ti(1), and four equivalent Ti(2) atoms to form OLiTi5 octahedra that share corners with six equivalent O(2)LiTi5 octahedra, edges with four equivalent O(2)LiTi5 octahedra, and edges with eight equivalent O(1)Li2Ti4 octahedra. The corner-sharing octahedra are not tilted.
LiTi3O4 is Caswellsilverite-like structured and crystallizes in the orthorhombic Cmmm 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 Li(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with eight equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. Both Li(1)-O(2) bond lengths are 1.99 Å. All Li(1)-O(1) bond lengths are 2.10 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 Li(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with eight equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. Both Ti(1)-O(2) bond lengths are 2.18 Å. All Ti(1)-O(1) bond lengths are 2.15 Å. In the second Ti site, Ti(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form TiO6 octahedra that share corners with six equivalent Ti(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, edges with four equivalent Ti(1)O6 octahedra, and edges with four equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-5°. Both Ti(2)-O(1) bond lengths are 2.09 Å. All Ti(2)-O(2) bond lengths are 2.12 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent Ti(1), and two equivalent Ti(2) atoms to form OLi2Ti4 octahedra that share corners with six equivalent O(1)Li2Ti4 octahedra, edges with four equivalent O(1)Li2Ti4 octahedra, and edges with eight equivalent O(2)LiTi5 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), one Ti(1), and four equivalent Ti(2) atoms to form OLiTi5 octahedra that share corners with six equivalent O(2)LiTi5 octahedra, edges with four equivalent O(2)LiTi5 octahedra, and edges with eight equivalent O(1)Li2Ti4 octahedra. The corner-sharing octahedra are not tilted.