Li6CoO4 crystallizes in the tetragonal P4_2/nmc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to four equivalent O(1) atoms to form LiO4 tetrahedra that share corners with four equivalent Co(1)O4 tetrahedra, corners with eight equivalent Li(2)O4 tetrahedra, edges with two equivalent Li(1)O4 tetrahedra, and edges with four equivalent Li(2)O4 tetrahedra. In the second Li site, Li(2) is bonded to four equivalent O(1) atoms to form distorted LiO4 tetrahedra that share corners with two equivalent Co(1)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, corners with eight equivalent Li(2)O4 tetrahedra,  an edgeedge with one Co(1)O4 tetrahedra, edges with two equivalent Li(1)O4 tetrahedra, and edges with two equivalent Li(2)O4 tetrahedra. Co(1) is bonded to four equivalent O(1) atoms to form CoO4 tetrahedra that share corners with eight equivalent Li(1)O4 tetrahedra, corners with eight equivalent Li(2)O4 tetrahedra, and edges with four equivalent Li(2)O4 tetrahedra. O(1) is bonded to two equivalent Li(1), four equivalent Li(2), and one Co(1) atom to form a mixture of distorted corner and edge-sharing OLi6Co pentagonal bipyramids.
Li6CoO4 crystallizes in the tetragonal P4_2/nmc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to four equivalent O(1) atoms to form LiO4 tetrahedra that share corners with four equivalent Co(1)O4 tetrahedra, corners with eight equivalent Li(2)O4 tetrahedra, edges with two equivalent Li(1)O4 tetrahedra, and edges with four equivalent Li(2)O4 tetrahedra. There are two shorter (1.88 Å) and two longer (1.95 Å) Li(1)-O(1) bond lengths. In the second Li site, Li(2) is bonded to four equivalent O(1) atoms to form distorted LiO4 tetrahedra that share corners with two equivalent Co(1)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, corners with eight equivalent Li(2)O4 tetrahedra,  an edgeedge with one Co(1)O4 tetrahedra, edges with two equivalent Li(1)O4 tetrahedra, and edges with two equivalent Li(2)O4 tetrahedra. There are two shorter (1.95 Å) and two longer (2.08 Å) Li(2)-O(1) bond lengths. Co(1) is bonded to four equivalent O(1) atoms to form CoO4 tetrahedra that share corners with eight equivalent Li(1)O4 tetrahedra, corners with eight equivalent Li(2)O4 tetrahedra, and edges with four equivalent Li(2)O4 tetrahedra. All Co(1)-O(1) bond lengths are 1.97 Å. O(1) is bonded to two equivalent Li(1), four equivalent Li(2), and one Co(1) atom to form a mixture of distorted corner and edge-sharing OLi6Co pentagonal bipyramids.