Li5(CoO3)2 crystallizes in the triclinic P1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Co(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent Co(2)O4 trigonal pyramids,  an edgeedge with one Li(2)O4 tetrahedra, and  an edgeedge with one Co(1)O4 tetrahedra. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), and one O(6) atom to form LiO4 tetrahedra that share corners with three equivalent Co(1)O4 tetrahedra,  a cornercorner with one Li(1)O4 trigonal pyramid, corners with two equivalent Co(2)O4 trigonal pyramids,  an edgeedge with one Li(4)O4 tetrahedra, and  an edgeedge with one Li(1)O4 trigonal pyramid. In the third Li site, Li(3) is bonded in a distorted trigonal planar geometry to one O(2), one O(5), and one O(6) atom. In the fourth Li site, Li(4) is bonded to one O(1), one O(4), one O(5), and one O(6) atom to form LiO4 tetrahedra that share corners with two equivalent Co(1)O4 tetrahedra, corners with two equivalent Li(1)O4 trigonal pyramids, corners with three equivalent Co(2)O4 trigonal pyramids, and  an edgeedge with one Li(2)O4 tetrahedra. In the fifth Li site, Li(5) is bonded in a 4-coordinate geometry to one O(2), one O(4), one O(5), and one O(6) atom. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form CoO4 tetrahedra that share corners with two equivalent Li(4)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  a cornercorner with one Li(1)O4 trigonal pyramid,  an edgeedge with one Li(1)O4 trigonal pyramid, and  an edgeedge with one Co(2)O4 trigonal pyramid. In the second Co site, Co(2) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form distorted CoO4 trigonal pyramids that share corners with two equivalent Li(2)O4 tetrahedra, corners with three equivalent Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 trigonal pyramids, and  an edgeedge with one Co(1)O4 tetrahedra. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(4), and one Co(1) atom to form distorted OLi3Co trigonal pyramids that share  a cornercorner with one O(2)Li4Co trigonal bipyramid, corners with two equivalent O(5)Li4Co trigonal bipyramids,  a cornercorner with one O(3)Li2Co2 trigonal pyramid, corners with two equivalent O(4)Li2Co2 trigonal pyramids,  an edgeedge with one O(2)Li4Co trigonal bipyramid, and  an edgeedge with one O(3)Li2Co2 trigonal pyramid. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(5), and one Co(1) atom to form distorted OLi4Co trigonal bipyramids that share  a cornercorner with one O(5)Li4Co trigonal bipyramid,  a cornercorner with one O(1)Li3Co trigonal pyramid, corners with two equivalent O(4)Li2Co2 trigonal pyramids, corners with three equivalent O(3)Li2Co2 trigonal pyramids,  an edgeedge with one O(5)Li4Co trigonal bipyramid, and  an edgeedge with one O(1)Li3Co trigonal pyramid. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Co(1), and one Co(2) atom to form distorted OLi2Co2 trigonal pyramids that share corners with two equivalent O(5)Li4Co trigonal bipyramids, corners with three equivalent O(2)Li4Co trigonal bipyramids,  a cornercorner with one O(1)Li3Co trigonal pyramid,  an edgeedge with one O(4)Li2Co2 trigonal pyramid, and  an edgeedge with one O(1)Li3Co trigonal pyramid. In the fourth O site, O(4) is bonded to one Li(4), one Li(5), one Co(1), and one Co(2) atom to form distorted OLi2Co2 trigonal pyramids that share corners with two equivalent O(2)Li4Co trigonal bipyramids, corners with three equivalent O(5)Li4Co trigonal bipyramids, corners with two equivalent O(1)Li3Co trigonal pyramids, and  an edgeedge with one O(3)Li2Co2 trigonal pyramid. In the fifth O site, O(5) is bonded to one Li(1), one Li(3), one Li(4), one Li(5), and one Co(2) atom to form OLi4Co trigonal bipyramids that share  a cornercorner with one O(2)Li4Co trigonal bipyramid, corners with two equivalent O(3)Li2Co2 trigonal pyramids, corners with two equivalent O(1)Li3Co trigonal pyramids, corners with three equivalent O(4)Li2Co2 trigonal pyramids, and  an edgeedge with one O(2)Li4Co trigonal bipyramid. In the sixth O site, O(6) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one Li(4), one Li(5), and one Co(2) atom.
Li5(CoO3)2 crystallizes in the triclinic P1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Co(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with two equivalent Co(2)O4 trigonal pyramids,  an edgeedge with one Li(2)O4 tetrahedra, and  an edgeedge with one Co(1)O4 tetrahedra. The Li(1)-O(1) bond length is 2.10 Å. The Li(1)-O(2) bond length is 1.98 Å. The Li(1)-O(3) bond length is 1.92 Å. The Li(1)-O(5) bond length is 1.95 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), and one O(6) atom to form LiO4 tetrahedra that share corners with three equivalent Co(1)O4 tetrahedra,  a cornercorner with one Li(1)O4 trigonal pyramid, corners with two equivalent Co(2)O4 trigonal pyramids,  an edgeedge with one Li(4)O4 tetrahedra, and  an edgeedge with one Li(1)O4 trigonal pyramid. The Li(2)-O(1) bond length is 2.01 Å. The Li(2)-O(2) bond length is 1.96 Å. The Li(2)-O(3) bond length is 1.91 Å. The Li(2)-O(6) bond length is 1.95 Å. In the third Li site, Li(3) is bonded in a distorted trigonal planar geometry to one O(2), one O(5), and one O(6) atom. The Li(3)-O(2) bond length is 2.08 Å. The Li(3)-O(5) bond length is 2.11 Å. The Li(3)-O(6) bond length is 1.99 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(4), one O(5), and one O(6) atom to form LiO4 tetrahedra that share corners with two equivalent Co(1)O4 tetrahedra, corners with two equivalent Li(1)O4 trigonal pyramids, corners with three equivalent Co(2)O4 trigonal pyramids, and  an edgeedge with one Li(2)O4 tetrahedra. The Li(4)-O(1) bond length is 2.04 Å. The Li(4)-O(4) bond length is 1.94 Å. The Li(4)-O(5) bond length is 2.05 Å. The Li(4)-O(6) bond length is 2.02 Å. In the fifth Li site, Li(5) is bonded in a 4-coordinate geometry to one O(2), one O(4), one O(5), and one O(6) atom. The Li(5)-O(2) bond length is 2.01 Å. The Li(5)-O(4) bond length is 1.93 Å. The Li(5)-O(5) bond length is 1.93 Å. The Li(5)-O(6) bond length is 2.40 Å. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form CoO4 tetrahedra that share corners with two equivalent Li(4)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  a cornercorner with one Li(1)O4 trigonal pyramid,  an edgeedge with one Li(1)O4 trigonal pyramid, and  an edgeedge with one Co(2)O4 trigonal pyramid. The Co(1)-O(1) bond length is 1.76 Å. The Co(1)-O(2) bond length is 1.79 Å. The Co(1)-O(3) bond length is 1.88 Å. The Co(1)-O(4) bond length is 1.85 Å. In the second Co site, Co(2) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form distorted CoO4 trigonal pyramids that share corners with two equivalent Li(2)O4 tetrahedra, corners with three equivalent Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 trigonal pyramids, and  an edgeedge with one Co(1)O4 tetrahedra. The Co(2)-O(3) bond length is 1.94 Å. The Co(2)-O(4) bond length is 2.02 Å. The Co(2)-O(5) bond length is 1.79 Å. The Co(2)-O(6) bond length is 1.77 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(4), and one Co(1) atom to form distorted OLi3Co trigonal pyramids that share  a cornercorner with one O(2)Li4Co trigonal bipyramid, corners with two equivalent O(5)Li4Co trigonal bipyramids,  a cornercorner with one O(3)Li2Co2 trigonal pyramid, corners with two equivalent O(4)Li2Co2 trigonal pyramids,  an edgeedge with one O(2)Li4Co trigonal bipyramid, and  an edgeedge with one O(3)Li2Co2 trigonal pyramid. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(5), and one Co(1) atom to form distorted OLi4Co trigonal bipyramids that share  a cornercorner with one O(5)Li4Co trigonal bipyramid,  a cornercorner with one O(1)Li3Co trigonal pyramid, corners with two equivalent O(4)Li2Co2 trigonal pyramids, corners with three equivalent O(3)Li2Co2 trigonal pyramids,  an edgeedge with one O(5)Li4Co trigonal bipyramid, and  an edgeedge with one O(1)Li3Co trigonal pyramid. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Co(1), and one Co(2) atom to form distorted OLi2Co2 trigonal pyramids that share corners with two equivalent O(5)Li4Co trigonal bipyramids, corners with three equivalent O(2)Li4Co trigonal bipyramids,  a cornercorner with one O(1)Li3Co trigonal pyramid,  an edgeedge with one O(4)Li2Co2 trigonal pyramid, and  an edgeedge with one O(1)Li3Co trigonal pyramid. In the fourth O site, O(4) is bonded to one Li(4), one Li(5), one Co(1), and one Co(2) atom to form distorted OLi2Co2 trigonal pyramids that share corners with two equivalent O(2)Li4Co trigonal bipyramids, corners with three equivalent O(5)Li4Co trigonal bipyramids, corners with two equivalent O(1)Li3Co trigonal pyramids, and  an edgeedge with one O(3)Li2Co2 trigonal pyramid. In the fifth O site, O(5) is bonded to one Li(1), one Li(3), one Li(4), one Li(5), and one Co(2) atom to form OLi4Co trigonal bipyramids that share  a cornercorner with one O(2)Li4Co trigonal bipyramid, corners with two equivalent O(3)Li2Co2 trigonal pyramids, corners with two equivalent O(1)Li3Co trigonal pyramids, corners with three equivalent O(4)Li2Co2 trigonal pyramids, and  an edgeedge with one O(2)Li4Co trigonal bipyramid. In the sixth O site, O(6) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one Li(4), one Li(5), and one Co(2) atom.