Mn5O3F5 is beta indium sulfide-derived structured and crystallizes in the monoclinic Cc space group. There are five inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one O(3), one F(3), one F(4), and one F(5) atom to form MnO3F3 octahedra that share corners with three equivalent Mn(2)O3F tetrahedra, edges with two equivalent Mn(3)O2F4 octahedra, edges with two equivalent Mn(4)O2F4 octahedra, and edges with two equivalent Mn(5)O2F4 octahedra. In the second Mn site, Mn(2) is bonded to one O(1), one O(2), one O(3), and one F(1) atom to form MnO3F tetrahedra that share corners with three equivalent Mn(3)O2F4 octahedra, corners with three equivalent Mn(4)O2F4 octahedra, corners with three equivalent Mn(5)O2F4 octahedra, and corners with three equivalent Mn(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 50-64°. In the third Mn site, Mn(3) is bonded to one O(1), one O(2), one F(1), one F(2), one F(3), and one F(4) atom to form MnO2F4 octahedra that share corners with three equivalent Mn(2)O3F tetrahedra, edges with two equivalent Mn(4)O2F4 octahedra, edges with two equivalent Mn(5)O2F4 octahedra, and edges with two equivalent Mn(1)O3F3 octahedra. In the fourth Mn site, Mn(4) is bonded to one O(1), one O(3), one F(1), one F(2), one F(4), and one F(5) atom to form MnO2F4 octahedra that share corners with three equivalent Mn(2)O3F tetrahedra, edges with two equivalent Mn(3)O2F4 octahedra, edges with two equivalent Mn(5)O2F4 octahedra, and edges with two equivalent Mn(1)O3F3 octahedra. In the fifth Mn site, Mn(5) is bonded to one O(2), one O(3), one F(1), one F(2), one F(3), and one F(5) atom to form MnO2F4 octahedra that share corners with three equivalent Mn(2)O3F tetrahedra, edges with two equivalent Mn(3)O2F4 octahedra, edges with two equivalent Mn(4)O2F4 octahedra, and edges with two equivalent Mn(1)O3F3 octahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Mn(1), one Mn(2), one Mn(3), and one Mn(4) atom. In the second O site, O(2) is bonded in a distorted trigonal pyramidal geometry to one Mn(1), one Mn(2), one Mn(3), and one Mn(5) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Mn(1), one Mn(2), one Mn(4), and one Mn(5) atom. There are five inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Mn(2), one Mn(3), one Mn(4), and one Mn(5) atom. In the second F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to one Mn(3), one Mn(4), and one Mn(5) atom. In the third F site, F(3) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1), one Mn(3), and one Mn(5) atom. In the fourth F site, F(4) is bonded in a trigonal non-coplanar geometry to one Mn(1), one Mn(3), and one Mn(4) atom. In the fifth F site, F(5) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1), one Mn(4), and one Mn(5) atom.
Mn5O3F5 is beta indium sulfide-derived structured and crystallizes in the monoclinic Cc space group. There are five inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one O(3), one F(3), one F(4), and one F(5) atom to form MnO3F3 octahedra that share corners with three equivalent Mn(2)O3F tetrahedra, edges with two equivalent Mn(3)O2F4 octahedra, edges with two equivalent Mn(4)O2F4 octahedra, and edges with two equivalent Mn(5)O2F4 octahedra. The Mn(1)-O(1) bond length is 2.12 Å. The Mn(1)-O(2) bond length is 2.20 Å. The Mn(1)-O(3) bond length is 2.23 Å. The Mn(1)-F(3) bond length is 2.25 Å. The Mn(1)-F(4) bond length is 2.16 Å. The Mn(1)-F(5) bond length is 2.24 Å. In the second Mn site, Mn(2) is bonded to one O(1), one O(2), one O(3), and one F(1) atom to form MnO3F tetrahedra that share corners with three equivalent Mn(3)O2F4 octahedra, corners with three equivalent Mn(4)O2F4 octahedra, corners with three equivalent Mn(5)O2F4 octahedra, and corners with three equivalent Mn(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 50-64°. The Mn(2)-O(1) bond length is 2.02 Å. The Mn(2)-O(2) bond length is 2.11 Å. The Mn(2)-O(3) bond length is 2.12 Å. The Mn(2)-F(1) bond length is 2.22 Å. In the third Mn site, Mn(3) is bonded to one O(1), one O(2), one F(1), one F(2), one F(3), and one F(4) atom to form MnO2F4 octahedra that share corners with three equivalent Mn(2)O3F tetrahedra, edges with two equivalent Mn(4)O2F4 octahedra, edges with two equivalent Mn(5)O2F4 octahedra, and edges with two equivalent Mn(1)O3F3 octahedra. The Mn(3)-O(1) bond length is 2.10 Å. The Mn(3)-O(2) bond length is 2.14 Å. The Mn(3)-F(1) bond length is 2.27 Å. The Mn(3)-F(2) bond length is 2.16 Å. The Mn(3)-F(3) bond length is 2.25 Å. The Mn(3)-F(4) bond length is 2.16 Å. In the fourth Mn site, Mn(4) is bonded to one O(1), one O(3), one F(1), one F(2), one F(4), and one F(5) atom to form MnO2F4 octahedra that share corners with three equivalent Mn(2)O3F tetrahedra, edges with two equivalent Mn(3)O2F4 octahedra, edges with two equivalent Mn(5)O2F4 octahedra, and edges with two equivalent Mn(1)O3F3 octahedra. The Mn(4)-O(1) bond length is 2.08 Å. The Mn(4)-O(3) bond length is 2.16 Å. The Mn(4)-F(1) bond length is 2.31 Å. The Mn(4)-F(2) bond length is 2.18 Å. The Mn(4)-F(4) bond length is 2.13 Å. The Mn(4)-F(5) bond length is 2.25 Å. In the fifth Mn site, Mn(5) is bonded to one O(2), one O(3), one F(1), one F(2), one F(3), and one F(5) atom to form MnO2F4 octahedra that share corners with three equivalent Mn(2)O3F tetrahedra, edges with two equivalent Mn(3)O2F4 octahedra, edges with two equivalent Mn(4)O2F4 octahedra, and edges with two equivalent Mn(1)O3F3 octahedra. The Mn(5)-O(2) bond length is 1.91 Å. The Mn(5)-O(3) bond length is 1.92 Å. The Mn(5)-F(1) bond length is 2.46 Å. The Mn(5)-F(2) bond length is 2.15 Å. The Mn(5)-F(3) bond length is 2.00 Å. The Mn(5)-F(5) bond length is 2.01 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Mn(1), one Mn(2), one Mn(3), and one Mn(4) atom. In the second O site, O(2) is bonded in a distorted trigonal pyramidal geometry to one Mn(1), one Mn(2), one Mn(3), and one Mn(5) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Mn(1), one Mn(2), one Mn(4), and one Mn(5) atom. There are five inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Mn(2), one Mn(3), one Mn(4), and one Mn(5) atom. In the second F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to one Mn(3), one Mn(4), and one Mn(5) atom. In the third F site, F(3) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1), one Mn(3), and one Mn(5) atom. In the fourth F site, F(4) is bonded in a trigonal non-coplanar geometry to one Mn(1), one Mn(3), and one Mn(4) atom. In the fifth F site, F(5) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1), one Mn(4), and one Mn(5) atom.