Li2Mn4O5F3 is Hausmannite-derived structured and crystallizes in the monoclinic Cc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one F(2), and one F(3) atom to form LiO2F2 tetrahedra that share corners with three equivalent Mn(1)O3F3 octahedra, corners with three equivalent Mn(3)O3F3 octahedra, corners with three equivalent Mn(2)O4F2 octahedra, and corners with three equivalent Mn(4)O5F octahedra. The corner-sharing octahedral tilt angles range from 48-72°. In the second Li site, Li(2) is bonded to one O(3), one O(4), one O(5), and one F(1) atom to form LiO3F tetrahedra that share corners with three equivalent Mn(1)O3F3 octahedra, corners with three equivalent Mn(3)O3F3 octahedra, corners with three equivalent Mn(2)O4F2 octahedra, and corners with three equivalent Mn(4)O5F octahedra. The corner-sharing octahedral tilt angles range from 47-65°. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one O(3), one O(4), one F(1), one F(2), and one F(3) atom to form MnO3F3 octahedra that share corners with three equivalent Li(1)O2F2 tetrahedra, corners with three equivalent Li(2)O3F tetrahedra, edges with two equivalent Mn(3)O3F3 octahedra, edges with two equivalent Mn(2)O4F2 octahedra, and edges with two equivalent Mn(4)O5F octahedra. In the second Mn site, Mn(2) is bonded to one O(1), one O(2), one O(3), one O(5), one F(1), and one F(2) atom to form MnO4F2 octahedra that share corners with three equivalent Li(1)O2F2 tetrahedra, corners with three equivalent Li(2)O3F tetrahedra, edges with two equivalent Mn(1)O3F3 octahedra, edges with two equivalent Mn(3)O3F3 octahedra, and edges with two equivalent Mn(4)O5F octahedra. In the third Mn site, Mn(3) is bonded to one O(1), one O(4), one O(5), one F(1), one F(2), and one F(3) atom to form MnO3F3 octahedra that share corners with three equivalent Li(1)O2F2 tetrahedra, corners with three equivalent Li(2)O3F tetrahedra, edges with two equivalent Mn(1)O3F3 octahedra, edges with two equivalent Mn(2)O4F2 octahedra, and edges with two equivalent Mn(4)O5F octahedra. 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 F(3) atom to form distorted MnO5F octahedra that share corners with three equivalent Li(1)O2F2 tetrahedra, corners with three equivalent Li(2)O3F tetrahedra, edges with two equivalent Mn(1)O3F3 octahedra, edges with two equivalent Mn(3)O3F3 octahedra, and edges with two equivalent Mn(2)O4F2 octahedra. There are five inequivalent O sites. In the first O site, O(5) is bonded to one Li(2), one Mn(2), one Mn(3), and one Mn(4) atom to form a mixture of distorted corner and edge-sharing OLiMn3 tetrahedra. In the second O site, O(1) is bonded to one Li(1), one Mn(2), one Mn(3), and one Mn(4) atom to form a mixture of corner and edge-sharing OLiMn3 tetrahedra. In the third O site, O(2) is bonded to one Li(1), one Mn(1), one Mn(2), and one Mn(4) atom to form a mixture of corner and edge-sharing OLiMn3 tetrahedra. In the fourth O site, O(3) is bonded to one Li(2), one Mn(1), one Mn(2), and one Mn(4) atom to form a mixture of distorted corner and edge-sharing OLiMn3 tetrahedra. In the fifth O site, O(4) is bonded to one Li(2), one Mn(1), one Mn(3), and one Mn(4) atom to form a mixture of distorted corner and edge-sharing OLiMn3 trigonal pyramids. There are three inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(2), one Mn(1), one Mn(2), and one Mn(3) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(1), one Mn(2), and one Mn(3) atom. In the third F site, F(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(1), one Mn(3), and one Mn(4) atom.
Li2Mn4O5F3 is Hausmannite-derived structured and crystallizes in the monoclinic Cc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one F(2), and one F(3) atom to form LiO2F2 tetrahedra that share corners with three equivalent Mn(1)O3F3 octahedra, corners with three equivalent Mn(3)O3F3 octahedra, corners with three equivalent Mn(2)O4F2 octahedra, and corners with three equivalent Mn(4)O5F octahedra. The corner-sharing octahedral tilt angles range from 48-72°. The Li(1)-O(1) bond length is 2.19 Å. The Li(1)-O(2) bond length is 2.06 Å. The Li(1)-F(2) bond length is 1.94 Å. The Li(1)-F(3) bond length is 1.99 Å. In the second Li site, Li(2) is bonded to one O(3), one O(4), one O(5), and one F(1) atom to form LiO3F tetrahedra that share corners with three equivalent Mn(1)O3F3 octahedra, corners with three equivalent Mn(3)O3F3 octahedra, corners with three equivalent Mn(2)O4F2 octahedra, and corners with three equivalent Mn(4)O5F octahedra. The corner-sharing octahedral tilt angles range from 47-65°. The Li(2)-O(3) bond length is 2.05 Å. The Li(2)-O(4) bond length is 1.96 Å. The Li(2)-O(5) bond length is 2.29 Å. The Li(2)-F(1) bond length is 1.92 Å. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one O(3), one O(4), one F(1), one F(2), and one F(3) atom to form MnO3F3 octahedra that share corners with three equivalent Li(1)O2F2 tetrahedra, corners with three equivalent Li(2)O3F tetrahedra, edges with two equivalent Mn(3)O3F3 octahedra, edges with two equivalent Mn(2)O4F2 octahedra, and edges with two equivalent Mn(4)O5F octahedra. The Mn(1)-O(2) bond length is 2.09 Å. The Mn(1)-O(3) bond length is 2.14 Å. The Mn(1)-O(4) bond length is 2.07 Å. The Mn(1)-F(1) bond length is 2.22 Å. The Mn(1)-F(2) bond length is 2.19 Å. The Mn(1)-F(3) bond length is 2.23 Å. In the second Mn site, Mn(2) is bonded to one O(1), one O(2), one O(3), one O(5), one F(1), and one F(2) atom to form MnO4F2 octahedra that share corners with three equivalent Li(1)O2F2 tetrahedra, corners with three equivalent Li(2)O3F tetrahedra, edges with two equivalent Mn(1)O3F3 octahedra, edges with two equivalent Mn(3)O3F3 octahedra, and edges with two equivalent Mn(4)O5F octahedra. The Mn(2)-O(1) bond length is 1.99 Å. The Mn(2)-O(2) bond length is 1.96 Å. The Mn(2)-O(3) bond length is 1.95 Å. The Mn(2)-O(5) bond length is 1.98 Å. The Mn(2)-F(1) bond length is 2.29 Å. The Mn(2)-F(2) bond length is 2.35 Å. In the third Mn site, Mn(3) is bonded to one O(1), one O(4), one O(5), one F(1), one F(2), and one F(3) atom to form MnO3F3 octahedra that share corners with three equivalent Li(1)O2F2 tetrahedra, corners with three equivalent Li(2)O3F tetrahedra, edges with two equivalent Mn(1)O3F3 octahedra, edges with two equivalent Mn(2)O4F2 octahedra, and edges with two equivalent Mn(4)O5F octahedra. The Mn(3)-O(1) bond length is 1.98 Å. The Mn(3)-O(4) bond length is 1.89 Å. The Mn(3)-O(5) bond length is 1.97 Å. The Mn(3)-F(1) bond length is 2.25 Å. The Mn(3)-F(2) bond length is 2.23 Å. The Mn(3)-F(3) bond length is 2.04 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 F(3) atom to form distorted MnO5F octahedra that share corners with three equivalent Li(1)O2F2 tetrahedra, corners with three equivalent Li(2)O3F tetrahedra, edges with two equivalent Mn(1)O3F3 octahedra, edges with two equivalent Mn(3)O3F3 octahedra, and edges with two equivalent Mn(2)O4F2 octahedra. The Mn(4)-O(1) bond length is 2.00 Å. The Mn(4)-O(2) bond length is 1.95 Å. The Mn(4)-O(3) bond length is 1.96 Å. The Mn(4)-O(4) bond length is 2.19 Å. The Mn(4)-O(5) bond length is 2.01 Å. The Mn(4)-F(3) bond length is 2.50 Å. There are five inequivalent O sites. In the first O site, O(5) is bonded to one Li(2), one Mn(2), one Mn(3), and one Mn(4) atom to form a mixture of distorted corner and edge-sharing OLiMn3 tetrahedra. In the second O site, O(1) is bonded to one Li(1), one Mn(2), one Mn(3), and one Mn(4) atom to form a mixture of corner and edge-sharing OLiMn3 tetrahedra. In the third O site, O(2) is bonded to one Li(1), one Mn(1), one Mn(2), and one Mn(4) atom to form a mixture of corner and edge-sharing OLiMn3 tetrahedra. In the fourth O site, O(3) is bonded to one Li(2), one Mn(1), one Mn(2), and one Mn(4) atom to form a mixture of distorted corner and edge-sharing OLiMn3 tetrahedra. In the fifth O site, O(4) is bonded to one Li(2), one Mn(1), one Mn(3), and one Mn(4) atom to form a mixture of distorted corner and edge-sharing OLiMn3 trigonal pyramids. There are three inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(2), one Mn(1), one Mn(2), and one Mn(3) atom. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(1), one Mn(2), and one Mn(3) atom. In the third F site, F(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(1), one Mn(3), and one Mn(4) atom.