LiCo8O9 is Caswellsilverite-like structured and crystallizes in the triclinic P-1 space group. Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(3)O6 octahedra, corners with two equivalent Co(4)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Co(4)O6 octahedra, edges with four equivalent Co(2)O6 octahedra, and edges with four equivalent Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. There are four inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(2), one O(5), two equivalent O(1), and two equivalent O(3) atoms to form CoO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one Co(4)O6 octahedra, corners with two equivalent Co(3)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Co(3)O6 octahedra, edges with three equivalent Co(2)O6 octahedra, and edges with four equivalent Co(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the second Co site, Co(2) is bonded to one O(1), one O(2), one O(3), one O(5), and two equivalent O(4) atoms to form CoO6 octahedra that share  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra, corners with two equivalent Co(3)O6 octahedra, corners with two equivalent Co(4)O6 octahedra,  an edgeedge with one Co(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with three equivalent Co(1)O6 octahedra, edges with three equivalent Co(3)O6 octahedra, and edges with three equivalent Co(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the third Co site, Co(3) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form CoO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Co(4)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, corners with two 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(3)O6 octahedra, edges with three equivalent Co(2)O6 octahedra, and edges with three equivalent Co(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the fourth Co site, Co(4) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent O(3) atoms to form CoO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one Co(4)O6 octahedra, corners with two equivalent Co(2)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Co(4)O6 octahedra, edges with three equivalent Co(2)O6 octahedra, edges with three equivalent Co(3)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Co(2), one Co(3), one Co(4), and two equivalent Co(1) atoms to form OLiCo5 octahedra that share  a cornercorner with one O(1)LiCo5 octahedra,  a cornercorner with one O(4)LiCo5 octahedra, corners with two equivalent O(3)Co6 octahedra, corners with two equivalent O(2)LiCo5 octahedra,  an edgeedge with one O(1)LiCo5 octahedra, edges with two equivalent O(5)Co6 octahedra, edges with three equivalent O(3)Co6 octahedra, edges with three equivalent O(2)LiCo5 octahedra, and edges with three equivalent O(4)LiCo5 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the second O site, O(2) is bonded to one Li(1), one Co(1), one Co(2), one Co(4), and two equivalent Co(3) atoms to form OLiCo5 octahedra that share  a cornercorner with one O(3)Co6 octahedra,  a cornercorner with one O(5)Co6 octahedra,  a cornercorner with one O(2)LiCo5 octahedra,  a cornercorner with one O(4)LiCo5 octahedra, corners with two equivalent O(1)LiCo5 octahedra,  an edgeedge with one O(5)Co6 octahedra,  an edgeedge with one O(2)LiCo5 octahedra, edges with three equivalent O(3)Co6 octahedra, edges with three equivalent O(1)LiCo5 octahedra, and edges with four equivalent O(4)LiCo5 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the third O site, O(3) is bonded to one Co(2), one Co(3), two equivalent Co(1), and two equivalent Co(4) atoms to form OCo6 octahedra that share  a cornercorner with one O(5)Co6 octahedra,  a cornercorner with one O(2)LiCo5 octahedra, corners with two equivalent O(1)LiCo5 octahedra, corners with two equivalent O(4)LiCo5 octahedra, edges with two equivalent O(3)Co6 octahedra, edges with two equivalent O(5)Co6 octahedra, edges with two equivalent O(4)LiCo5 octahedra, edges with three equivalent O(1)LiCo5 octahedra, and edges with three equivalent O(2)LiCo5 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the fourth O site, O(4) is bonded to one Li(1), one Co(4), two equivalent Co(2), and two equivalent Co(3) atoms to form OLiCo5 octahedra that share  a cornercorner with one O(5)Co6 octahedra,  a cornercorner with one O(1)LiCo5 octahedra,  a cornercorner with one O(2)LiCo5 octahedra,  a cornercorner with one O(4)LiCo5 octahedra, corners with two equivalent O(3)Co6 octahedra,  an edgeedge with one O(5)Co6 octahedra, edges with two equivalent O(3)Co6 octahedra, edges with two equivalent O(4)LiCo5 octahedra, edges with three equivalent O(1)LiCo5 octahedra, and edges with four equivalent O(2)LiCo5 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the fifth O site, O(5) is bonded to two equivalent Co(1), two equivalent Co(2), and two equivalent Co(4) atoms to form OCo6 octahedra that share corners with two equivalent O(3)Co6 octahedra, corners with two equivalent O(2)LiCo5 octahedra, corners with two equivalent O(4)LiCo5 octahedra, edges with two equivalent O(2)LiCo5 octahedra, edges with two equivalent O(4)LiCo5 octahedra, edges with four equivalent O(3)Co6 octahedra, and edges with four equivalent O(1)LiCo5 octahedra. The corner-sharing octahedral tilt angles range from 0-2°.
LiCo8O9 is Caswellsilverite-like structured and crystallizes in the triclinic P-1 space group. Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(3)O6 octahedra, corners with two equivalent Co(4)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Co(4)O6 octahedra, edges with four equivalent Co(2)O6 octahedra, and edges with four equivalent Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. Both Li(1)-O(1) bond lengths are 2.17 Å. Both Li(1)-O(2) bond lengths are 2.16 Å. Both Li(1)-O(4) bond lengths are 2.18 Å. There are four inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(2), one O(5), two equivalent O(1), and two equivalent O(3) atoms to form CoO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra,  a cornercorner with one Co(4)O6 octahedra, corners with two equivalent Co(3)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Co(3)O6 octahedra, edges with three equivalent Co(2)O6 octahedra, and edges with four equivalent Co(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. The Co(1)-O(2) bond length is 2.10 Å. The Co(1)-O(5) bond length is 2.14 Å. There is one shorter (2.08 Å) and one longer (2.12 Å) Co(1)-O(1) bond length. There is one shorter (2.14 Å) and one longer (2.15 Å) Co(1)-O(3) bond length. In the second Co site, Co(2) is bonded to one O(1), one O(2), one O(3), one O(5), and two equivalent O(4) atoms to form CoO6 octahedra that share  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(2)O6 octahedra, corners with two equivalent Co(3)O6 octahedra, corners with two equivalent Co(4)O6 octahedra,  an edgeedge with one Co(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with three equivalent Co(1)O6 octahedra, edges with three equivalent Co(3)O6 octahedra, and edges with three equivalent Co(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. The Co(2)-O(1) bond length is 2.12 Å. The Co(2)-O(2) bond length is 2.15 Å. The Co(2)-O(3) bond length is 2.14 Å. The Co(2)-O(5) bond length is 2.14 Å. There is one shorter (2.09 Å) and one longer (2.12 Å) Co(2)-O(4) bond length. In the third Co site, Co(3) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form CoO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Co(4)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, corners with two 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(3)O6 octahedra, edges with three equivalent Co(2)O6 octahedra, and edges with three equivalent Co(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. The Co(3)-O(1) bond length is 2.12 Å. The Co(3)-O(3) bond length is 2.15 Å. There is one shorter (2.10 Å) and one longer (2.13 Å) Co(3)-O(2) bond length. There is one shorter (2.09 Å) and one longer (2.15 Å) Co(3)-O(4) bond length. In the fourth Co site, Co(4) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent O(3) atoms to form CoO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Co(1)O6 octahedra,  a cornercorner with one Co(3)O6 octahedra,  a cornercorner with one Co(4)O6 octahedra, corners with two equivalent Co(2)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Co(4)O6 octahedra, edges with three equivalent Co(2)O6 octahedra, edges with three equivalent Co(3)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. The Co(4)-O(1) bond length is 2.12 Å. The Co(4)-O(2) bond length is 2.07 Å. The Co(4)-O(4) bond length is 2.11 Å. The Co(4)-O(5) bond length is 2.16 Å. There is one shorter (2.14 Å) and one longer (2.16 Å) Co(4)-O(3) bond length. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Co(2), one Co(3), one Co(4), and two equivalent Co(1) atoms to form OLiCo5 octahedra that share  a cornercorner with one O(1)LiCo5 octahedra,  a cornercorner with one O(4)LiCo5 octahedra, corners with two equivalent O(3)Co6 octahedra, corners with two equivalent O(2)LiCo5 octahedra,  an edgeedge with one O(1)LiCo5 octahedra, edges with two equivalent O(5)Co6 octahedra, edges with three equivalent O(3)Co6 octahedra, edges with three equivalent O(2)LiCo5 octahedra, and edges with three equivalent O(4)LiCo5 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the second O site, O(2) is bonded to one Li(1), one Co(1), one Co(2), one Co(4), and two equivalent Co(3) atoms to form OLiCo5 octahedra that share  a cornercorner with one O(3)Co6 octahedra,  a cornercorner with one O(5)Co6 octahedra,  a cornercorner with one O(2)LiCo5 octahedra,  a cornercorner with one O(4)LiCo5 octahedra, corners with two equivalent O(1)LiCo5 octahedra,  an edgeedge with one O(5)Co6 octahedra,  an edgeedge with one O(2)LiCo5 octahedra, edges with three equivalent O(3)Co6 octahedra, edges with three equivalent O(1)LiCo5 octahedra, and edges with four equivalent O(4)LiCo5 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the third O site, O(3) is bonded to one Co(2), one Co(3), two equivalent Co(1), and two equivalent Co(4) atoms to form OCo6 octahedra that share  a cornercorner with one O(5)Co6 octahedra,  a cornercorner with one O(2)LiCo5 octahedra, corners with two equivalent O(1)LiCo5 octahedra, corners with two equivalent O(4)LiCo5 octahedra, edges with two equivalent O(3)Co6 octahedra, edges with two equivalent O(5)Co6 octahedra, edges with two equivalent O(4)LiCo5 octahedra, edges with three equivalent O(1)LiCo5 octahedra, and edges with three equivalent O(2)LiCo5 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the fourth O site, O(4) is bonded to one Li(1), one Co(4), two equivalent Co(2), and two equivalent Co(3) atoms to form OLiCo5 octahedra that share  a cornercorner with one O(5)Co6 octahedra,  a cornercorner with one O(1)LiCo5 octahedra,  a cornercorner with one O(2)LiCo5 octahedra,  a cornercorner with one O(4)LiCo5 octahedra, corners with two equivalent O(3)Co6 octahedra,  an edgeedge with one O(5)Co6 octahedra, edges with two equivalent O(3)Co6 octahedra, edges with two equivalent O(4)LiCo5 octahedra, edges with three equivalent O(1)LiCo5 octahedra, and edges with four equivalent O(2)LiCo5 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the fifth O site, O(5) is bonded to two equivalent Co(1), two equivalent Co(2), and two equivalent Co(4) atoms to form OCo6 octahedra that share corners with two equivalent O(3)Co6 octahedra, corners with two equivalent O(2)LiCo5 octahedra, corners with two equivalent O(4)LiCo5 octahedra, edges with two equivalent O(2)LiCo5 octahedra, edges with two equivalent O(4)LiCo5 octahedra, edges with four equivalent O(3)Co6 octahedra, and edges with four equivalent O(1)LiCo5 octahedra. The corner-sharing octahedral tilt angles range from 0-2°.