Li(CoO2)2 crystallizes in the triclinic P-1 space group. Li(1) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form distorted LiO6 octahedra that share corners with six equivalent Co(1)O6 octahedra, corners with six equivalent Co(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra,  a faceface with one Co(1)O6 octahedra, and  a faceface with one Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 38-59°. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form CoO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with four equivalent Co(2)O6 octahedra, and  a faceface with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-53°. In the second Co site, Co(2) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form CoO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, edges with four equivalent Co(1)O6 octahedra, and  a faceface with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 38-59°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Co(2), and two equivalent Co(1) atoms. In the second O site, O(2) is bonded to two equivalent Li(1), one Co(2), and two equivalent Co(1) atoms to form distorted OLi2Co3 trigonal bipyramids that share corners with four equivalent O(3)Li2Co3 trigonal bipyramids, corners with two equivalent O(4)LiCo3 trigonal pyramids, edges with two equivalent O(2)Li2Co3 trigonal bipyramids, edges with two equivalent O(3)Li2Co3 trigonal bipyramids, and edges with two equivalent O(4)LiCo3 trigonal pyramids. In the third O site, O(3) is bonded to two equivalent Li(1), one Co(1), and two equivalent Co(2) atoms to form distorted OLi2Co3 trigonal bipyramids that share corners with four equivalent O(2)Li2Co3 trigonal bipyramids, corners with three equivalent O(4)LiCo3 trigonal pyramids, edges with two equivalent O(2)Li2Co3 trigonal bipyramids, edges with two equivalent O(3)Li2Co3 trigonal bipyramids, and edges with two equivalent O(4)LiCo3 trigonal pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Co(1), and two equivalent Co(2) atoms to form OLiCo3 trigonal pyramids that share corners with two equivalent O(2)Li2Co3 trigonal bipyramids, corners with three equivalent O(3)Li2Co3 trigonal bipyramids, edges with two equivalent O(2)Li2Co3 trigonal bipyramids, edges with two equivalent O(3)Li2Co3 trigonal bipyramids, and  an edgeedge with one O(4)LiCo3 trigonal pyramid.
Li(CoO2)2 crystallizes in the triclinic P-1 space group. Li(1) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form distorted LiO6 octahedra that share corners with six equivalent Co(1)O6 octahedra, corners with six equivalent Co(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra,  a faceface with one Co(1)O6 octahedra, and  a faceface with one Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 38-59°. The Li(1)-O(1) bond length is 2.01 Å. The Li(1)-O(4) bond length is 2.10 Å. There is one shorter (2.18 Å) and one longer (2.36 Å) Li(1)-O(2) bond length. There is one shorter (2.20 Å) and one longer (2.32 Å) Li(1)-O(3) bond length. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form CoO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with four equivalent Co(2)O6 octahedra, and  a faceface with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-53°. The Co(1)-O(3) bond length is 1.93 Å. The Co(1)-O(4) bond length is 1.89 Å. Both Co(1)-O(1) bond lengths are 1.92 Å. Both Co(1)-O(2) bond lengths are 1.91 Å. In the second Co site, Co(2) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form CoO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, edges with four equivalent Co(1)O6 octahedra, and  a faceface with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 38-59°. The Co(2)-O(1) bond length is 1.87 Å. The Co(2)-O(2) bond length is 1.98 Å. There is one shorter (1.90 Å) and one longer (2.00 Å) Co(2)-O(3) bond length. There is one shorter (1.85 Å) and one longer (2.08 Å) Co(2)-O(4) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Co(2), and two equivalent Co(1) atoms. In the second O site, O(2) is bonded to two equivalent Li(1), one Co(2), and two equivalent Co(1) atoms to form distorted OLi2Co3 trigonal bipyramids that share corners with four equivalent O(3)Li2Co3 trigonal bipyramids, corners with two equivalent O(4)LiCo3 trigonal pyramids, edges with two equivalent O(2)Li2Co3 trigonal bipyramids, edges with two equivalent O(3)Li2Co3 trigonal bipyramids, and edges with two equivalent O(4)LiCo3 trigonal pyramids. In the third O site, O(3) is bonded to two equivalent Li(1), one Co(1), and two equivalent Co(2) atoms to form distorted OLi2Co3 trigonal bipyramids that share corners with four equivalent O(2)Li2Co3 trigonal bipyramids, corners with three equivalent O(4)LiCo3 trigonal pyramids, edges with two equivalent O(2)Li2Co3 trigonal bipyramids, edges with two equivalent O(3)Li2Co3 trigonal bipyramids, and edges with two equivalent O(4)LiCo3 trigonal pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Co(1), and two equivalent Co(2) atoms to form OLiCo3 trigonal pyramids that share corners with two equivalent O(2)Li2Co3 trigonal bipyramids, corners with three equivalent O(3)Li2Co3 trigonal bipyramids, edges with two equivalent O(2)Li2Co3 trigonal bipyramids, edges with two equivalent O(3)Li2Co3 trigonal bipyramids, and  an edgeedge with one O(4)LiCo3 trigonal pyramid.