LiTi3O4 is Caswellsilverite-like structured and crystallizes in the monoclinic Pm space group. Li(1) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) 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, edges with four equivalent Ti(2)O6 octahedra, and edges with four equivalent Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) 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, edges with four equivalent Ti(2)O6 octahedra, and edges with four equivalent Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the second Ti site, Ti(2) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form TiO6 octahedra that share corners with six equivalent Ti(3)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, edges with two equivalent Ti(3)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 1-16°. In the third Ti site, Ti(3) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form TiO6 octahedra that share corners with six equivalent Ti(2)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, edges with two equivalent Ti(3)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 1-16°. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Ti(2), one Ti(3), and two equivalent Ti(1) atoms to form OLi2Ti4 octahedra that share corners with six equivalent O(3)Li2Ti4 octahedra, edges with two equivalent O(1)Li2Ti4 octahedra, edges with two equivalent O(3)Li2Ti4 octahedra, edges with four equivalent O(2)LiTi5 octahedra, and edges with four equivalent O(4)LiTi5 octahedra. The corner-sharing octahedral tilt angles range from 5-13°. In the second O site, O(2) is bonded to one Li(1), one Ti(1), two equivalent Ti(2), and two equivalent Ti(3) atoms to form OLiTi5 octahedra that share corners with six equivalent O(4)LiTi5 octahedra, edges with two equivalent O(2)LiTi5 octahedra, edges with two equivalent O(4)LiTi5 octahedra, edges with four equivalent O(1)Li2Ti4 octahedra, and edges with four equivalent O(3)Li2Ti4 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the third O site, O(3) is bonded to two equivalent Li(1), one Ti(2), one Ti(3), and two equivalent Ti(1) atoms to form OLi2Ti4 octahedra that share corners with six equivalent O(1)Li2Ti4 octahedra, edges with two equivalent O(1)Li2Ti4 octahedra, edges with two equivalent O(3)Li2Ti4 octahedra, edges with four equivalent O(2)LiTi5 octahedra, and edges with four equivalent O(4)LiTi5 octahedra. The corner-sharing octahedral tilt angles range from 5-13°. In the fourth O site, O(4) is bonded to one Li(1), one Ti(1), two equivalent Ti(2), and two equivalent Ti(3) atoms to form OLiTi5 octahedra that share corners with six equivalent O(2)LiTi5 octahedra, edges with two equivalent O(2)LiTi5 octahedra, edges with two equivalent O(4)LiTi5 octahedra, edges with four equivalent O(1)Li2Ti4 octahedra, and edges with four equivalent O(3)Li2Ti4 octahedra. The corner-sharing octahedral tilt angles range from 0-11°.
LiTi3O4 is Caswellsilverite-like structured and crystallizes in the monoclinic Pm space group. Li(1) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) 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, edges with four equivalent Ti(2)O6 octahedra, and edges with four equivalent Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. The Li(1)-O(2) bond length is 1.95 Å. The Li(1)-O(4) bond length is 2.06 Å. Both Li(1)-O(1) bond lengths are 2.13 Å. Both Li(1)-O(3) bond lengths are 2.13 Å. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) 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, edges with four equivalent Ti(2)O6 octahedra, and edges with four equivalent Ti(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. The Ti(1)-O(2) bond length is 2.14 Å. The Ti(1)-O(4) bond length is 2.29 Å. Both Ti(1)-O(1) bond lengths are 2.11 Å. Both Ti(1)-O(3) bond lengths are 2.11 Å. In the second Ti site, Ti(2) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form TiO6 octahedra that share corners with six equivalent Ti(3)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, edges with two equivalent Ti(3)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 1-16°. The Ti(2)-O(1) bond length is 2.14 Å. The Ti(2)-O(3) bond length is 2.09 Å. Both Ti(2)-O(2) bond lengths are 2.06 Å. Both Ti(2)-O(4) bond lengths are 2.19 Å. In the third Ti site, Ti(3) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form TiO6 octahedra that share corners with six equivalent Ti(2)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, edges with two equivalent Ti(3)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 1-16°. The Ti(3)-O(1) bond length is 2.08 Å. The Ti(3)-O(3) bond length is 2.14 Å. Both Ti(3)-O(2) bond lengths are 2.06 Å. Both Ti(3)-O(4) bond lengths are 2.18 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Ti(2), one Ti(3), and two equivalent Ti(1) atoms to form OLi2Ti4 octahedra that share corners with six equivalent O(3)Li2Ti4 octahedra, edges with two equivalent O(1)Li2Ti4 octahedra, edges with two equivalent O(3)Li2Ti4 octahedra, edges with four equivalent O(2)LiTi5 octahedra, and edges with four equivalent O(4)LiTi5 octahedra. The corner-sharing octahedral tilt angles range from 5-13°. In the second O site, O(2) is bonded to one Li(1), one Ti(1), two equivalent Ti(2), and two equivalent Ti(3) atoms to form OLiTi5 octahedra that share corners with six equivalent O(4)LiTi5 octahedra, edges with two equivalent O(2)LiTi5 octahedra, edges with two equivalent O(4)LiTi5 octahedra, edges with four equivalent O(1)Li2Ti4 octahedra, and edges with four equivalent O(3)Li2Ti4 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the third O site, O(3) is bonded to two equivalent Li(1), one Ti(2), one Ti(3), and two equivalent Ti(1) atoms to form OLi2Ti4 octahedra that share corners with six equivalent O(1)Li2Ti4 octahedra, edges with two equivalent O(1)Li2Ti4 octahedra, edges with two equivalent O(3)Li2Ti4 octahedra, edges with four equivalent O(2)LiTi5 octahedra, and edges with four equivalent O(4)LiTi5 octahedra. The corner-sharing octahedral tilt angles range from 5-13°. In the fourth O site, O(4) is bonded to one Li(1), one Ti(1), two equivalent Ti(2), and two equivalent Ti(3) atoms to form OLiTi5 octahedra that share corners with six equivalent O(2)LiTi5 octahedra, edges with two equivalent O(2)LiTi5 octahedra, edges with two equivalent O(4)LiTi5 octahedra, edges with four equivalent O(1)Li2Ti4 octahedra, and edges with four equivalent O(3)Li2Ti4 octahedra. The corner-sharing octahedral tilt angles range from 0-11°.