Li3(CoO2)4 crystallizes in the monoclinic P2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and four equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent Co(4)O6 octahedra, corners with four equivalent Co(5)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-10°. In the second Li site, Li(2) is bonded to two equivalent O(2) and four equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent Co(5)O6 octahedra, corners with four equivalent Co(4)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-8°. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form LiO6 octahedra that share corners with six equivalent Co(3)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Co(1)O6 octahedra,  an edgeedge with one Co(2)O6 octahedra,  an edgeedge with one Co(4)O6 octahedra,  an edgeedge with one Co(5)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, and edges with two equivalent Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-12°. There are five inequivalent Co sites. In the first Co site, Co(1) is bonded to two equivalent O(4) and four equivalent O(6) atoms to form CoO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(5)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Co(3)O6 octahedra. In the second Co site, Co(2) is bonded to two equivalent O(3) and four equivalent O(5) atoms to form CoO6 octahedra that share edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Co(4)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Co(3)O6 octahedra. In the third Co site, Co(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form CoO6 octahedra that share corners with six equivalent Li(3)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Co(1)O6 octahedra,  an edgeedge with one Co(2)O6 octahedra,  an edgeedge with one Co(4)O6 octahedra,  an edgeedge with one Co(5)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, and edges with two equivalent Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-12°. In the fourth Co site, Co(4) is bonded to two equivalent O(1) and four equivalent O(5) atoms to form CoO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. In the fifth Co site, Co(5) is bonded to two equivalent O(2) and four equivalent O(6) atoms to form CoO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-10°. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(3), one Co(4), and two equivalent Co(3) atoms to form OLi3Co3 octahedra that share corners with two equivalent O(1)Li3Co3 octahedra, corners with four equivalent O(2)Li3Co3 octahedra, edges with two equivalent O(3)Li2Co3 square pyramids, edges with two equivalent O(4)Li2Co3 square pyramids, edges with four equivalent O(5)Li2Co3 square pyramids, and edges with four equivalent O(6)Li2Co3 square pyramids. The corner-sharing octahedral tilt angles range from 0-2°. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(3), one Co(5), and two equivalent Co(3) atoms to form OLi3Co3 octahedra that share corners with two equivalent O(2)Li3Co3 octahedra, corners with four equivalent O(1)Li3Co3 octahedra, edges with two equivalent O(3)Li2Co3 square pyramids, edges with two equivalent O(4)Li2Co3 square pyramids, edges with four equivalent O(5)Li2Co3 square pyramids, and edges with four equivalent O(6)Li2Co3 square pyramids. The corner-sharing octahedral tilt angles range from 0-2°. In the third O site, O(3) is bonded to two equivalent Li(3), one Co(2), and two equivalent Co(3) atoms to form OLi2Co3 square pyramids that share  a cornercorner with one O(3)Li2Co3 square pyramid, corners with four equivalent O(4)Li2Co3 square pyramids, corners with four equivalent O(6)Li2Co3 square pyramids, edges with two equivalent O(1)Li3Co3 octahedra, edges with two equivalent O(2)Li3Co3 octahedra, and edges with four equivalent O(5)Li2Co3 square pyramids. In the fourth O site, O(4) is bonded to two equivalent Li(3), one Co(1), and two equivalent Co(3) atoms to form OLi2Co3 square pyramids that share  a cornercorner with one O(4)Li2Co3 square pyramid, corners with four equivalent O(3)Li2Co3 square pyramids, corners with four equivalent O(5)Li2Co3 square pyramids, edges with two equivalent O(1)Li3Co3 octahedra, edges with two equivalent O(2)Li3Co3 octahedra, and edges with four equivalent O(6)Li2Co3 square pyramids. In the fifth O site, O(5) is bonded to one Li(2), one Li(3), one Co(2), one Co(3), and one Co(4) atom to form OLi2Co3 square pyramids that share corners with two equivalent O(4)Li2Co3 square pyramids, corners with two equivalent O(6)Li2Co3 square pyramids, corners with five equivalent O(5)Li2Co3 square pyramids, edges with two equivalent O(1)Li3Co3 octahedra, edges with two equivalent O(2)Li3Co3 octahedra, edges with two equivalent O(3)Li2Co3 square pyramids, and edges with two equivalent O(5)Li2Co3 square pyramids. In the sixth O site, O(6) is bonded to one Li(1), one Li(3), one Co(1), one Co(3), and one Co(5) atom to form OLi2Co3 square pyramids that share corners with two equivalent O(3)Li2Co3 square pyramids, corners with two equivalent O(5)Li2Co3 square pyramids, corners with five equivalent O(6)Li2Co3 square pyramids, edges with two equivalent O(1)Li3Co3 octahedra, edges with two equivalent O(2)Li3Co3 octahedra, edges with two equivalent O(4)Li2Co3 square pyramids, and edges with two equivalent O(6)Li2Co3 square pyramids.
Li3(CoO2)4 crystallizes in the monoclinic P2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and four equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent Co(4)O6 octahedra, corners with four equivalent Co(5)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-10°. Both Li(1)-O(1) bond lengths are 2.15 Å. All Li(1)-O(6) bond lengths are 2.15 Å. In the second Li site, Li(2) is bonded to two equivalent O(2) and four equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent Co(5)O6 octahedra, corners with four equivalent Co(4)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-8°. Both Li(2)-O(2) bond lengths are 2.14 Å. All Li(2)-O(5) bond lengths are 2.15 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form LiO6 octahedra that share corners with six equivalent Co(3)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Co(1)O6 octahedra,  an edgeedge with one Co(2)O6 octahedra,  an edgeedge with one Co(4)O6 octahedra,  an edgeedge with one Co(5)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, and edges with two equivalent Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-12°. The Li(3)-O(1) bond length is 2.14 Å. The Li(3)-O(2) bond length is 2.15 Å. The Li(3)-O(3) bond length is 2.14 Å. The Li(3)-O(4) bond length is 2.15 Å. The Li(3)-O(5) bond length is 2.13 Å. The Li(3)-O(6) bond length is 2.15 Å. There are five inequivalent Co sites. In the first Co site, Co(1) is bonded to two equivalent O(4) and four equivalent O(6) atoms to form CoO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(5)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Co(3)O6 octahedra. Both Co(1)-O(4) bond lengths are 1.88 Å. All Co(1)-O(6) bond lengths are 1.91 Å. In the second Co site, Co(2) is bonded to two equivalent O(3) and four equivalent O(5) atoms to form CoO6 octahedra that share edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Co(4)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Co(3)O6 octahedra. Both Co(2)-O(3) bond lengths are 1.94 Å. All Co(2)-O(5) bond lengths are 1.94 Å. In the third Co site, Co(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form CoO6 octahedra that share corners with six equivalent Li(3)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Co(1)O6 octahedra,  an edgeedge with one Co(2)O6 octahedra,  an edgeedge with one Co(4)O6 octahedra,  an edgeedge with one Co(5)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, and edges with two equivalent Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-12°. The Co(3)-O(1) bond length is 2.01 Å. The Co(3)-O(2) bond length is 2.01 Å. The Co(3)-O(3) bond length is 2.00 Å. The Co(3)-O(4) bond length is 2.05 Å. The Co(3)-O(5) bond length is 1.98 Å. The Co(3)-O(6) bond length is 2.04 Å. In the fourth Co site, Co(4) is bonded to two equivalent O(1) and four equivalent O(5) atoms to form CoO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. Both Co(4)-O(1) bond lengths are 1.99 Å. All Co(4)-O(5) bond lengths are 2.01 Å. In the fifth Co site, Co(5) is bonded to two equivalent O(2) and four equivalent O(6) atoms to form CoO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-10°. Both Co(5)-O(2) bond lengths are 2.01 Å. All Co(5)-O(6) bond lengths are 2.02 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(3), one Co(4), and two equivalent Co(3) atoms to form OLi3Co3 octahedra that share corners with two equivalent O(1)Li3Co3 octahedra, corners with four equivalent O(2)Li3Co3 octahedra, edges with two equivalent O(3)Li2Co3 square pyramids, edges with two equivalent O(4)Li2Co3 square pyramids, edges with four equivalent O(5)Li2Co3 square pyramids, and edges with four equivalent O(6)Li2Co3 square pyramids. The corner-sharing octahedral tilt angles range from 0-2°. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(3), one Co(5), and two equivalent Co(3) atoms to form OLi3Co3 octahedra that share corners with two equivalent O(2)Li3Co3 octahedra, corners with four equivalent O(1)Li3Co3 octahedra, edges with two equivalent O(3)Li2Co3 square pyramids, edges with two equivalent O(4)Li2Co3 square pyramids, edges with four equivalent O(5)Li2Co3 square pyramids, and edges with four equivalent O(6)Li2Co3 square pyramids. The corner-sharing octahedral tilt angles range from 0-2°. In the third O site, O(3) is bonded to two equivalent Li(3), one Co(2), and two equivalent Co(3) atoms to form OLi2Co3 square pyramids that share  a cornercorner with one O(3)Li2Co3 square pyramid, corners with four equivalent O(4)Li2Co3 square pyramids, corners with four equivalent O(6)Li2Co3 square pyramids, edges with two equivalent O(1)Li3Co3 octahedra, edges with two equivalent O(2)Li3Co3 octahedra, and edges with four equivalent O(5)Li2Co3 square pyramids. In the fourth O site, O(4) is bonded to two equivalent Li(3), one Co(1), and two equivalent Co(3) atoms to form OLi2Co3 square pyramids that share  a cornercorner with one O(4)Li2Co3 square pyramid, corners with four equivalent O(3)Li2Co3 square pyramids, corners with four equivalent O(5)Li2Co3 square pyramids, edges with two equivalent O(1)Li3Co3 octahedra, edges with two equivalent O(2)Li3Co3 octahedra, and edges with four equivalent O(6)Li2Co3 square pyramids. In the fifth O site, O(5) is bonded to one Li(2), one Li(3), one Co(2), one Co(3), and one Co(4) atom to form OLi2Co3 square pyramids that share corners with two equivalent O(4)Li2Co3 square pyramids, corners with two equivalent O(6)Li2Co3 square pyramids, corners with five equivalent O(5)Li2Co3 square pyramids, edges with two equivalent O(1)Li3Co3 octahedra, edges with two equivalent O(2)Li3Co3 octahedra, edges with two equivalent O(3)Li2Co3 square pyramids, and edges with two equivalent O(5)Li2Co3 square pyramids. In the sixth O site, O(6) is bonded to one Li(1), one Li(3), one Co(1), one Co(3), and one Co(5) atom to form OLi2Co3 square pyramids that share corners with two equivalent O(3)Li2Co3 square pyramids, corners with two equivalent O(5)Li2Co3 square pyramids, corners with five equivalent O(6)Li2Co3 square pyramids, edges with two equivalent O(1)Li3Co3 octahedra, edges with two equivalent O(2)Li3Co3 octahedra, edges with two equivalent O(4)Li2Co3 square pyramids, and edges with two equivalent O(6)Li2Co3 square pyramids.