Li4TiNi3O8 is Caswellsilverite-derived structured and crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Ti(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. In the second Li site, Li(2) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Ni(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Ni(2)O6 octahedra, 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 Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-13°. Ti(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form TiO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms to form NiO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. In the second Ni site, Ni(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NiO6 octahedra that share corners with six equivalent Li(3)O6 octahedra, 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 Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-13°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), two equivalent Li(2), one Ni(2), and two equivalent Ni(1) atoms to form OLi3Ni3 octahedra that share corners with six equivalent O(1)Li3Ni3 octahedra, edges with four equivalent O(2)Li3TiNi2 octahedra, edges with four equivalent O(3)Li3TiNi2 octahedra, and edges with four equivalent O(4)Li3TiNi2 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Ti(1), one Ni(1), and one Ni(2) atom to form OLi3TiNi2 octahedra that share corners with two equivalent O(3)Li3TiNi2 octahedra, corners with four equivalent O(2)Li3TiNi2 octahedra, edges with four equivalent O(1)Li3Ni3 octahedra, edges with four equivalent O(3)Li3TiNi2 octahedra, and edges with four equivalent O(4)Li3TiNi2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Ti(1), one Ni(1), and one Ni(2) atom to form OLi3TiNi2 octahedra that share corners with two equivalent O(2)Li3TiNi2 octahedra, corners with four equivalent O(3)Li3TiNi2 octahedra, edges with four equivalent O(1)Li3Ni3 octahedra, edges with four equivalent O(2)Li3TiNi2 octahedra, and edges with four equivalent O(4)Li3TiNi2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the fourth O site, O(4) is bonded to one Li(1), two equivalent Li(2), one Ti(1), and two equivalent Ni(1) atoms to form OLi3TiNi2 octahedra that share corners with six equivalent O(4)Li3TiNi2 octahedra, edges with four equivalent O(1)Li3Ni3 octahedra, edges with four equivalent O(2)Li3TiNi2 octahedra, and edges with four equivalent O(3)Li3TiNi2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°.
Li4TiNi3O8 is Caswellsilverite-derived structured and crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Ti(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. Both Li(1)-O(2) bond lengths are 2.20 Å. Both Li(1)-O(3) bond lengths are 2.19 Å. Both Li(1)-O(4) bond lengths are 2.15 Å. In the second Li site, Li(2) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Ni(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. The Li(2)-O(2) bond length is 2.15 Å. The Li(2)-O(3) bond length is 2.16 Å. There is one shorter (2.25 Å) and one longer (2.29 Å) Li(2)-O(1) bond length. Both Li(2)-O(4) bond lengths are 2.05 Å. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Ni(2)O6 octahedra, 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 Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-13°. Both Li(3)-O(1) bond lengths are 2.07 Å. Both Li(3)-O(2) bond lengths are 2.11 Å. Both Li(3)-O(3) bond lengths are 2.13 Å. Ti(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form TiO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. Both Ti(1)-O(2) bond lengths are 2.01 Å. Both Ti(1)-O(3) bond lengths are 2.01 Å. Both Ti(1)-O(4) bond lengths are 1.94 Å. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms to form NiO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. The Ni(1)-O(2) bond length is 1.93 Å. The Ni(1)-O(3) bond length is 1.93 Å. Both Ni(1)-O(1) bond lengths are 1.94 Å. Both Ni(1)-O(4) bond lengths are 2.16 Å. In the second Ni site, Ni(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NiO6 octahedra that share corners with six equivalent Li(3)O6 octahedra, 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 Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-13°. Both Ni(2)-O(1) bond lengths are 2.04 Å. Both Ni(2)-O(2) bond lengths are 2.10 Å. Both Ni(2)-O(3) bond lengths are 2.08 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), two equivalent Li(2), one Ni(2), and two equivalent Ni(1) atoms to form OLi3Ni3 octahedra that share corners with six equivalent O(1)Li3Ni3 octahedra, edges with four equivalent O(2)Li3TiNi2 octahedra, edges with four equivalent O(3)Li3TiNi2 octahedra, and edges with four equivalent O(4)Li3TiNi2 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Ti(1), one Ni(1), and one Ni(2) atom to form OLi3TiNi2 octahedra that share corners with two equivalent O(3)Li3TiNi2 octahedra, corners with four equivalent O(2)Li3TiNi2 octahedra, edges with four equivalent O(1)Li3Ni3 octahedra, edges with four equivalent O(3)Li3TiNi2 octahedra, and edges with four equivalent O(4)Li3TiNi2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Ti(1), one Ni(1), and one Ni(2) atom to form OLi3TiNi2 octahedra that share corners with two equivalent O(2)Li3TiNi2 octahedra, corners with four equivalent O(3)Li3TiNi2 octahedra, edges with four equivalent O(1)Li3Ni3 octahedra, edges with four equivalent O(2)Li3TiNi2 octahedra, and edges with four equivalent O(4)Li3TiNi2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the fourth O site, O(4) is bonded to one Li(1), two equivalent Li(2), one Ti(1), and two equivalent Ni(1) atoms to form OLi3TiNi2 octahedra that share corners with six equivalent O(4)Li3TiNi2 octahedra, edges with four equivalent O(1)Li3Ni3 octahedra, edges with four equivalent O(2)Li3TiNi2 octahedra, and edges with four equivalent O(3)Li3TiNi2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°.