LiCo2CuO6 crystallizes in the monoclinic Cm space group. Li(1) is bonded to one O(1), one O(4), two equivalent O(3), and two equivalent O(5) atoms to form LiO6 octahedra that share  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Cu(1)O6 octahedra, corners with four equivalent Co(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, and edges with two equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-17°. 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(6) 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 Co(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, and edges with two equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles are 17°. In the second Co site, Co(2) is bonded to one O(2), one O(6), two equivalent O(3), and two equivalent O(5) atoms to form CoO6 octahedra that share corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, and edges with two equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-11°. Cu(1) is bonded to one O(1), one O(5), two equivalent O(2), and two equivalent O(4) atoms to form CuO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, and edges with two equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles are 15°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Co(1), and one Cu(1) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Co(2) and two equivalent Cu(1) atoms. 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 OLi2Co3 square pyramids that share corners with four equivalent O(5)Li2Co2Cu square pyramids, edges with two equivalent O(5)Li2Co2Cu square pyramids, and edges with two equivalent O(3)Li2Co3 square pyramids. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Li(1), one Co(1), and two equivalent Cu(1) atoms. In the fifth O site, O(5) is bonded to two equivalent Li(1), two equivalent Co(2), and one Cu(1) atom to form OLi2Co2Cu square pyramids that share corners with four equivalent O(3)Li2Co3 square pyramids, edges with two equivalent O(5)Li2Co2Cu square pyramids, and edges with two equivalent O(3)Li2Co3 square pyramids. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Co(2) and two equivalent Co(1) atoms.
LiCo2CuO6 crystallizes in the monoclinic Cm space group. Li(1) is bonded to one O(1), one O(4), two equivalent O(3), and two equivalent O(5) atoms to form LiO6 octahedra that share  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Cu(1)O6 octahedra, corners with four equivalent Co(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, and edges with two equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-17°. The Li(1)-O(1) bond length is 2.08 Å. The Li(1)-O(4) bond length is 2.32 Å. Both Li(1)-O(3) bond lengths are 2.17 Å. Both Li(1)-O(5) bond lengths are 2.12 Å. 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(6) 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 Co(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, and edges with two equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles are 17°. The Co(1)-O(3) bond length is 1.89 Å. The Co(1)-O(4) bond length is 1.92 Å. Both Co(1)-O(1) bond lengths are 1.88 Å. Both Co(1)-O(6) bond lengths are 1.88 Å. In the second Co site, Co(2) is bonded to one O(2), one O(6), two equivalent O(3), and two equivalent O(5) atoms to form CoO6 octahedra that share corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, and edges with two equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-11°. The Co(2)-O(2) bond length is 1.88 Å. The Co(2)-O(6) bond length is 1.90 Å. Both Co(2)-O(3) bond lengths are 1.92 Å. Both Co(2)-O(5) bond lengths are 1.90 Å. Cu(1) is bonded to one O(1), one O(5), two equivalent O(2), and two equivalent O(4) atoms to form CuO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, and edges with two equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles are 15°. The Cu(1)-O(1) bond length is 2.12 Å. The Cu(1)-O(5) bond length is 2.11 Å. Both Cu(1)-O(2) bond lengths are 1.89 Å. Both Cu(1)-O(4) bond lengths are 1.90 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Co(1), and one Cu(1) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Co(2) and two equivalent Cu(1) atoms. 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 OLi2Co3 square pyramids that share corners with four equivalent O(5)Li2Co2Cu square pyramids, edges with two equivalent O(5)Li2Co2Cu square pyramids, and edges with two equivalent O(3)Li2Co3 square pyramids. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Li(1), one Co(1), and two equivalent Cu(1) atoms. In the fifth O site, O(5) is bonded to two equivalent Li(1), two equivalent Co(2), and one Cu(1) atom to form OLi2Co2Cu square pyramids that share corners with four equivalent O(3)Li2Co3 square pyramids, edges with two equivalent O(5)Li2Co2Cu square pyramids, and edges with two equivalent O(3)Li2Co3 square pyramids. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Co(2) and two equivalent Co(1) atoms.