Li2Mn5(CuO6)2 crystallizes in the monoclinic P2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(10), one O(11), one O(12), one O(2), and one O(8) atom. In the second Li site, Li(2) is bonded to one O(1), one O(12), one O(5), one O(6), one O(7), and one O(8) atom to form LiO6 octahedra that share  a cornercorner with one Mn(3)O6 octahedra,  a cornercorner with one Mn(5)O6 octahedra,  an edgeedge with one Mn(3)O6 octahedra,  an edgeedge with one Mn(5)O6 octahedra, and edges with three equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-19°. There are five inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(10), one O(11), one O(2), one O(3), one O(4), and one O(9) atom to form MnO6 octahedra that share  a cornercorner with one Mn(3)O6 octahedra,  a cornercorner with one Mn(5)O6 octahedra,  an edgeedge with one Mn(3)O6 octahedra,  an edgeedge with one Mn(5)O6 octahedra, edges with three equivalent Mn(4)O6 octahedra, and edges with three equivalent Cu(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-19°. In the second Mn site, Mn(2) is bonded to one O(1), one O(12), one O(5), one O(6), one O(7), and one O(8) atom to form MnO6 octahedra that share  a cornercorner with one Mn(3)O6 octahedra,  a cornercorner with one Mn(5)O6 octahedra,  an edgeedge with one Mn(3)O6 octahedra,  an edgeedge with one Mn(5)O6 octahedra, and edges with three equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-12°. In the third Mn site, Mn(3) is bonded to one O(1), one O(10), one O(2), one O(7), one O(8), and one O(9) atom to form distorted 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(4)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(4)O6 octahedra, and  an edgeedge with one Cu(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-19°. In the fourth Mn site, Mn(4) is bonded to one O(10), one O(11), one O(2), one O(3), one O(4), and one O(9) atom to form MnO6 octahedra that share  a cornercorner with one Mn(3)O6 octahedra,  a cornercorner with one Mn(5)O6 octahedra,  an edgeedge with one Mn(3)O6 octahedra,  an edgeedge with one Mn(5)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 range from 15-16°. In the fifth Mn site, Mn(5) is bonded to one O(11), one O(12), 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(4)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(4)O6 octahedra, and  an edgeedge with one Cu(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-19°. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 6-coordinate geometry to one O(1), one O(12), one O(5), one O(6), one O(7), and one O(8) atom. In the second Cu site, Cu(2) is bonded to one O(10), one O(11), one O(2), one O(3), one O(4), and one O(9) atom to form distorted CuO6 octahedra that share  a cornercorner with one Mn(3)O6 octahedra,  a cornercorner with one Mn(5)O6 octahedra,  an edgeedge with one Mn(3)O6 octahedra,  an edgeedge with one Mn(5)O6 octahedra, edges with three equivalent Mn(1)O6 octahedra, and edges with three equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-12°. There are twelve 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 Cu(1) atom to form OLi2Mn2Cu square pyramids that share  a cornercorner with one O(11)LiMn3Cu square pyramid, corners with two equivalent O(12)Li2Mn2Cu square pyramids,  an edgeedge with one O(12)Li2Mn2Cu square pyramid, and  an edgeedge with one O(10)LiMn3Cu square pyramid. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Li(1), one Mn(1), one Mn(3), one Mn(4), and one Cu(2) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Mn(1), one Mn(4), one Mn(5), and one Cu(2) atom. In the fourth O site, O(4) is bonded in a see-saw-like geometry to one Mn(1), one Mn(4), one Mn(5), and one Cu(2) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Mn(2), one Mn(5), and one Cu(1) atom. In the sixth O site, O(6) is bonded in a see-saw-like geometry to one Li(2), one Mn(2), one Mn(5), and one Cu(1) atom. In the seventh O site, O(7) is bonded in a see-saw-like geometry to one Li(2), one Mn(2), one Mn(3), and one Cu(1) atom. In the eighth O site, O(8) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Mn(2), one Mn(3), and one Cu(1) atom. In the ninth O site, O(9) is bonded in a see-saw-like geometry to one Mn(1), one Mn(3), one Mn(4), and one Cu(2) atom. In the tenth O site, O(10) is bonded to one Li(1), one Mn(1), one Mn(3), one Mn(4), and one Cu(2) atom to form distorted OLiMn3Cu square pyramids that share  a cornercorner with one O(12)Li2Mn2Cu square pyramid,  an edgeedge with one O(1)Li2Mn2Cu square pyramid, and edges with two equivalent O(11)LiMn3Cu square pyramids. In the eleventh O site, O(11) is bonded to one Li(1), one Mn(1), one Mn(4), one Mn(5), and one Cu(2) atom to form OLiMn3Cu square pyramids that share  a cornercorner with one O(1)Li2Mn2Cu square pyramid,  an edgeedge with one O(12)Li2Mn2Cu square pyramid, and edges with two equivalent O(10)LiMn3Cu square pyramids. In the twelfth O site, O(12) is bonded to one Li(1), one Li(2), one Mn(2), one Mn(5), and one Cu(1) atom to form OLi2Mn2Cu square pyramids that share  a cornercorner with one O(10)LiMn3Cu square pyramid, corners with two equivalent O(1)Li2Mn2Cu square pyramids,  an edgeedge with one O(1)Li2Mn2Cu square pyramid, and  an edgeedge with one O(11)LiMn3Cu square pyramid.
Li2Mn5(CuO6)2 crystallizes in the monoclinic P2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(10), one O(11), one O(12), one O(2), and one O(8) atom. The Li(1)-O(1) bond length is 2.17 Å. The Li(1)-O(10) bond length is 2.07 Å. The Li(1)-O(11) bond length is 2.27 Å. The Li(1)-O(12) bond length is 2.20 Å. The Li(1)-O(2) bond length is 2.63 Å. The Li(1)-O(8) bond length is 1.99 Å. In the second Li site, Li(2) is bonded to one O(1), one O(12), one O(5), one O(6), one O(7), and one O(8) atom to form LiO6 octahedra that share  a cornercorner with one Mn(3)O6 octahedra,  a cornercorner with one Mn(5)O6 octahedra,  an edgeedge with one Mn(3)O6 octahedra,  an edgeedge with one Mn(5)O6 octahedra, and edges with three equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-19°. The Li(2)-O(1) bond length is 2.18 Å. The Li(2)-O(12) bond length is 2.15 Å. The Li(2)-O(5) bond length is 2.15 Å. The Li(2)-O(6) bond length is 2.08 Å. The Li(2)-O(7) bond length is 2.08 Å. The Li(2)-O(8) bond length is 2.12 Å. There are five inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(10), one O(11), one O(2), one O(3), one O(4), and one O(9) atom to form MnO6 octahedra that share  a cornercorner with one Mn(3)O6 octahedra,  a cornercorner with one Mn(5)O6 octahedra,  an edgeedge with one Mn(3)O6 octahedra,  an edgeedge with one Mn(5)O6 octahedra, edges with three equivalent Mn(4)O6 octahedra, and edges with three equivalent Cu(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-19°. The Mn(1)-O(10) bond length is 2.04 Å. The Mn(1)-O(11) bond length is 2.08 Å. The Mn(1)-O(2) bond length is 1.98 Å. The Mn(1)-O(3) bond length is 2.00 Å. The Mn(1)-O(4) bond length is 1.96 Å. The Mn(1)-O(9) bond length is 2.06 Å. In the second Mn site, Mn(2) is bonded to one O(1), one O(12), one O(5), one O(6), one O(7), and one O(8) atom to form MnO6 octahedra that share  a cornercorner with one Mn(3)O6 octahedra,  a cornercorner with one Mn(5)O6 octahedra,  an edgeedge with one Mn(3)O6 octahedra,  an edgeedge with one Mn(5)O6 octahedra, and edges with three equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-12°. The Mn(2)-O(1) bond length is 2.03 Å. The Mn(2)-O(12) bond length is 2.00 Å. The Mn(2)-O(5) bond length is 1.90 Å. The Mn(2)-O(6) bond length is 1.98 Å. The Mn(2)-O(7) bond length is 1.96 Å. The Mn(2)-O(8) bond length is 1.93 Å. In the third Mn site, Mn(3) is bonded to one O(1), one O(10), one O(2), one O(7), one O(8), and one O(9) atom to form distorted 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(4)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(4)O6 octahedra, and  an edgeedge with one Cu(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-19°. The Mn(3)-O(1) bond length is 2.03 Å. The Mn(3)-O(10) bond length is 1.96 Å. The Mn(3)-O(2) bond length is 2.25 Å. The Mn(3)-O(7) bond length is 2.14 Å. The Mn(3)-O(8) bond length is 1.90 Å. The Mn(3)-O(9) bond length is 2.06 Å. In the fourth Mn site, Mn(4) is bonded to one O(10), one O(11), one O(2), one O(3), one O(4), and one O(9) atom to form MnO6 octahedra that share  a cornercorner with one Mn(3)O6 octahedra,  a cornercorner with one Mn(5)O6 octahedra,  an edgeedge with one Mn(3)O6 octahedra,  an edgeedge with one Mn(5)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 range from 15-16°. The Mn(4)-O(10) bond length is 2.04 Å. The Mn(4)-O(11) bond length is 1.98 Å. The Mn(4)-O(2) bond length is 2.04 Å. The Mn(4)-O(3) bond length is 1.96 Å. The Mn(4)-O(4) bond length is 2.00 Å. The Mn(4)-O(9) bond length is 1.97 Å. In the fifth Mn site, Mn(5) is bonded to one O(11), one O(12), 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(4)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(4)O6 octahedra, and  an edgeedge with one Cu(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-19°. The Mn(5)-O(11) bond length is 2.10 Å. The Mn(5)-O(12) bond length is 2.17 Å. The Mn(5)-O(3) bond length is 1.99 Å. The Mn(5)-O(4) bond length is 2.20 Å. The Mn(5)-O(5) bond length is 1.89 Å. The Mn(5)-O(6) bond length is 2.00 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 6-coordinate geometry to one O(1), one O(12), one O(5), one O(6), one O(7), and one O(8) atom. The Cu(1)-O(1) bond length is 1.90 Å. The Cu(1)-O(12) bond length is 1.89 Å. The Cu(1)-O(5) bond length is 2.43 Å. The Cu(1)-O(6) bond length is 1.90 Å. The Cu(1)-O(7) bond length is 1.87 Å. The Cu(1)-O(8) bond length is 2.52 Å. In the second Cu site, Cu(2) is bonded to one O(10), one O(11), one O(2), one O(3), one O(4), and one O(9) atom to form distorted CuO6 octahedra that share  a cornercorner with one Mn(3)O6 octahedra,  a cornercorner with one Mn(5)O6 octahedra,  an edgeedge with one Mn(3)O6 octahedra,  an edgeedge with one Mn(5)O6 octahedra, edges with three equivalent Mn(1)O6 octahedra, and edges with three equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-12°. The Cu(2)-O(10) bond length is 2.56 Å. The Cu(2)-O(11) bond length is 2.01 Å. The Cu(2)-O(2) bond length is 1.98 Å. The Cu(2)-O(3) bond length is 2.43 Å. The Cu(2)-O(4) bond length is 1.98 Å. The Cu(2)-O(9) bond length is 1.99 Å. There are twelve 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 Cu(1) atom to form OLi2Mn2Cu square pyramids that share  a cornercorner with one O(11)LiMn3Cu square pyramid, corners with two equivalent O(12)Li2Mn2Cu square pyramids,  an edgeedge with one O(12)Li2Mn2Cu square pyramid, and  an edgeedge with one O(10)LiMn3Cu square pyramid. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Li(1), one Mn(1), one Mn(3), one Mn(4), and one Cu(2) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Mn(1), one Mn(4), one Mn(5), and one Cu(2) atom. In the fourth O site, O(4) is bonded in a see-saw-like geometry to one Mn(1), one Mn(4), one Mn(5), and one Cu(2) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Mn(2), one Mn(5), and one Cu(1) atom. In the sixth O site, O(6) is bonded in a see-saw-like geometry to one Li(2), one Mn(2), one Mn(5), and one Cu(1) atom. In the seventh O site, O(7) is bonded in a see-saw-like geometry to one Li(2), one Mn(2), one Mn(3), and one Cu(1) atom. In the eighth O site, O(8) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Mn(2), one Mn(3), and one Cu(1) atom. In the ninth O site, O(9) is bonded in a see-saw-like geometry to one Mn(1), one Mn(3), one Mn(4), and one Cu(2) atom. In the tenth O site, O(10) is bonded to one Li(1), one Mn(1), one Mn(3), one Mn(4), and one Cu(2) atom to form distorted OLiMn3Cu square pyramids that share  a cornercorner with one O(12)Li2Mn2Cu square pyramid,  an edgeedge with one O(1)Li2Mn2Cu square pyramid, and edges with two equivalent O(11)LiMn3Cu square pyramids. In the eleventh O site, O(11) is bonded to one Li(1), one Mn(1), one Mn(4), one Mn(5), and one Cu(2) atom to form OLiMn3Cu square pyramids that share  a cornercorner with one O(1)Li2Mn2Cu square pyramid,  an edgeedge with one O(12)Li2Mn2Cu square pyramid, and edges with two equivalent O(10)LiMn3Cu square pyramids. In the twelfth O site, O(12) is bonded to one Li(1), one Li(2), one Mn(2), one Mn(5), and one Cu(1) atom to form OLi2Mn2Cu square pyramids that share  a cornercorner with one O(10)LiMn3Cu square pyramid, corners with two equivalent O(1)Li2Mn2Cu square pyramids,  an edgeedge with one O(1)Li2Mn2Cu square pyramid, and  an edgeedge with one O(11)LiMn3Cu square pyramid.