Li3Cr3CoO8 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(2) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Co(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-8°. In the second Li site, Li(2) 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 Cr(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-10°. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CrO6 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 Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-10°. In the second Cr site, Cr(2) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form CrO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. Co(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form CoO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-8°. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(2), one Cr(2), and two equivalent Cr(1) atoms to form OLi2Cr3 square pyramids that share corners with four equivalent O(3)Li2Cr2Co square pyramids, corners with five equivalent O(1)Li2Cr3 square pyramids, edges with four equivalent O(2)Li3Cr2Co octahedra, and edges with four equivalent O(3)Li2Cr2Co square pyramids. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), two equivalent Cr(1), and one Co(1) atom to form OLi3Cr2Co octahedra that share corners with six equivalent O(2)Li3Cr2Co octahedra, edges with four equivalent O(1)Li2Cr3 square pyramids, and edges with eight equivalent O(3)Li2Cr2Co square pyramids. The corner-sharing octahedra are not tilted. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Cr(1), one Cr(2), and one Co(1) atom to form OLi2Cr2Co square pyramids that share corners with two equivalent O(1)Li2Cr3 square pyramids, corners with seven equivalent O(3)Li2Cr2Co square pyramids, edges with four equivalent O(2)Li3Cr2Co octahedra, edges with two equivalent O(3)Li2Cr2Co square pyramids, and edges with two equivalent O(1)Li2Cr3 square pyramids.
Li3Cr3CoO8 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(2) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Co(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-8°. Both Li(1)-O(2) bond lengths are 2.17 Å. All Li(1)-O(3) bond lengths are 2.20 Å. In the second Li site, Li(2) 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 Cr(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-10°. Both Li(2)-O(1) bond lengths are 2.16 Å. Both Li(2)-O(2) bond lengths are 2.15 Å. Both Li(2)-O(3) bond lengths are 2.14 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CrO6 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 Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-10°. Both Cr(1)-O(1) bond lengths are 2.01 Å. Both Cr(1)-O(2) bond lengths are 2.02 Å. Both Cr(1)-O(3) bond lengths are 2.02 Å. In the second Cr site, Cr(2) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form CrO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. Both Cr(2)-O(1) bond lengths are 1.92 Å. All Cr(2)-O(3) bond lengths are 1.94 Å. Co(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form CoO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-8°. Both Co(1)-O(2) bond lengths are 1.97 Å. All Co(1)-O(3) bond lengths are 1.97 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(2), one Cr(2), and two equivalent Cr(1) atoms to form OLi2Cr3 square pyramids that share corners with four equivalent O(3)Li2Cr2Co square pyramids, corners with five equivalent O(1)Li2Cr3 square pyramids, edges with four equivalent O(2)Li3Cr2Co octahedra, and edges with four equivalent O(3)Li2Cr2Co square pyramids. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), two equivalent Cr(1), and one Co(1) atom to form OLi3Cr2Co octahedra that share corners with six equivalent O(2)Li3Cr2Co octahedra, edges with four equivalent O(1)Li2Cr3 square pyramids, and edges with eight equivalent O(3)Li2Cr2Co square pyramids. The corner-sharing octahedra are not tilted. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Cr(1), one Cr(2), and one Co(1) atom to form OLi2Cr2Co square pyramids that share corners with two equivalent O(1)Li2Cr3 square pyramids, corners with seven equivalent O(3)Li2Cr2Co square pyramids, edges with four equivalent O(2)Li3Cr2Co octahedra, edges with two equivalent O(3)Li2Cr2Co square pyramids, and edges with two equivalent O(1)Li2Cr3 square pyramids.