Li5Co3O8 is Caswellsilverite-like structured and crystallizes in the monoclinic P2/m space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent Li(4)O6 octahedra, corners with four equivalent Co(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles are 6°. 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 Co(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 Li(4)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with two equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-11°. In the third Li site, Li(3) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent Co(2)O6 octahedra, corners with four equivalent Li(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-11°. In the fourth Li site, Li(4) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-11°. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CoO6 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 Li(4)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with two equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-11°. In the second Co site, Co(2) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form CoO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-6°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Co(1), and one Co(2) atom to form OLi4Co2 octahedra that share corners with six equivalent O(1)Li4Co2 octahedra, edges with four equivalent O(3)Li3Co3 octahedra, edges with four equivalent O(1)Li4Co2 octahedra, and edges with four equivalent O(2)Li4Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the second O site, O(2) is bonded to one Li(1), one Li(4), two equivalent Li(2), and two equivalent Co(1) atoms to form OLi4Co2 octahedra that share corners with two equivalent O(2)Li4Co2 octahedra, corners with four equivalent O(3)Li3Co3 octahedra, edges with two equivalent O(3)Li3Co3 octahedra, edges with two equivalent O(2)Li4Co2 octahedra, and edges with eight equivalent O(1)Li4Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the third O site, O(3) is bonded to one Li(3), two equivalent Li(2), one Co(2), and two equivalent Co(1) atoms to form OLi3Co3 octahedra that share corners with two equivalent O(3)Li3Co3 octahedra, corners with four equivalent O(2)Li4Co2 octahedra, edges with two equivalent O(3)Li3Co3 octahedra, edges with two equivalent O(2)Li4Co2 octahedra, and edges with eight equivalent O(1)Li4Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-6°.
Li5Co3O8 is Caswellsilverite-like structured and crystallizes in the monoclinic P2/m space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent Li(4)O6 octahedra, corners with four equivalent Co(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles are 6°. Both Li(1)-O(2) bond lengths are 1.97 Å. All Li(1)-O(1) bond lengths are 2.22 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 Co(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 Li(4)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with two equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-11°. Both Li(2)-O(1) bond lengths are 2.16 Å. Both Li(2)-O(2) bond lengths are 2.11 Å. Both Li(2)-O(3) bond lengths are 2.14 Å. In the third Li site, Li(3) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent Co(2)O6 octahedra, corners with four equivalent Li(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-11°. Both Li(3)-O(3) bond lengths are 2.17 Å. All Li(3)-O(1) bond lengths are 2.06 Å. In the fourth Li site, Li(4) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-11°. Both Li(4)-O(2) bond lengths are 2.12 Å. All Li(4)-O(1) bond lengths are 2.08 Å. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CoO6 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 Li(4)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with two equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-11°. Both Co(1)-O(1) bond lengths are 1.94 Å. Both Co(1)-O(2) bond lengths are 1.96 Å. Both Co(1)-O(3) bond lengths are 2.04 Å. In the second Co site, Co(2) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form CoO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-6°. Both Co(2)-O(3) bond lengths are 1.92 Å. All Co(2)-O(1) bond lengths are 1.90 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Co(1), and one Co(2) atom to form OLi4Co2 octahedra that share corners with six equivalent O(1)Li4Co2 octahedra, edges with four equivalent O(3)Li3Co3 octahedra, edges with four equivalent O(1)Li4Co2 octahedra, and edges with four equivalent O(2)Li4Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the second O site, O(2) is bonded to one Li(1), one Li(4), two equivalent Li(2), and two equivalent Co(1) atoms to form OLi4Co2 octahedra that share corners with two equivalent O(2)Li4Co2 octahedra, corners with four equivalent O(3)Li3Co3 octahedra, edges with two equivalent O(3)Li3Co3 octahedra, edges with two equivalent O(2)Li4Co2 octahedra, and edges with eight equivalent O(1)Li4Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the third O site, O(3) is bonded to one Li(3), two equivalent Li(2), one Co(2), and two equivalent Co(1) atoms to form OLi3Co3 octahedra that share corners with two equivalent O(3)Li3Co3 octahedra, corners with four equivalent O(2)Li4Co2 octahedra, edges with two equivalent O(3)Li3Co3 octahedra, edges with two equivalent O(2)Li4Co2 octahedra, and edges with eight equivalent O(1)Li4Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-6°.