LiCr2CoO6 crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(1), one O(3), two equivalent O(4), and two equivalent O(5) atoms to form LiO6 octahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra, corners with four equivalent Cr(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-18°. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(6) atoms to form CrO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles are 18°. In the second Cr site, Cr(2) is bonded to one O(2), one O(6), two equivalent O(4), and two equivalent O(5) atoms to form CrO6 octahedra that share corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-13°. Co(1) is bonded to one O(1), one O(5), two equivalent O(2), and two 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 Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles are 13°. 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 Cr(1), and one Co(1) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Cr(2) and two equivalent Co(1) atoms. In the third O site, O(3) is bonded to one Li(1), one Cr(1), and two equivalent Co(1) atoms to form OLiCrCo2 trigonal pyramids that share corners with three equivalent O(4)Li2Cr3 square pyramids, corners with two equivalent O(3)LiCrCo2 trigonal pyramids, and edges with two equivalent O(5)Li2Cr2Co square pyramids. In the fourth O site, O(4) is bonded to two equivalent Li(1), one Cr(1), and two equivalent Cr(2) atoms to form OLi2Cr3 square pyramids that share corners with four equivalent O(5)Li2Cr2Co square pyramids, corners with three equivalent O(3)LiCrCo2 trigonal pyramids, edges with two equivalent O(5)Li2Cr2Co square pyramids, and edges with two equivalent O(4)Li2Cr3 square pyramids. In the fifth O site, O(5) is bonded to two equivalent Li(1), two equivalent Cr(2), and one Co(1) atom to form OLi2Cr2Co square pyramids that share corners with four equivalent O(4)Li2Cr3 square pyramids, edges with two equivalent O(5)Li2Cr2Co square pyramids, edges with two equivalent O(4)Li2Cr3 square pyramids, and edges with two equivalent O(3)LiCrCo2 trigonal pyramids. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Cr(2) and two equivalent Cr(1) atoms.
LiCr2CoO6 crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(1), one O(3), two equivalent O(4), and two equivalent O(5) atoms to form LiO6 octahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra, corners with four equivalent Cr(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-18°. The Li(1)-O(1) bond length is 2.29 Å. The Li(1)-O(3) bond length is 2.09 Å. There is one shorter (2.14 Å) and one longer (2.16 Å) Li(1)-O(4) bond length. There is one shorter (2.17 Å) and one longer (2.18 Å) Li(1)-O(5) bond length. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(6) atoms to form CrO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles are 18°. The Cr(1)-O(3) bond length is 1.97 Å. The Cr(1)-O(4) bond length is 1.98 Å. There is one shorter (1.97 Å) and one longer (1.98 Å) Cr(1)-O(1) bond length. There is one shorter (1.87 Å) and one longer (1.93 Å) Cr(1)-O(6) bond length. In the second Cr site, Cr(2) is bonded to one O(2), one O(6), two equivalent O(4), and two equivalent O(5) atoms to form CrO6 octahedra that share corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-13°. The Cr(2)-O(2) bond length is 2.00 Å. The Cr(2)-O(6) bond length is 2.02 Å. Both Cr(2)-O(4) bond lengths are 2.02 Å. Both Cr(2)-O(5) bond lengths are 2.01 Å. Co(1) is bonded to one O(1), one O(5), two equivalent O(2), and two 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 Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles are 13°. The Co(1)-O(1) bond length is 1.91 Å. The Co(1)-O(5) bond length is 1.89 Å. There is one shorter (1.88 Å) and one longer (1.89 Å) Co(1)-O(2) bond length. There is one shorter (1.93 Å) and one longer (1.94 Å) Co(1)-O(3) bond length. 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 Cr(1), and one Co(1) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Cr(2) and two equivalent Co(1) atoms. In the third O site, O(3) is bonded to one Li(1), one Cr(1), and two equivalent Co(1) atoms to form OLiCrCo2 trigonal pyramids that share corners with three equivalent O(4)Li2Cr3 square pyramids, corners with two equivalent O(3)LiCrCo2 trigonal pyramids, and edges with two equivalent O(5)Li2Cr2Co square pyramids. In the fourth O site, O(4) is bonded to two equivalent Li(1), one Cr(1), and two equivalent Cr(2) atoms to form OLi2Cr3 square pyramids that share corners with four equivalent O(5)Li2Cr2Co square pyramids, corners with three equivalent O(3)LiCrCo2 trigonal pyramids, edges with two equivalent O(5)Li2Cr2Co square pyramids, and edges with two equivalent O(4)Li2Cr3 square pyramids. In the fifth O site, O(5) is bonded to two equivalent Li(1), two equivalent Cr(2), and one Co(1) atom to form OLi2Cr2Co square pyramids that share corners with four equivalent O(4)Li2Cr3 square pyramids, edges with two equivalent O(5)Li2Cr2Co square pyramids, edges with two equivalent O(4)Li2Cr3 square pyramids, and edges with two equivalent O(3)LiCrCo2 trigonal pyramids. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Cr(2) and two equivalent Cr(1) atoms.