Li4Mn5CuO12 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(10), one O(2), one O(5), and one O(7) atom. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(3), one O(4), and one O(8) atom. In the third Li site, Li(3) is bonded in a distorted rectangular see-saw-like geometry to one O(10), one O(2), one O(5), and one O(7) atom. In the fourth Li site, Li(4) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(3), one O(4), and one O(8) atom. There are five inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(12), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form edge-sharing MnO6 octahedra. In the second Mn site, Mn(2) is bonded to one O(1), one O(10), one O(11), one O(2), one O(8), and one O(9) atom to form MnO6 octahedra that share edges with three equivalent Mn(3)O6 octahedra and edges with three equivalent Cu(1)O6 octahedra. In the third Mn site, Mn(3) is bonded to one O(1), one O(10), one O(11), one O(2), one O(8), and one O(9) atom to form MnO6 octahedra that share edges with three equivalent Mn(2)O6 octahedra and edges with three equivalent Cu(1)O6 octahedra. In the fourth Mn site, Mn(4) is bonded to one O(12), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form edge-sharing MnO6 octahedra. In the fifth Mn site, Mn(5) is bonded to one O(12), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form edge-sharing MnO6 octahedra. Cu(1) is bonded to one O(1), one O(10), one O(11), one O(2), one O(8), and one O(9) atom to form CuO6 octahedra that share edges with three equivalent Mn(2)O6 octahedra and edges with three equivalent Mn(3)O6 octahedra. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(4), one Mn(2), one Mn(3), and one Cu(1) atom to form distorted OLi2Mn2Cu trigonal bipyramids that share  a cornercorner with one O(10)Li2Mn2Cu trigonal bipyramid,  a cornercorner with one O(2)Li2Mn2Cu trigonal bipyramid,  a cornercorner with one O(8)Li2Mn2Cu trigonal bipyramid, corners with two equivalent O(4)Li2Mn3 trigonal bipyramids,  an edgeedge with one O(10)Li2Mn2Cu trigonal bipyramid,  an edgeedge with one O(2)Li2Mn2Cu trigonal bipyramid,  an edgeedge with one O(3)Li2Mn3 trigonal bipyramid, and edges with two equivalent O(8)Li2Mn2Cu trigonal bipyramids. In the second O site, O(2) is bonded to one Li(1), one Li(3), one Mn(2), one Mn(3), and one Cu(1) atom to form distorted OLi2Mn2Cu trigonal bipyramids that share  a cornercorner with one O(1)Li2Mn2Cu trigonal bipyramid,  a cornercorner with one O(10)Li2Mn2Cu trigonal bipyramid,  a cornercorner with one O(8)Li2Mn2Cu trigonal bipyramid, corners with two equivalent O(7)Li2Mn3 trigonal bipyramids,  an edgeedge with one O(1)Li2Mn2Cu trigonal bipyramid,  an edgeedge with one O(8)Li2Mn2Cu trigonal bipyramid,  an edgeedge with one O(5)Li2Mn3 trigonal bipyramid, and edges with two equivalent O(10)Li2Mn2Cu trigonal bipyramids. In the third O site, O(3) is bonded to one Li(2), one Li(4), one Mn(1), one Mn(4), and one Mn(5) atom to form distorted OLi2Mn3 trigonal bipyramids that share  a cornercorner with one O(4)Li2Mn3 trigonal bipyramid,  a cornercorner with one O(5)Li2Mn3 trigonal bipyramid,  a cornercorner with one O(7)Li2Mn3 trigonal bipyramid, corners with two equivalent O(8)Li2Mn2Cu trigonal bipyramids,  an edgeedge with one O(1)Li2Mn2Cu trigonal bipyramid,  an edgeedge with one O(5)Li2Mn3 trigonal bipyramid,  an edgeedge with one O(7)Li2Mn3 trigonal bipyramid, and edges with two equivalent O(4)Li2Mn3 trigonal bipyramids. In the fourth O site, O(4) is bonded to one Li(2), one Li(4), one Mn(1), one Mn(4), and one Mn(5) atom to form OLi2Mn3 trigonal bipyramids that share  a cornercorner with one O(3)Li2Mn3 trigonal bipyramid,  a cornercorner with one O(5)Li2Mn3 trigonal bipyramid,  a cornercorner with one O(7)Li2Mn3 trigonal bipyramid, corners with two equivalent O(1)Li2Mn2Cu trigonal bipyramids,  an edgeedge with one O(8)Li2Mn2Cu trigonal bipyramid,  an edgeedge with one O(5)Li2Mn3 trigonal bipyramid,  an edgeedge with one O(7)Li2Mn3 trigonal bipyramid, and edges with two equivalent O(3)Li2Mn3 trigonal bipyramids. In the fifth O site, O(5) is bonded to one Li(1), one Li(3), 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,  a cornercorner with one O(4)Li2Mn3 trigonal bipyramid,  a cornercorner with one O(7)Li2Mn3 trigonal bipyramid, corners with two equivalent O(10)Li2Mn2Cu trigonal bipyramids,  an edgeedge with one O(2)Li2Mn2Cu trigonal bipyramid,  an edgeedge with one O(3)Li2Mn3 trigonal bipyramid,  an edgeedge with one O(4)Li2Mn3 trigonal bipyramid, and edges with two equivalent O(7)Li2Mn3 trigonal bipyramids. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1), one Mn(4), and one Mn(5) atom. In the seventh O site, O(7) is bonded to one Li(1), one Li(3), one Mn(1), one Mn(4), and one Mn(5) atom to form OLi2Mn3 trigonal bipyramids that share  a cornercorner with one O(3)Li2Mn3 trigonal bipyramid,  a cornercorner with one O(4)Li2Mn3 trigonal bipyramid,  a cornercorner with one O(5)Li2Mn3 trigonal bipyramid, corners with two equivalent O(2)Li2Mn2Cu trigonal bipyramids,  an edgeedge with one O(10)Li2Mn2Cu trigonal bipyramid,  an edgeedge with one O(3)Li2Mn3 trigonal bipyramid,  an edgeedge with one O(4)Li2Mn3 trigonal bipyramid, and edges with two equivalent O(5)Li2Mn3 trigonal bipyramids. In the eighth O site, O(8) is bonded to one Li(2), one Li(4), one Mn(2), one Mn(3), and one Cu(1) atom to form distorted OLi2Mn2Cu trigonal bipyramids that share  a cornercorner with one O(1)Li2Mn2Cu trigonal bipyramid,  a cornercorner with one O(10)Li2Mn2Cu trigonal bipyramid,  a cornercorner with one O(2)Li2Mn2Cu trigonal bipyramid, corners with two equivalent O(3)Li2Mn3 trigonal bipyramids,  an edgeedge with one O(10)Li2Mn2Cu trigonal bipyramid,  an edgeedge with one O(2)Li2Mn2Cu trigonal bipyramid,  an edgeedge with one O(4)Li2Mn3 trigonal bipyramid, and edges with two equivalent O(1)Li2Mn2Cu trigonal bipyramids. In the ninth O site, O(9) is bonded in a distorted trigonal non-coplanar geometry to one Mn(2), one Mn(3), and one Cu(1) atom. In the tenth O site, O(10) is bonded to one Li(1), one Li(3), one Mn(2), one Mn(3), and one Cu(1) atom to form distorted OLi2Mn2Cu trigonal bipyramids that share  a cornercorner with one O(1)Li2Mn2Cu trigonal bipyramid,  a cornercorner with one O(2)Li2Mn2Cu trigonal bipyramid,  a cornercorner with one O(8)Li2Mn2Cu trigonal bipyramid, corners with two equivalent O(5)Li2Mn3 trigonal bipyramids,  an edgeedge with one O(1)Li2Mn2Cu trigonal bipyramid,  an edgeedge with one O(8)Li2Mn2Cu trigonal bipyramid,  an edgeedge with one O(7)Li2Mn3 trigonal bipyramid, and edges with two equivalent O(2)Li2Mn2Cu trigonal bipyramids. In the eleventh O site, O(11) is bonded in a distorted trigonal non-coplanar geometry to one Mn(2), one Mn(3), and one Cu(1) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1), one Mn(4), and one Mn(5) atom.
Li4Mn5CuO12 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(10), one O(2), one O(5), and one O(7) atom. The Li(1)-O(10) bond length is 2.00 Å. The Li(1)-O(2) bond length is 2.04 Å. The Li(1)-O(5) bond length is 1.98 Å. The Li(1)-O(7) bond length is 2.00 Å. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(3), one O(4), and one O(8) atom. The Li(2)-O(1) bond length is 2.03 Å. The Li(2)-O(3) bond length is 1.98 Å. The Li(2)-O(4) bond length is 1.99 Å. The Li(2)-O(8) bond length is 2.01 Å. In the third Li site, Li(3) is bonded in a distorted rectangular see-saw-like geometry to one O(10), one O(2), one O(5), and one O(7) atom. The Li(3)-O(10) bond length is 2.03 Å. The Li(3)-O(2) bond length is 2.01 Å. The Li(3)-O(5) bond length is 2.00 Å. The Li(3)-O(7) bond length is 2.17 Å. In the fourth Li site, Li(4) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(3), one O(4), and one O(8) atom. The Li(4)-O(1) bond length is 2.01 Å. The Li(4)-O(3) bond length is 2.01 Å. The Li(4)-O(4) bond length is 2.16 Å. The Li(4)-O(8) bond length is 2.04 Å. There are five inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(12), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form edge-sharing MnO6 octahedra. The Mn(1)-O(12) bond length is 1.96 Å. The Mn(1)-O(3) bond length is 1.91 Å. The Mn(1)-O(4) bond length is 1.97 Å. The Mn(1)-O(5) bond length is 1.91 Å. The Mn(1)-O(6) bond length is 1.96 Å. The Mn(1)-O(7) bond length is 1.97 Å. In the second Mn site, Mn(2) is bonded to one O(1), one O(10), one O(11), one O(2), one O(8), and one O(9) atom to form MnO6 octahedra that share edges with three equivalent Mn(3)O6 octahedra and edges with three equivalent Cu(1)O6 octahedra. The Mn(2)-O(1) bond length is 1.96 Å. The Mn(2)-O(10) bond length is 1.96 Å. The Mn(2)-O(11) bond length is 1.94 Å. The Mn(2)-O(2) bond length is 1.96 Å. The Mn(2)-O(8) bond length is 1.97 Å. The Mn(2)-O(9) bond length is 1.94 Å. In the third Mn site, Mn(3) is bonded to one O(1), one O(10), one O(11), one O(2), one O(8), and one O(9) atom to form MnO6 octahedra that share edges with three equivalent Mn(2)O6 octahedra and edges with three equivalent Cu(1)O6 octahedra. The Mn(3)-O(1) bond length is 1.96 Å. The Mn(3)-O(10) bond length is 1.96 Å. The Mn(3)-O(11) bond length is 1.94 Å. The Mn(3)-O(2) bond length is 1.96 Å. The Mn(3)-O(8) bond length is 1.97 Å. The Mn(3)-O(9) bond length is 1.94 Å. In the fourth Mn site, Mn(4) is bonded to one O(12), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form edge-sharing MnO6 octahedra. The Mn(4)-O(12) bond length is 1.96 Å. The Mn(4)-O(3) bond length is 2.16 Å. The Mn(4)-O(4) bond length is 1.99 Å. The Mn(4)-O(5) bond length is 2.15 Å. The Mn(4)-O(6) bond length is 1.96 Å. The Mn(4)-O(7) bond length is 2.00 Å. In the fifth Mn site, Mn(5) is bonded to one O(12), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form edge-sharing MnO6 octahedra. The Mn(5)-O(12) bond length is 1.93 Å. The Mn(5)-O(3) bond length is 2.12 Å. The Mn(5)-O(4) bond length is 2.13 Å. The Mn(5)-O(5) bond length is 2.14 Å. The Mn(5)-O(6) bond length is 1.93 Å. The Mn(5)-O(7) bond length is 2.11 Å. Cu(1) is bonded to one O(1), one O(10), one O(11), one O(2), one O(8), and one O(9) atom to form CuO6 octahedra that share edges with three equivalent Mn(2)O6 octahedra and edges with three equivalent Mn(3)O6 octahedra. The Cu(1)-O(1) bond length is 2.21 Å. The Cu(1)-O(10) bond length is 2.22 Å. The Cu(1)-O(11) bond length is 1.95 Å. The Cu(1)-O(2) bond length is 2.21 Å. The Cu(1)-O(8) bond length is 2.21 Å. The Cu(1)-O(9) bond length is 1.95 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(4), one Mn(2), one Mn(3), and one Cu(1) atom to form distorted OLi2Mn2Cu trigonal bipyramids that share  a cornercorner with one O(10)Li2Mn2Cu trigonal bipyramid,  a cornercorner with one O(2)Li2Mn2Cu trigonal bipyramid,  a cornercorner with one O(8)Li2Mn2Cu trigonal bipyramid, corners with two equivalent O(4)Li2Mn3 trigonal bipyramids,  an edgeedge with one O(10)Li2Mn2Cu trigonal bipyramid,  an edgeedge with one O(2)Li2Mn2Cu trigonal bipyramid,  an edgeedge with one O(3)Li2Mn3 trigonal bipyramid, and edges with two equivalent O(8)Li2Mn2Cu trigonal bipyramids. In the second O site, O(2) is bonded to one Li(1), one Li(3), one Mn(2), one Mn(3), and one Cu(1) atom to form distorted OLi2Mn2Cu trigonal bipyramids that share  a cornercorner with one O(1)Li2Mn2Cu trigonal bipyramid,  a cornercorner with one O(10)Li2Mn2Cu trigonal bipyramid,  a cornercorner with one O(8)Li2Mn2Cu trigonal bipyramid, corners with two equivalent O(7)Li2Mn3 trigonal bipyramids,  an edgeedge with one O(1)Li2Mn2Cu trigonal bipyramid,  an edgeedge with one O(8)Li2Mn2Cu trigonal bipyramid,  an edgeedge with one O(5)Li2Mn3 trigonal bipyramid, and edges with two equivalent O(10)Li2Mn2Cu trigonal bipyramids. In the third O site, O(3) is bonded to one Li(2), one Li(4), one Mn(1), one Mn(4), and one Mn(5) atom to form distorted OLi2Mn3 trigonal bipyramids that share  a cornercorner with one O(4)Li2Mn3 trigonal bipyramid,  a cornercorner with one O(5)Li2Mn3 trigonal bipyramid,  a cornercorner with one O(7)Li2Mn3 trigonal bipyramid, corners with two equivalent O(8)Li2Mn2Cu trigonal bipyramids,  an edgeedge with one O(1)Li2Mn2Cu trigonal bipyramid,  an edgeedge with one O(5)Li2Mn3 trigonal bipyramid,  an edgeedge with one O(7)Li2Mn3 trigonal bipyramid, and edges with two equivalent O(4)Li2Mn3 trigonal bipyramids. In the fourth O site, O(4) is bonded to one Li(2), one Li(4), one Mn(1), one Mn(4), and one Mn(5) atom to form OLi2Mn3 trigonal bipyramids that share  a cornercorner with one O(3)Li2Mn3 trigonal bipyramid,  a cornercorner with one O(5)Li2Mn3 trigonal bipyramid,  a cornercorner with one O(7)Li2Mn3 trigonal bipyramid, corners with two equivalent O(1)Li2Mn2Cu trigonal bipyramids,  an edgeedge with one O(8)Li2Mn2Cu trigonal bipyramid,  an edgeedge with one O(5)Li2Mn3 trigonal bipyramid,  an edgeedge with one O(7)Li2Mn3 trigonal bipyramid, and edges with two equivalent O(3)Li2Mn3 trigonal bipyramids. In the fifth O site, O(5) is bonded to one Li(1), one Li(3), 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,  a cornercorner with one O(4)Li2Mn3 trigonal bipyramid,  a cornercorner with one O(7)Li2Mn3 trigonal bipyramid, corners with two equivalent O(10)Li2Mn2Cu trigonal bipyramids,  an edgeedge with one O(2)Li2Mn2Cu trigonal bipyramid,  an edgeedge with one O(3)Li2Mn3 trigonal bipyramid,  an edgeedge with one O(4)Li2Mn3 trigonal bipyramid, and edges with two equivalent O(7)Li2Mn3 trigonal bipyramids. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1), one Mn(4), and one Mn(5) atom. In the seventh O site, O(7) is bonded to one Li(1), one Li(3), one Mn(1), one Mn(4), and one Mn(5) atom to form OLi2Mn3 trigonal bipyramids that share  a cornercorner with one O(3)Li2Mn3 trigonal bipyramid,  a cornercorner with one O(4)Li2Mn3 trigonal bipyramid,  a cornercorner with one O(5)Li2Mn3 trigonal bipyramid, corners with two equivalent O(2)Li2Mn2Cu trigonal bipyramids,  an edgeedge with one O(10)Li2Mn2Cu trigonal bipyramid,  an edgeedge with one O(3)Li2Mn3 trigonal bipyramid,  an edgeedge with one O(4)Li2Mn3 trigonal bipyramid, and edges with two equivalent O(5)Li2Mn3 trigonal bipyramids. In the eighth O site, O(8) is bonded to one Li(2), one Li(4), one Mn(2), one Mn(3), and one Cu(1) atom to form distorted OLi2Mn2Cu trigonal bipyramids that share  a cornercorner with one O(1)Li2Mn2Cu trigonal bipyramid,  a cornercorner with one O(10)Li2Mn2Cu trigonal bipyramid,  a cornercorner with one O(2)Li2Mn2Cu trigonal bipyramid, corners with two equivalent O(3)Li2Mn3 trigonal bipyramids,  an edgeedge with one O(10)Li2Mn2Cu trigonal bipyramid,  an edgeedge with one O(2)Li2Mn2Cu trigonal bipyramid,  an edgeedge with one O(4)Li2Mn3 trigonal bipyramid, and edges with two equivalent O(1)Li2Mn2Cu trigonal bipyramids. In the ninth O site, O(9) is bonded in a distorted trigonal non-coplanar geometry to one Mn(2), one Mn(3), and one Cu(1) atom. In the tenth O site, O(10) is bonded to one Li(1), one Li(3), one Mn(2), one Mn(3), and one Cu(1) atom to form distorted OLi2Mn2Cu trigonal bipyramids that share  a cornercorner with one O(1)Li2Mn2Cu trigonal bipyramid,  a cornercorner with one O(2)Li2Mn2Cu trigonal bipyramid,  a cornercorner with one O(8)Li2Mn2Cu trigonal bipyramid, corners with two equivalent O(5)Li2Mn3 trigonal bipyramids,  an edgeedge with one O(1)Li2Mn2Cu trigonal bipyramid,  an edgeedge with one O(8)Li2Mn2Cu trigonal bipyramid,  an edgeedge with one O(7)Li2Mn3 trigonal bipyramid, and edges with two equivalent O(2)Li2Mn2Cu trigonal bipyramids. In the eleventh O site, O(11) is bonded in a distorted trigonal non-coplanar geometry to one Mn(2), one Mn(3), and one Cu(1) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1), one Mn(4), and one Mn(5) atom.