Li4Mn5CoO12 crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(5) atom. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(5) atom. There are five inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form edge-sharing MnO6 octahedra. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(6) atoms to form MnO6 octahedra that share edges with three equivalent Mn(3)O6 octahedra and edges with three equivalent Co(1)O6 octahedra. In the third Mn site, Mn(3) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(6) atoms to form MnO6 octahedra that share edges with three equivalent Mn(2)O6 octahedra and edges with three equivalent Co(1)O6 octahedra. In the fourth Mn site, Mn(4) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form edge-sharing MnO6 octahedra. In the fifth Mn site, Mn(5) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form edge-sharing MnO6 octahedra. Co(1) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(6) atoms to form CoO6 octahedra that share edges with three equivalent Mn(2)O6 octahedra and edges with three equivalent Mn(3)O6 octahedra. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Mn(2), one Mn(3), and one Co(1) atom to form distorted OLi2Mn2Co trigonal bipyramids that share  a cornercorner with one O(1)Li2Mn2Co trigonal bipyramid, corners with two equivalent O(5)Li2Mn2Co trigonal bipyramids, corners with two equivalent O(3)Li2Mn3 trigonal bipyramids,  an edgeedge with one O(1)Li2Mn2Co trigonal bipyramid,  an edgeedge with one O(2)Li2Mn3 trigonal bipyramid, and edges with three equivalent O(5)Li2Mn2Co trigonal bipyramids. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Mn(1), one Mn(4), and one Mn(5) atom to form OLi2Mn3 trigonal bipyramids that share  a cornercorner with one O(2)Li2Mn3 trigonal bipyramid, corners with two equivalent O(5)Li2Mn2Co trigonal bipyramids, corners with two equivalent O(3)Li2Mn3 trigonal bipyramids,  an edgeedge with one O(1)Li2Mn2Co trigonal bipyramid,  an edgeedge with one O(2)Li2Mn3 trigonal bipyramid, and edges with three equivalent O(3)Li2Mn3 trigonal bipyramids. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Mn(1), one Mn(4), and one Mn(5) atom to form distorted OLi2Mn3 trigonal bipyramids that share  a cornercorner with one O(3)Li2Mn3 trigonal bipyramid, corners with two equivalent O(1)Li2Mn2Co trigonal bipyramids, corners with two equivalent O(2)Li2Mn3 trigonal bipyramids,  an edgeedge with one O(5)Li2Mn2Co trigonal bipyramid,  an edgeedge with one O(3)Li2Mn3 trigonal bipyramid, and edges with three equivalent O(2)Li2Mn3 trigonal bipyramids. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1), one Mn(4), and one Mn(5) atom. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one Mn(2), one Mn(3), and one Co(1) atom to form distorted OLi2Mn2Co trigonal bipyramids that share  a cornercorner with one O(5)Li2Mn2Co trigonal bipyramid, corners with two equivalent O(1)Li2Mn2Co trigonal bipyramids, corners with two equivalent O(2)Li2Mn3 trigonal bipyramids,  an edgeedge with one O(5)Li2Mn2Co trigonal bipyramid,  an edgeedge with one O(3)Li2Mn3 trigonal bipyramid, and edges with three equivalent O(1)Li2Mn2Co trigonal bipyramids. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Mn(2), one Mn(3), and one Co(1) atom.
Li4Mn5CoO12 crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(5) atom. The Li(1)-O(1) bond length is 2.11 Å. The Li(1)-O(2) bond length is 2.14 Å. The Li(1)-O(3) bond length is 2.05 Å. The Li(1)-O(5) bond length is 2.01 Å. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(5) atom. The Li(2)-O(1) bond length is 2.04 Å. The Li(2)-O(2) bond length is 1.96 Å. The Li(2)-O(3) bond length is 2.03 Å. The Li(2)-O(5) bond length is 2.06 Å. There are five inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form edge-sharing MnO6 octahedra. Both Mn(1)-O(2) bond lengths are 2.00 Å. Both Mn(1)-O(3) bond lengths are 2.16 Å. Both Mn(1)-O(4) bond lengths are 1.95 Å. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(6) atoms to form MnO6 octahedra that share edges with three equivalent Mn(3)O6 octahedra and edges with three equivalent Co(1)O6 octahedra. Both Mn(2)-O(1) bond lengths are 1.97 Å. Both Mn(2)-O(5) bond lengths are 1.97 Å. Both Mn(2)-O(6) bond lengths are 1.93 Å. In the third Mn site, Mn(3) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(6) atoms to form MnO6 octahedra that share edges with three equivalent Mn(2)O6 octahedra and edges with three equivalent Co(1)O6 octahedra. Both Mn(3)-O(1) bond lengths are 1.98 Å. Both Mn(3)-O(5) bond lengths are 1.97 Å. Both Mn(3)-O(6) bond lengths are 1.92 Å. In the fourth Mn site, Mn(4) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form edge-sharing MnO6 octahedra. Both Mn(4)-O(2) bond lengths are 1.98 Å. Both Mn(4)-O(3) bond lengths are 1.91 Å. Both Mn(4)-O(4) bond lengths are 1.95 Å. In the fifth Mn site, Mn(5) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form edge-sharing MnO6 octahedra. Both Mn(5)-O(2) bond lengths are 2.16 Å. Both Mn(5)-O(3) bond lengths are 2.09 Å. Both Mn(5)-O(4) bond lengths are 1.95 Å. Co(1) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(6) atoms to form CoO6 octahedra that share edges with three equivalent Mn(2)O6 octahedra and edges with three equivalent Mn(3)O6 octahedra. Both Co(1)-O(1) bond lengths are 2.15 Å. Both Co(1)-O(5) bond lengths are 2.17 Å. Both Co(1)-O(6) bond lengths are 2.07 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Mn(2), one Mn(3), and one Co(1) atom to form distorted OLi2Mn2Co trigonal bipyramids that share  a cornercorner with one O(1)Li2Mn2Co trigonal bipyramid, corners with two equivalent O(5)Li2Mn2Co trigonal bipyramids, corners with two equivalent O(3)Li2Mn3 trigonal bipyramids,  an edgeedge with one O(1)Li2Mn2Co trigonal bipyramid,  an edgeedge with one O(2)Li2Mn3 trigonal bipyramid, and edges with three equivalent O(5)Li2Mn2Co trigonal bipyramids. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Mn(1), one Mn(4), and one Mn(5) atom to form OLi2Mn3 trigonal bipyramids that share  a cornercorner with one O(2)Li2Mn3 trigonal bipyramid, corners with two equivalent O(5)Li2Mn2Co trigonal bipyramids, corners with two equivalent O(3)Li2Mn3 trigonal bipyramids,  an edgeedge with one O(1)Li2Mn2Co trigonal bipyramid,  an edgeedge with one O(2)Li2Mn3 trigonal bipyramid, and edges with three equivalent O(3)Li2Mn3 trigonal bipyramids. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Mn(1), one Mn(4), and one Mn(5) atom to form distorted OLi2Mn3 trigonal bipyramids that share  a cornercorner with one O(3)Li2Mn3 trigonal bipyramid, corners with two equivalent O(1)Li2Mn2Co trigonal bipyramids, corners with two equivalent O(2)Li2Mn3 trigonal bipyramids,  an edgeedge with one O(5)Li2Mn2Co trigonal bipyramid,  an edgeedge with one O(3)Li2Mn3 trigonal bipyramid, and edges with three equivalent O(2)Li2Mn3 trigonal bipyramids. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1), one Mn(4), and one Mn(5) atom. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one Mn(2), one Mn(3), and one Co(1) atom to form distorted OLi2Mn2Co trigonal bipyramids that share  a cornercorner with one O(5)Li2Mn2Co trigonal bipyramid, corners with two equivalent O(1)Li2Mn2Co trigonal bipyramids, corners with two equivalent O(2)Li2Mn3 trigonal bipyramids,  an edgeedge with one O(5)Li2Mn2Co trigonal bipyramid,  an edgeedge with one O(3)Li2Mn3 trigonal bipyramid, and edges with three equivalent O(1)Li2Mn2Co trigonal bipyramids. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Mn(2), one Mn(3), and one Co(1) atom.