LiCo2CuO6 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent Co(1)O6 octahedra, corners with four equivalent Cu(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cu(1)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles are 15°. Co(1) is bonded to one O(2), two equivalent O(1), and three equivalent O(3) atoms to form CoO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cu(1)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles are 15°. Cu(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form CuO6 octahedra that share corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cu(1)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles are 15°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Co(1) and one Cu(1) atom. In the second O site, O(2) is bonded to two equivalent Li(1), one Co(1), and two equivalent Cu(1) atoms to form a mixture of corner and edge-sharing OLi2CoCu2 square pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1) and three equivalent Co(1) atoms.
LiCo2CuO6 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent Co(1)O6 octahedra, corners with four equivalent Cu(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cu(1)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles are 15°. Both Li(1)-O(3) bond lengths are 2.16 Å. All Li(1)-O(2) bond lengths are 2.13 Å. Co(1) is bonded to one O(2), two equivalent O(1), and three equivalent O(3) atoms to form CoO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cu(1)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles are 15°. The Co(1)-O(2) bond length is 1.87 Å. Both Co(1)-O(1) bond lengths are 1.86 Å. There is one shorter (1.89 Å) and two longer (1.91 Å) Co(1)-O(3) bond lengths. Cu(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form CuO6 octahedra that share corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cu(1)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles are 15°. Both Cu(1)-O(1) bond lengths are 2.03 Å. All Cu(1)-O(2) bond lengths are 1.99 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Co(1) and one Cu(1) atom. In the second O site, O(2) is bonded to two equivalent Li(1), one Co(1), and two equivalent Cu(1) atoms to form a mixture of corner and edge-sharing OLi2CoCu2 square pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1) and three equivalent Co(1) atoms.