Li5CoO4 is Ilmenite-like structured and crystallizes in the orthorhombic Aea2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted LiO4 trigonal pyramids that share corners with two equivalent Co(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(3)O4 tetrahedra,  an edgeedge with one Co(1)O4 tetrahedra, edges with two equivalent Li(2)O4 tetrahedra, and edges with two equivalent Li(1)O4 trigonal pyramids. In the second Li site, Li(2) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with two equivalent Li(3)O4 tetrahedra, corners with four equivalent Co(1)O4 tetrahedra, corners with four equivalent Li(1)O4 trigonal pyramids,  an edgeedge with one Li(3)O4 tetrahedra, edges with two equivalent Li(2)O4 tetrahedra, and edges with two equivalent Li(1)O4 trigonal pyramids. In the third Li site, Li(3) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with two equivalent Co(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, corners with eight equivalent Li(1)O4 trigonal pyramids,  an edgeedge with one Co(1)O4 tetrahedra, and edges with two equivalent Li(2)O4 tetrahedra. Co(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted CoO4 tetrahedra that share corners with two equivalent Li(3)O4 tetrahedra, corners with eight equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(1)O4 trigonal pyramids,  an edgeedge with one Li(3)O4 tetrahedra, and edges with two equivalent Li(1)O4 trigonal pyramids. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), two equivalent Li(1), two equivalent Li(2), and one Co(1) atom to form a mixture of distorted edge and corner-sharing OLi5Co octahedra. The corner-sharing octahedral tilt angles range from 63-68°. In the second O site, O(2) is bonded to one Li(3), two equivalent Li(1), two equivalent Li(2), and one Co(1) atom to form a mixture of distorted edge and corner-sharing OLi5Co pentagonal pyramids. The corner-sharing octahedral tilt angles range from 36-62°.
Li5CoO4 is Ilmenite-like structured and crystallizes in the orthorhombic Aea2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted LiO4 trigonal pyramids that share corners with two equivalent Co(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(3)O4 tetrahedra,  an edgeedge with one Co(1)O4 tetrahedra, edges with two equivalent Li(2)O4 tetrahedra, and edges with two equivalent Li(1)O4 trigonal pyramids. There is one shorter (1.92 Å) and one longer (2.04 Å) Li(1)-O(1) bond length. There is one shorter (1.91 Å) and one longer (1.95 Å) Li(1)-O(2) bond length. In the second Li site, Li(2) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with two equivalent Li(3)O4 tetrahedra, corners with four equivalent Co(1)O4 tetrahedra, corners with four equivalent Li(1)O4 trigonal pyramids,  an edgeedge with one Li(3)O4 tetrahedra, edges with two equivalent Li(2)O4 tetrahedra, and edges with two equivalent Li(1)O4 trigonal pyramids. There is one shorter (1.94 Å) and one longer (2.03 Å) Li(2)-O(1) bond length. There is one shorter (1.88 Å) and one longer (1.98 Å) Li(2)-O(2) bond length. In the third Li site, Li(3) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with two equivalent Co(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, corners with eight equivalent Li(1)O4 trigonal pyramids,  an edgeedge with one Co(1)O4 tetrahedra, and edges with two equivalent Li(2)O4 tetrahedra. Both Li(3)-O(1) bond lengths are 2.00 Å. Both Li(3)-O(2) bond lengths are 1.95 Å. Co(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted CoO4 tetrahedra that share corners with two equivalent Li(3)O4 tetrahedra, corners with eight equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(1)O4 trigonal pyramids,  an edgeedge with one Li(3)O4 tetrahedra, and edges with two equivalent Li(1)O4 trigonal pyramids. Both Co(1)-O(1) bond lengths are 1.87 Å. Both Co(1)-O(2) bond lengths are 1.88 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), two equivalent Li(1), two equivalent Li(2), and one Co(1) atom to form a mixture of distorted edge and corner-sharing OLi5Co octahedra. The corner-sharing octahedral tilt angles range from 63-68°. In the second O site, O(2) is bonded to one Li(3), two equivalent Li(1), two equivalent Li(2), and one Co(1) atom to form a mixture of distorted edge and corner-sharing OLi5Co pentagonal pyramids. The corner-sharing octahedral tilt angles range from 36-62°.