Li3Mn5(CuO6)2 crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. In the second Li site, Li(2) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent Mn(4)O6 octahedra, edges with two equivalent Mn(4)O6 octahedra, edges with three equivalent Mn(3)O6 octahedra, and edges with three equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles are 15°. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(5) atoms to form MnO6 octahedra that share corners with two equivalent Mn(4)O6 octahedra, edges with two equivalent Mn(4)O6 octahedra, edges with three equivalent Mn(2)O6 octahedra, and edges with three equivalent Cu(2)O6 octahedra. The corner-sharing octahedral tilt angles are 14°. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(5) atoms to form MnO6 octahedra that share corners with two equivalent Mn(4)O6 octahedra, edges with two equivalent Mn(4)O6 octahedra, edges with three equivalent Mn(1)O6 octahedra, and edges with three equivalent Cu(2)O6 octahedra. The corner-sharing octahedral tilt angles are 16°. In the third Mn site, Mn(3) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms to form MnO6 octahedra that share corners with two equivalent Mn(4)O6 octahedra, edges with two equivalent Mn(4)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles are 6°. In the fourth Mn site, Mn(4) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form MnO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra,  a cornercorner with one Cu(1)O6 octahedra,  a cornercorner with one Cu(2)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(2)O6 octahedra,  an edgeedge with one Mn(3)O6 octahedra,  an edgeedge with one Cu(1)O6 octahedra, and  an edgeedge with one Cu(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-16°. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms to form distorted CuO6 octahedra that share corners with two equivalent Mn(4)O6 octahedra, edges with two equivalent Mn(4)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles are 11°. In the second Cu site, Cu(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(5) atoms to form distorted CuO6 octahedra that share corners with two equivalent Mn(4)O6 octahedra, edges with two equivalent Mn(4)O6 octahedra, edges with three equivalent Mn(1)O6 octahedra, and edges with three equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles are 7°. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Mn(1), one Mn(2), one Mn(4), and one Cu(2) atom to form distorted OLiMn3Cu square pyramids that share  a cornercorner with one O(1)LiMn3Cu square pyramid, corners with two equivalent O(3)Li2Mn2Cu square pyramids, corners with two equivalent O(6)Li2Mn2Cu square pyramids, corners with two equivalent O(2)LiMn3Cu square pyramids, corners with two equivalent O(5)LiMn3Cu square pyramids,  an edgeedge with one O(4)Li2Mn2Cu square pyramid,  an edgeedge with one O(1)LiMn3Cu square pyramid, edges with three equivalent O(2)LiMn3Cu square pyramids, and edges with three equivalent O(5)LiMn3Cu square pyramids. In the second O site, O(2) is bonded to one Li(1), one Mn(1), one Mn(2), one Mn(4), and one Cu(2) atom to form OLiMn3Cu square pyramids that share  a cornercorner with one O(2)LiMn3Cu square pyramid, corners with two equivalent O(4)Li2Mn2Cu square pyramids, corners with two equivalent O(6)Li2Mn2Cu square pyramids, corners with two equivalent O(1)LiMn3Cu square pyramids, corners with two equivalent O(5)LiMn3Cu square pyramids,  an edgeedge with one O(3)Li2Mn2Cu square pyramid,  an edgeedge with one O(2)LiMn3Cu square pyramid, edges with three equivalent O(1)LiMn3Cu square pyramids, and edges with three equivalent O(5)LiMn3Cu square pyramids. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Mn(3), one Mn(4), and one Cu(1) atom to form OLi2Mn2Cu square pyramids that share  a cornercorner with one O(3)Li2Mn2Cu square pyramid, corners with two equivalent O(4)Li2Mn2Cu square pyramids, corners with two equivalent O(6)Li2Mn2Cu square pyramids, corners with two equivalent O(1)LiMn3Cu square pyramids, corners with two equivalent O(5)LiMn3Cu square pyramids,  an edgeedge with one O(3)Li2Mn2Cu square pyramid,  an edgeedge with one O(2)LiMn3Cu square pyramid, edges with three equivalent O(4)Li2Mn2Cu square pyramids, and edges with three equivalent O(6)Li2Mn2Cu square pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Mn(3), one Mn(4), and one Cu(1) atom to form OLi2Mn2Cu square pyramids that share  a cornercorner with one O(4)Li2Mn2Cu square pyramid, corners with two equivalent O(3)Li2Mn2Cu square pyramids, corners with two equivalent O(6)Li2Mn2Cu square pyramids, corners with two equivalent O(2)LiMn3Cu square pyramids, corners with two equivalent O(5)LiMn3Cu square pyramids,  an edgeedge with one O(4)Li2Mn2Cu square pyramid,  an edgeedge with one O(1)LiMn3Cu square pyramid, edges with three equivalent O(3)Li2Mn2Cu square pyramids, and edges with three equivalent O(6)Li2Mn2Cu square pyramids. In the fifth O site, O(5) is bonded to one Li(1), one Mn(1), one Mn(2), one Mn(4), and one Cu(2) atom to form distorted OLiMn3Cu square pyramids that share  a cornercorner with one O(5)LiMn3Cu square pyramid, corners with two equivalent O(3)Li2Mn2Cu square pyramids, corners with two equivalent O(4)Li2Mn2Cu square pyramids, corners with two equivalent O(1)LiMn3Cu square pyramids, corners with two equivalent O(2)LiMn3Cu square pyramids,  an edgeedge with one O(6)Li2Mn2Cu square pyramid,  an edgeedge with one O(5)LiMn3Cu square pyramid, edges with three equivalent O(1)LiMn3Cu square pyramids, and edges with three equivalent O(2)LiMn3Cu square pyramids. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one Mn(3), one Mn(4), and one Cu(1) atom to form distorted OLi2Mn2Cu square pyramids that share  a cornercorner with one O(6)Li2Mn2Cu square pyramid, corners with two equivalent O(3)Li2Mn2Cu square pyramids, corners with two equivalent O(4)Li2Mn2Cu square pyramids, corners with two equivalent O(1)LiMn3Cu square pyramids, corners with two equivalent O(2)LiMn3Cu square pyramids,  an edgeedge with one O(6)Li2Mn2Cu square pyramid,  an edgeedge with one O(5)LiMn3Cu square pyramid, edges with three equivalent O(3)Li2Mn2Cu square pyramids, and edges with three equivalent O(4)Li2Mn2Cu square pyramids.
Li3Mn5(CuO6)2 crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. The Li(1)-O(1) bond length is 2.10 Å. The Li(1)-O(2) bond length is 2.28 Å. The Li(1)-O(3) bond length is 2.17 Å. The Li(1)-O(4) bond length is 2.23 Å. The Li(1)-O(5) bond length is 2.57 Å. The Li(1)-O(6) bond length is 1.99 Å. In the second Li site, Li(2) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent Mn(4)O6 octahedra, edges with two equivalent Mn(4)O6 octahedra, edges with three equivalent Mn(3)O6 octahedra, and edges with three equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles are 15°. Both Li(2)-O(3) bond lengths are 2.08 Å. Both Li(2)-O(4) bond lengths are 2.18 Å. Both Li(2)-O(6) bond lengths are 2.16 Å. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(5) atoms to form MnO6 octahedra that share corners with two equivalent Mn(4)O6 octahedra, edges with two equivalent Mn(4)O6 octahedra, edges with three equivalent Mn(2)O6 octahedra, and edges with three equivalent Cu(2)O6 octahedra. The corner-sharing octahedral tilt angles are 14°. Both Mn(1)-O(1) bond lengths are 2.03 Å. Both Mn(1)-O(2) bond lengths are 2.11 Å. Both Mn(1)-O(5) bond lengths are 1.97 Å. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(5) atoms to form MnO6 octahedra that share corners with two equivalent Mn(4)O6 octahedra, edges with two equivalent Mn(4)O6 octahedra, edges with three equivalent Mn(1)O6 octahedra, and edges with three equivalent Cu(2)O6 octahedra. The corner-sharing octahedral tilt angles are 16°. Both Mn(2)-O(1) bond lengths are 2.06 Å. Both Mn(2)-O(2) bond lengths are 1.97 Å. Both Mn(2)-O(5) bond lengths are 2.05 Å. In the third Mn site, Mn(3) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms to form MnO6 octahedra that share corners with two equivalent Mn(4)O6 octahedra, edges with two equivalent Mn(4)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent Cu(1)O6 octahedra. The corner-sharing octahedral tilt angles are 6°. Both Mn(3)-O(3) bond lengths are 1.97 Å. Both Mn(3)-O(4) bond lengths are 2.03 Å. Both Mn(3)-O(6) bond lengths are 1.94 Å. In the fourth Mn site, Mn(4) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form MnO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra,  a cornercorner with one Cu(1)O6 octahedra,  a cornercorner with one Cu(2)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(2)O6 octahedra,  an edgeedge with one Mn(3)O6 octahedra,  an edgeedge with one Cu(1)O6 octahedra, and  an edgeedge with one Cu(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-16°. The Mn(4)-O(1) bond length is 1.98 Å. The Mn(4)-O(2) bond length is 2.07 Å. The Mn(4)-O(3) bond length is 2.16 Å. The Mn(4)-O(4) bond length is 1.98 Å. The Mn(4)-O(5) bond length is 2.24 Å. The Mn(4)-O(6) bond length is 1.91 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms to form distorted CuO6 octahedra that share corners with two equivalent Mn(4)O6 octahedra, edges with two equivalent Mn(4)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles are 11°. Both Cu(1)-O(3) bond lengths are 1.93 Å. Both Cu(1)-O(4) bond lengths are 1.94 Å. Both Cu(1)-O(6) bond lengths are 2.45 Å. In the second Cu site, Cu(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(5) atoms to form distorted CuO6 octahedra that share corners with two equivalent Mn(4)O6 octahedra, edges with two equivalent Mn(4)O6 octahedra, edges with three equivalent Mn(1)O6 octahedra, and edges with three equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles are 7°. Both Cu(2)-O(1) bond lengths are 2.46 Å. Both Cu(2)-O(2) bond lengths are 2.04 Å. Both Cu(2)-O(5) bond lengths are 1.99 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Mn(1), one Mn(2), one Mn(4), and one Cu(2) atom to form distorted OLiMn3Cu square pyramids that share  a cornercorner with one O(1)LiMn3Cu square pyramid, corners with two equivalent O(3)Li2Mn2Cu square pyramids, corners with two equivalent O(6)Li2Mn2Cu square pyramids, corners with two equivalent O(2)LiMn3Cu square pyramids, corners with two equivalent O(5)LiMn3Cu square pyramids,  an edgeedge with one O(4)Li2Mn2Cu square pyramid,  an edgeedge with one O(1)LiMn3Cu square pyramid, edges with three equivalent O(2)LiMn3Cu square pyramids, and edges with three equivalent O(5)LiMn3Cu square pyramids. In the second O site, O(2) is bonded to one Li(1), one Mn(1), one Mn(2), one Mn(4), and one Cu(2) atom to form OLiMn3Cu square pyramids that share  a cornercorner with one O(2)LiMn3Cu square pyramid, corners with two equivalent O(4)Li2Mn2Cu square pyramids, corners with two equivalent O(6)Li2Mn2Cu square pyramids, corners with two equivalent O(1)LiMn3Cu square pyramids, corners with two equivalent O(5)LiMn3Cu square pyramids,  an edgeedge with one O(3)Li2Mn2Cu square pyramid,  an edgeedge with one O(2)LiMn3Cu square pyramid, edges with three equivalent O(1)LiMn3Cu square pyramids, and edges with three equivalent O(5)LiMn3Cu square pyramids. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Mn(3), one Mn(4), and one Cu(1) atom to form OLi2Mn2Cu square pyramids that share  a cornercorner with one O(3)Li2Mn2Cu square pyramid, corners with two equivalent O(4)Li2Mn2Cu square pyramids, corners with two equivalent O(6)Li2Mn2Cu square pyramids, corners with two equivalent O(1)LiMn3Cu square pyramids, corners with two equivalent O(5)LiMn3Cu square pyramids,  an edgeedge with one O(3)Li2Mn2Cu square pyramid,  an edgeedge with one O(2)LiMn3Cu square pyramid, edges with three equivalent O(4)Li2Mn2Cu square pyramids, and edges with three equivalent O(6)Li2Mn2Cu square pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Mn(3), one Mn(4), and one Cu(1) atom to form OLi2Mn2Cu square pyramids that share  a cornercorner with one O(4)Li2Mn2Cu square pyramid, corners with two equivalent O(3)Li2Mn2Cu square pyramids, corners with two equivalent O(6)Li2Mn2Cu square pyramids, corners with two equivalent O(2)LiMn3Cu square pyramids, corners with two equivalent O(5)LiMn3Cu square pyramids,  an edgeedge with one O(4)Li2Mn2Cu square pyramid,  an edgeedge with one O(1)LiMn3Cu square pyramid, edges with three equivalent O(3)Li2Mn2Cu square pyramids, and edges with three equivalent O(6)Li2Mn2Cu square pyramids. In the fifth O site, O(5) is bonded to one Li(1), one Mn(1), one Mn(2), one Mn(4), and one Cu(2) atom to form distorted OLiMn3Cu square pyramids that share  a cornercorner with one O(5)LiMn3Cu square pyramid, corners with two equivalent O(3)Li2Mn2Cu square pyramids, corners with two equivalent O(4)Li2Mn2Cu square pyramids, corners with two equivalent O(1)LiMn3Cu square pyramids, corners with two equivalent O(2)LiMn3Cu square pyramids,  an edgeedge with one O(6)Li2Mn2Cu square pyramid,  an edgeedge with one O(5)LiMn3Cu square pyramid, edges with three equivalent O(1)LiMn3Cu square pyramids, and edges with three equivalent O(2)LiMn3Cu square pyramids. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one Mn(3), one Mn(4), and one Cu(1) atom to form distorted OLi2Mn2Cu square pyramids that share  a cornercorner with one O(6)Li2Mn2Cu square pyramid, corners with two equivalent O(3)Li2Mn2Cu square pyramids, corners with two equivalent O(4)Li2Mn2Cu square pyramids, corners with two equivalent O(1)LiMn3Cu square pyramids, corners with two equivalent O(2)LiMn3Cu square pyramids,  an edgeedge with one O(6)Li2Mn2Cu square pyramid,  an edgeedge with one O(5)LiMn3Cu square pyramid, edges with three equivalent O(3)Li2Mn2Cu square pyramids, and edges with three equivalent O(4)Li2Mn2Cu square pyramids.