Li2Co4O5 crystallizes in the monoclinic Cm space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(5), one O(6), two equivalent O(2), and two equivalent O(9) atoms. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one O(5) and two equivalent O(2) atoms. In the third Li site, Li(3) is bonded in a 3-coordinate geometry to one O(11), one O(2), one O(5), and one O(6) atom. In the fourth Li site, Li(4) is bonded in a 3-coordinate geometry to one O(8), two equivalent O(2), and two equivalent O(4) atoms. In the fifth Li site, Li(5) is bonded in a 4-coordinate geometry to one O(11), one O(6), and two equivalent O(9) atoms. There are nine inequivalent Co sites. In the first Co site, Co(1) is bonded in a 4-coordinate geometry to one O(11), two equivalent O(2), and two equivalent O(9) atoms. In the second Co site, Co(2) is bonded to one O(1), one O(6), two equivalent O(2), and two equivalent O(4) atoms to form CoO6 octahedra that share corners with three equivalent Co(8)O6 octahedra,  an edgeedge with one Co(4)O6 octahedra, edges with two equivalent Co(7)O6 octahedra, and edges with four equivalent Co(5)O5 square pyramids. The corner-sharing octahedral tilt angles range from 1-2°. In the third Co site, Co(3) is bonded to one O(10), one O(11), one O(3), one O(5), one O(7), and one O(9) atom to form a mixture of corner and edge-sharing CoO6 octahedra. The corner-sharing octahedral tilt angles range from 2-6°. In the fourth Co site, Co(4) is bonded to one O(3), one O(8), two equivalent O(4), and two equivalent O(7) atoms to form CoO6 octahedra that share  an edgeedge with one Co(2)O6 octahedra,  an edgeedge with one Co(6)O6 octahedra, edges with two equivalent Co(3)O6 octahedra, edges with two equivalent Co(8)O6 octahedra, edges with four equivalent Co(7)O6 octahedra, and edges with two equivalent Co(5)O5 square pyramids. In the fifth Co site, Co(5) is bonded to one O(1), one O(2), one O(4), one O(6), and one O(8) atom to form CoO5 square pyramids that share corners with three equivalent Co(7)O6 octahedra,  a cornercorner with one Co(5)O5 square pyramid,  an edgeedge with one Co(4)O6 octahedra,  an edgeedge with one Co(7)O6 octahedra,  an edgeedge with one Co(8)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, and  an edgeedge with one Co(5)O5 square pyramid. The corner-sharing octahedral tilt angles range from 4-9°. In the sixth Co site, Co(6) is bonded to one O(10), one O(5), two equivalent O(7), and two equivalent O(9) atoms to form a mixture of corner and edge-sharing CoO6 octahedra. The corner-sharing octahedral tilt angles range from 3-6°. In the seventh Co site, Co(7) is bonded to one O(1), one O(10), one O(3), one O(4), one O(7), and one O(8) atom to form CoO6 octahedra that share corners with three equivalent Co(3)O6 octahedra, corners with three equivalent Co(5)O5 square pyramids,  an edgeedge with one Co(2)O6 octahedra,  an edgeedge with one Co(3)O6 octahedra,  an edgeedge with one Co(6)O6 octahedra, edges with two equivalent Co(4)O6 octahedra, edges with two equivalent Co(7)O6 octahedra, edges with two equivalent Co(8)O6 octahedra, and  an edgeedge with one Co(5)O5 square pyramid. The corner-sharing octahedral tilt angles range from 2-6°. In the eighth Co site, Co(8) is bonded to one O(1), one O(10), two equivalent O(4), and two equivalent O(7) atoms to form CoO6 octahedra that share corners with three equivalent Co(2)O6 octahedra, corners with three equivalent Co(6)O6 octahedra, edges with two equivalent Co(3)O6 octahedra, edges with two equivalent Co(4)O6 octahedra, edges with four equivalent Co(7)O6 octahedra, and edges with two equivalent Co(5)O5 square pyramids. The corner-sharing octahedral tilt angles range from 1-6°. In the ninth Co site, Co(9) is bonded in a 4-coordinate geometry to one O(11), one O(3), and two equivalent O(7) atoms. There are eleven inequivalent O sites. In the first O site, O(1) is bonded to one Co(2), one Co(8), two equivalent Co(5), and two equivalent Co(7) atoms to form OCo6 octahedra that share corners with three equivalent O(10)Co6 octahedra,  an edgeedge with one O(3)Co6 octahedra, edges with two equivalent O(7)Co6 octahedra, edges with two equivalent O(8)LiCo5 octahedra, edges with four equivalent O(4)LiCo5 octahedra, and edges with two equivalent O(2)Li4Co3 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 1-2°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Co(1), one Co(2), and one Co(5) atom to form distorted OLi4Co3 pentagonal bipyramids that share corners with three equivalent O(4)LiCo5 octahedra,  an edgeedge with one O(1)Co6 octahedra,  an edgeedge with one O(4)LiCo5 octahedra,  an edgeedge with one O(8)LiCo5 octahedra,  an edgeedge with one O(2)Li4Co3 pentagonal bipyramid,  a faceface with one O(2)Li4Co3 pentagonal bipyramid, and  a faceface with one O(5)Li4Co3 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 3-28°. In the third O site, O(3) is bonded to one Co(4), one Co(9), two equivalent Co(3), and two equivalent Co(7) atoms to form OCo6 octahedra that share corners with three equivalent O(8)LiCo5 octahedra,  an edgeedge with one O(1)Co6 octahedra, edges with two equivalent O(10)Co6 octahedra, edges with two equivalent O(4)LiCo5 octahedra, edges with four equivalent O(7)Co6 octahedra, and  an edgeedge with one O(5)Li4Co3 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 4-5°. In the fourth O site, O(4) is bonded to one Li(4), one Co(2), one Co(4), one Co(5), one Co(7), and one Co(8) atom to form OLiCo5 octahedra that share corners with three equivalent O(7)Co6 octahedra, corners with three equivalent O(2)Li4Co3 pentagonal bipyramids,  an edgeedge with one O(10)Co6 octahedra,  an edgeedge with one O(3)Co6 octahedra,  an edgeedge with one O(7)Co6 octahedra, edges with two equivalent O(1)Co6 octahedra, edges with two equivalent O(4)LiCo5 octahedra, edges with two equivalent O(8)LiCo5 octahedra, and  an edgeedge with one O(2)Li4Co3 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 2-3°. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), two equivalent Li(3), one Co(6), and two equivalent Co(3) atoms to form distorted OLi4Co3 pentagonal bipyramids that share corners with three equivalent O(10)Co6 octahedra,  an edgeedge with one O(3)Co6 octahedra, edges with two equivalent O(7)Co6 octahedra, and faces with two equivalent O(2)Li4Co3 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 2-3°. In the sixth O site, O(6) is bonded in a 7-coordinate geometry to one Li(1), one Li(5), two equivalent Li(3), one Co(2), and two equivalent Co(5) atoms. In the seventh O site, O(7) is bonded to one Co(3), one Co(4), one Co(6), one Co(7), one Co(8), and one Co(9) atom to form OCo6 octahedra that share corners with three equivalent O(4)LiCo5 octahedra,  an edgeedge with one O(1)Co6 octahedra,  an edgeedge with one O(4)LiCo5 octahedra,  an edgeedge with one O(8)LiCo5 octahedra, edges with two equivalent O(10)Co6 octahedra, edges with two equivalent O(3)Co6 octahedra, edges with two equivalent O(7)Co6 octahedra, and  an edgeedge with one O(5)Li4Co3 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 2-3°. In the eighth O site, O(8) is bonded to one Li(4), one Co(4), two equivalent Co(5), and two equivalent Co(7) atoms to form OLiCo5 octahedra that share corners with three equivalent O(3)Co6 octahedra,  an edgeedge with one O(10)Co6 octahedra, edges with two equivalent O(1)Co6 octahedra, edges with two equivalent O(7)Co6 octahedra, edges with four equivalent O(4)LiCo5 octahedra, and edges with two equivalent O(2)Li4Co3 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 4-5°. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Li(1), one Li(5), one Co(1), one Co(3), and one Co(6) atom. In the tenth O site, O(10) is bonded to one Co(6), one Co(8), two equivalent Co(3), and two equivalent Co(7) atoms to form OCo6 octahedra that share corners with three equivalent O(1)Co6 octahedra, corners with three equivalent O(5)Li4Co3 pentagonal bipyramids,  an edgeedge with one O(8)LiCo5 octahedra, edges with two equivalent O(3)Co6 octahedra, edges with two equivalent O(4)LiCo5 octahedra, and edges with four equivalent O(7)Co6 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. In the eleventh O site, O(11) is bonded in a 7-coordinate geometry to one Li(5), two equivalent Li(3), one Co(1), one Co(9), and two equivalent Co(3) atoms.
Li2Co4O5 crystallizes in the monoclinic Cm space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(5), one O(6), two equivalent O(2), and two equivalent O(9) atoms. The Li(1)-O(5) bond length is 2.03 Å. The Li(1)-O(6) bond length is 2.23 Å. Both Li(1)-O(2) bond lengths are 1.98 Å. Both Li(1)-O(9) bond lengths are 2.36 Å. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one O(5) and two equivalent O(2) atoms. The Li(2)-O(5) bond length is 2.08 Å. Both Li(2)-O(2) bond lengths are 2.15 Å. In the third Li site, Li(3) is bonded in a 3-coordinate geometry to one O(11), one O(2), one O(5), and one O(6) atom. The Li(3)-O(11) bond length is 1.82 Å. The Li(3)-O(2) bond length is 1.96 Å. The Li(3)-O(5) bond length is 1.94 Å. The Li(3)-O(6) bond length is 2.44 Å. In the fourth Li site, Li(4) is bonded in a 3-coordinate geometry to one O(8), two equivalent O(2), and two equivalent O(4) atoms. The Li(4)-O(8) bond length is 1.83 Å. Both Li(4)-O(2) bond lengths are 2.40 Å. Both Li(4)-O(4) bond lengths are 1.99 Å. In the fifth Li site, Li(5) is bonded in a 4-coordinate geometry to one O(11), one O(6), and two equivalent O(9) atoms. The Li(5)-O(11) bond length is 2.02 Å. The Li(5)-O(6) bond length is 1.89 Å. Both Li(5)-O(9) bond lengths are 1.86 Å. There are nine inequivalent Co sites. In the first Co site, Co(1) is bonded in a 4-coordinate geometry to one O(11), two equivalent O(2), and two equivalent O(9) atoms. The Co(1)-O(11) bond length is 2.49 Å. Both Co(1)-O(2) bond lengths are 2.14 Å. Both Co(1)-O(9) bond lengths are 1.98 Å. In the second Co site, Co(2) is bonded to one O(1), one O(6), two equivalent O(2), and two equivalent O(4) atoms to form CoO6 octahedra that share corners with three equivalent Co(8)O6 octahedra,  an edgeedge with one Co(4)O6 octahedra, edges with two equivalent Co(7)O6 octahedra, and edges with four equivalent Co(5)O5 square pyramids. The corner-sharing octahedral tilt angles range from 1-2°. The Co(2)-O(1) bond length is 2.27 Å. The Co(2)-O(6) bond length is 2.13 Å. Both Co(2)-O(2) bond lengths are 2.10 Å. Both Co(2)-O(4) bond lengths are 2.14 Å. In the third Co site, Co(3) is bonded to one O(10), one O(11), one O(3), one O(5), one O(7), and one O(9) atom to form a mixture of corner and edge-sharing CoO6 octahedra. The corner-sharing octahedral tilt angles range from 2-6°. The Co(3)-O(10) bond length is 2.27 Å. The Co(3)-O(11) bond length is 2.14 Å. The Co(3)-O(3) bond length is 2.21 Å. The Co(3)-O(5) bond length is 2.26 Å. The Co(3)-O(7) bond length is 2.14 Å. The Co(3)-O(9) bond length is 2.06 Å. In the fourth Co site, Co(4) is bonded to one O(3), one O(8), two equivalent O(4), and two equivalent O(7) atoms to form CoO6 octahedra that share  an edgeedge with one Co(2)O6 octahedra,  an edgeedge with one Co(6)O6 octahedra, edges with two equivalent Co(3)O6 octahedra, edges with two equivalent Co(8)O6 octahedra, edges with four equivalent Co(7)O6 octahedra, and edges with two equivalent Co(5)O5 square pyramids. The Co(4)-O(3) bond length is 2.18 Å. The Co(4)-O(8) bond length is 2.05 Å. Both Co(4)-O(4) bond lengths are 2.15 Å. Both Co(4)-O(7) bond lengths are 2.13 Å. In the fifth Co site, Co(5) is bonded to one O(1), one O(2), one O(4), one O(6), and one O(8) atom to form CoO5 square pyramids that share corners with three equivalent Co(7)O6 octahedra,  a cornercorner with one Co(5)O5 square pyramid,  an edgeedge with one Co(4)O6 octahedra,  an edgeedge with one Co(7)O6 octahedra,  an edgeedge with one Co(8)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, and  an edgeedge with one Co(5)O5 square pyramid. The corner-sharing octahedral tilt angles range from 4-9°. The Co(5)-O(1) bond length is 2.14 Å. The Co(5)-O(2) bond length is 2.07 Å. The Co(5)-O(4) bond length is 2.20 Å. The Co(5)-O(6) bond length is 2.07 Å. The Co(5)-O(8) bond length is 2.14 Å. In the sixth Co site, Co(6) is bonded to one O(10), one O(5), two equivalent O(7), and two equivalent O(9) atoms to form a mixture of corner and edge-sharing CoO6 octahedra. The corner-sharing octahedral tilt angles range from 3-6°. The Co(6)-O(10) bond length is 2.22 Å. The Co(6)-O(5) bond length is 2.08 Å. Both Co(6)-O(7) bond lengths are 2.25 Å. Both Co(6)-O(9) bond lengths are 2.13 Å. In the seventh Co site, Co(7) is bonded to one O(1), one O(10), one O(3), one O(4), one O(7), and one O(8) atom to form CoO6 octahedra that share corners with three equivalent Co(3)O6 octahedra, corners with three equivalent Co(5)O5 square pyramids,  an edgeedge with one Co(2)O6 octahedra,  an edgeedge with one Co(3)O6 octahedra,  an edgeedge with one Co(6)O6 octahedra, edges with two equivalent Co(4)O6 octahedra, edges with two equivalent Co(7)O6 octahedra, edges with two equivalent Co(8)O6 octahedra, and  an edgeedge with one Co(5)O5 square pyramid. The corner-sharing octahedral tilt angles range from 2-6°. The Co(7)-O(1) bond length is 2.23 Å. The Co(7)-O(10) bond length is 2.12 Å. The Co(7)-O(3) bond length is 2.17 Å. The Co(7)-O(4) bond length is 2.22 Å. The Co(7)-O(7) bond length is 2.17 Å. The Co(7)-O(8) bond length is 2.12 Å. In the eighth Co site, Co(8) is bonded to one O(1), one O(10), two equivalent O(4), and two equivalent O(7) atoms to form CoO6 octahedra that share corners with three equivalent Co(2)O6 octahedra, corners with three equivalent Co(6)O6 octahedra, edges with two equivalent Co(3)O6 octahedra, edges with two equivalent Co(4)O6 octahedra, edges with four equivalent Co(7)O6 octahedra, and edges with two equivalent Co(5)O5 square pyramids. The corner-sharing octahedral tilt angles range from 1-6°. The Co(8)-O(1) bond length is 2.14 Å. The Co(8)-O(10) bond length is 2.13 Å. Both Co(8)-O(4) bond lengths are 2.12 Å. Both Co(8)-O(7) bond lengths are 2.24 Å. In the ninth Co site, Co(9) is bonded in a 4-coordinate geometry to one O(11), one O(3), and two equivalent O(7) atoms. The Co(9)-O(11) bond length is 2.01 Å. The Co(9)-O(3) bond length is 2.01 Å. Both Co(9)-O(7) bond lengths are 2.00 Å. There are eleven inequivalent O sites. In the first O site, O(1) is bonded to one Co(2), one Co(8), two equivalent Co(5), and two equivalent Co(7) atoms to form OCo6 octahedra that share corners with three equivalent O(10)Co6 octahedra,  an edgeedge with one O(3)Co6 octahedra, edges with two equivalent O(7)Co6 octahedra, edges with two equivalent O(8)LiCo5 octahedra, edges with four equivalent O(4)LiCo5 octahedra, and edges with two equivalent O(2)Li4Co3 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 1-2°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Co(1), one Co(2), and one Co(5) atom to form distorted OLi4Co3 pentagonal bipyramids that share corners with three equivalent O(4)LiCo5 octahedra,  an edgeedge with one O(1)Co6 octahedra,  an edgeedge with one O(4)LiCo5 octahedra,  an edgeedge with one O(8)LiCo5 octahedra,  an edgeedge with one O(2)Li4Co3 pentagonal bipyramid,  a faceface with one O(2)Li4Co3 pentagonal bipyramid, and  a faceface with one O(5)Li4Co3 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 3-28°. In the third O site, O(3) is bonded to one Co(4), one Co(9), two equivalent Co(3), and two equivalent Co(7) atoms to form OCo6 octahedra that share corners with three equivalent O(8)LiCo5 octahedra,  an edgeedge with one O(1)Co6 octahedra, edges with two equivalent O(10)Co6 octahedra, edges with two equivalent O(4)LiCo5 octahedra, edges with four equivalent O(7)Co6 octahedra, and  an edgeedge with one O(5)Li4Co3 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 4-5°. In the fourth O site, O(4) is bonded to one Li(4), one Co(2), one Co(4), one Co(5), one Co(7), and one Co(8) atom to form OLiCo5 octahedra that share corners with three equivalent O(7)Co6 octahedra, corners with three equivalent O(2)Li4Co3 pentagonal bipyramids,  an edgeedge with one O(10)Co6 octahedra,  an edgeedge with one O(3)Co6 octahedra,  an edgeedge with one O(7)Co6 octahedra, edges with two equivalent O(1)Co6 octahedra, edges with two equivalent O(4)LiCo5 octahedra, edges with two equivalent O(8)LiCo5 octahedra, and  an edgeedge with one O(2)Li4Co3 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 2-3°. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), two equivalent Li(3), one Co(6), and two equivalent Co(3) atoms to form distorted OLi4Co3 pentagonal bipyramids that share corners with three equivalent O(10)Co6 octahedra,  an edgeedge with one O(3)Co6 octahedra, edges with two equivalent O(7)Co6 octahedra, and faces with two equivalent O(2)Li4Co3 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 2-3°. In the sixth O site, O(6) is bonded in a 7-coordinate geometry to one Li(1), one Li(5), two equivalent Li(3), one Co(2), and two equivalent Co(5) atoms. In the seventh O site, O(7) is bonded to one Co(3), one Co(4), one Co(6), one Co(7), one Co(8), and one Co(9) atom to form OCo6 octahedra that share corners with three equivalent O(4)LiCo5 octahedra,  an edgeedge with one O(1)Co6 octahedra,  an edgeedge with one O(4)LiCo5 octahedra,  an edgeedge with one O(8)LiCo5 octahedra, edges with two equivalent O(10)Co6 octahedra, edges with two equivalent O(3)Co6 octahedra, edges with two equivalent O(7)Co6 octahedra, and  an edgeedge with one O(5)Li4Co3 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 2-3°. In the eighth O site, O(8) is bonded to one Li(4), one Co(4), two equivalent Co(5), and two equivalent Co(7) atoms to form OLiCo5 octahedra that share corners with three equivalent O(3)Co6 octahedra,  an edgeedge with one O(10)Co6 octahedra, edges with two equivalent O(1)Co6 octahedra, edges with two equivalent O(7)Co6 octahedra, edges with four equivalent O(4)LiCo5 octahedra, and edges with two equivalent O(2)Li4Co3 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 4-5°. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Li(1), one Li(5), one Co(1), one Co(3), and one Co(6) atom. In the tenth O site, O(10) is bonded to one Co(6), one Co(8), two equivalent Co(3), and two equivalent Co(7) atoms to form OCo6 octahedra that share corners with three equivalent O(1)Co6 octahedra, corners with three equivalent O(5)Li4Co3 pentagonal bipyramids,  an edgeedge with one O(8)LiCo5 octahedra, edges with two equivalent O(3)Co6 octahedra, edges with two equivalent O(4)LiCo5 octahedra, and edges with four equivalent O(7)Co6 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. In the eleventh O site, O(11) is bonded in a 7-coordinate geometry to one Li(5), two equivalent Li(3), one Co(1), one Co(9), and two equivalent Co(3) atoms.