Li5CoO4 crystallizes in the orthorhombic Pnnm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(2), one O(3), and two equivalent O(1) atoms. In the third Li site, Li(3) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form LiO4 tetrahedra that share corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Co(1)O4 tetrahedra, corners with two equivalent Li(4)O4 trigonal pyramids,  an edgeedge with one Li(3)O4 tetrahedra,  an edgeedge with one Co(1)O4 tetrahedra, and  an edgeedge with one Li(4)O4 trigonal pyramid. In the fourth Li site, Li(4) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form distorted LiO4 trigonal pyramids that share corners with four equivalent Li(3)O4 tetrahedra, corners with four equivalent Co(1)O4 tetrahedra, and edges with two equivalent Li(3)O4 tetrahedra. Co(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form distorted CoO4 tetrahedra that share corners with four equivalent Li(3)O4 tetrahedra, corners with four equivalent Li(4)O4 trigonal pyramids, and edges with two equivalent Li(3)O4 tetrahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(4), two equivalent Li(3), and one Co(1) atom. In the second O site, O(2) is bonded in a 7-coordinate geometry to one Li(2), one Li(4), two equivalent Li(1), two equivalent Li(3), and one Co(1) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Li(2), one Li(4), two equivalent Li(1), two equivalent Li(3), and one Co(1) atom.
Li5CoO4 crystallizes in the orthorhombic Pnnm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. Both Li(1)-O(1) bond lengths are 2.01 Å. Both Li(1)-O(2) bond lengths are 2.38 Å. Both Li(1)-O(3) bond lengths are 2.56 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(2), one O(3), and two equivalent O(1) atoms. The Li(2)-O(2) bond length is 2.18 Å. The Li(2)-O(3) bond length is 1.92 Å. Both Li(2)-O(1) bond lengths are 1.90 Å. In the third Li site, Li(3) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form LiO4 tetrahedra that share corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Co(1)O4 tetrahedra, corners with two equivalent Li(4)O4 trigonal pyramids,  an edgeedge with one Li(3)O4 tetrahedra,  an edgeedge with one Co(1)O4 tetrahedra, and  an edgeedge with one Li(4)O4 trigonal pyramid. The Li(3)-O(2) bond length is 1.93 Å. The Li(3)-O(3) bond length is 1.94 Å. There is one shorter (1.99 Å) and one longer (2.00 Å) Li(3)-O(1) bond length. In the fourth Li site, Li(4) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form distorted LiO4 trigonal pyramids that share corners with four equivalent Li(3)O4 tetrahedra, corners with four equivalent Co(1)O4 tetrahedra, and edges with two equivalent Li(3)O4 tetrahedra. The Li(4)-O(2) bond length is 2.04 Å. The Li(4)-O(3) bond length is 2.01 Å. Both Li(4)-O(1) bond lengths are 2.16 Å. Co(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form distorted CoO4 tetrahedra that share corners with four equivalent Li(3)O4 tetrahedra, corners with four equivalent Li(4)O4 trigonal pyramids, and edges with two equivalent Li(3)O4 tetrahedra. The Co(1)-O(2) bond length is 1.90 Å. The Co(1)-O(3) bond length is 1.96 Å. Both Co(1)-O(1) bond lengths are 1.85 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(4), two equivalent Li(3), and one Co(1) atom. In the second O site, O(2) is bonded in a 7-coordinate geometry to one Li(2), one Li(4), two equivalent Li(1), two equivalent Li(3), and one Co(1) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Li(2), one Li(4), two equivalent Li(1), two equivalent Li(3), and one Co(1) atom.