Mn5O3F5 is beta indium sulfide-derived structured and crystallizes in the trigonal R3m space group. There are six inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to three equivalent O(1) and one F(2) atom to form MnO3F tetrahedra that share corners with three equivalent Mn(6)O2F4 octahedra, corners with three equivalent Mn(4)O3F3 octahedra, and corners with six equivalent Mn(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 51-61°. In the second Mn site, Mn(2) is bonded to three equivalent O(2) and one F(1) atom to form MnO3F tetrahedra that share corners with three equivalent Mn(3)O2F4 octahedra, corners with three equivalent Mn(5)O3F3 octahedra, and corners with six equivalent Mn(6)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 52-61°. In the third Mn site, Mn(3) is bonded to two equivalent O(1), one F(1), one F(4), and two equivalent F(6) atoms to form MnO2F4 octahedra that share  a cornercorner with one Mn(2)O3F tetrahedra, corners with two equivalent Mn(1)O3F tetrahedra,  an edgeedge with one Mn(4)O3F3 octahedra,  an edgeedge with one Mn(5)O3F3 octahedra, and edges with four equivalent Mn(3)O2F4 octahedra. In the fourth Mn site, Mn(4) is bonded to three equivalent O(1) and three equivalent F(5) atoms to form MnO3F3 octahedra that share corners with three equivalent Mn(1)O3F tetrahedra, edges with three equivalent Mn(3)O2F4 octahedra, and edges with three equivalent Mn(6)O2F4 octahedra. In the fifth Mn site, Mn(5) is bonded to three equivalent O(2) and three equivalent F(6) atoms to form MnO3F3 octahedra that share corners with three equivalent Mn(2)O3F tetrahedra, edges with three equivalent Mn(3)O2F4 octahedra, and edges with three equivalent Mn(6)O2F4 octahedra. In the sixth Mn site, Mn(6) is bonded to two equivalent O(2), one F(2), one F(3), and two equivalent F(5) atoms to form MnO2F4 octahedra that share  a cornercorner with one Mn(1)O3F tetrahedra, corners with two equivalent Mn(2)O3F tetrahedra,  an edgeedge with one Mn(4)O3F3 octahedra,  an edgeedge with one Mn(5)O3F3 octahedra, and edges with four equivalent Mn(6)O2F4 octahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Mn(1), one Mn(4), and two equivalent Mn(3) atoms to form a mixture of distorted edge and corner-sharing OMn4 trigonal pyramids. In the second O site, O(2) is bonded to one Mn(2), one Mn(5), and two equivalent Mn(6) atoms to form a mixture of distorted edge and corner-sharing OMn4 trigonal pyramids. There are six inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Mn(2) and three equivalent Mn(3) atoms. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Mn(1) and three equivalent Mn(6) atoms. In the third F site, F(3) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Mn(6) atoms. In the fourth F site, F(4) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Mn(3) atoms. In the fifth F site, F(5) is bonded in a trigonal non-coplanar geometry to one Mn(4) and two equivalent Mn(6) atoms. In the sixth F site, F(6) is bonded in a distorted trigonal non-coplanar geometry to one Mn(5) and two equivalent Mn(3) atoms.
Mn5O3F5 is beta indium sulfide-derived structured and crystallizes in the trigonal R3m space group. There are six inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to three equivalent O(1) and one F(2) atom to form MnO3F tetrahedra that share corners with three equivalent Mn(6)O2F4 octahedra, corners with three equivalent Mn(4)O3F3 octahedra, and corners with six equivalent Mn(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 51-61°. All Mn(1)-O(1) bond lengths are 2.05 Å. The Mn(1)-F(2) bond length is 2.21 Å. In the second Mn site, Mn(2) is bonded to three equivalent O(2) and one F(1) atom to form MnO3F tetrahedra that share corners with three equivalent Mn(3)O2F4 octahedra, corners with three equivalent Mn(5)O3F3 octahedra, and corners with six equivalent Mn(6)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 52-61°. All Mn(2)-O(2) bond lengths are 2.09 Å. The Mn(2)-F(1) bond length is 2.25 Å. In the third Mn site, Mn(3) is bonded to two equivalent O(1), one F(1), one F(4), and two equivalent F(6) atoms to form MnO2F4 octahedra that share  a cornercorner with one Mn(2)O3F tetrahedra, corners with two equivalent Mn(1)O3F tetrahedra,  an edgeedge with one Mn(4)O3F3 octahedra,  an edgeedge with one Mn(5)O3F3 octahedra, and edges with four equivalent Mn(3)O2F4 octahedra. Both Mn(3)-O(1) bond lengths are 2.07 Å. The Mn(3)-F(1) bond length is 2.32 Å. The Mn(3)-F(4) bond length is 2.15 Å. Both Mn(3)-F(6) bond lengths are 2.13 Å. In the fourth Mn site, Mn(4) is bonded to three equivalent O(1) and three equivalent F(5) atoms to form MnO3F3 octahedra that share corners with three equivalent Mn(1)O3F tetrahedra, edges with three equivalent Mn(3)O2F4 octahedra, and edges with three equivalent Mn(6)O2F4 octahedra. All Mn(4)-O(1) bond lengths are 2.17 Å. All Mn(4)-F(5) bond lengths are 2.21 Å. In the fifth Mn site, Mn(5) is bonded to three equivalent O(2) and three equivalent F(6) atoms to form MnO3F3 octahedra that share corners with three equivalent Mn(2)O3F tetrahedra, edges with three equivalent Mn(3)O2F4 octahedra, and edges with three equivalent Mn(6)O2F4 octahedra. All Mn(5)-O(2) bond lengths are 2.18 Å. All Mn(5)-F(6) bond lengths are 2.21 Å. In the sixth Mn site, Mn(6) is bonded to two equivalent O(2), one F(2), one F(3), and two equivalent F(5) atoms to form MnO2F4 octahedra that share  a cornercorner with one Mn(1)O3F tetrahedra, corners with two equivalent Mn(2)O3F tetrahedra,  an edgeedge with one Mn(4)O3F3 octahedra,  an edgeedge with one Mn(5)O3F3 octahedra, and edges with four equivalent Mn(6)O2F4 octahedra. Both Mn(6)-O(2) bond lengths are 2.04 Å. The Mn(6)-F(2) bond length is 2.34 Å. The Mn(6)-F(3) bond length is 2.16 Å. Both Mn(6)-F(5) bond lengths are 2.13 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Mn(1), one Mn(4), and two equivalent Mn(3) atoms to form a mixture of distorted edge and corner-sharing OMn4 trigonal pyramids. In the second O site, O(2) is bonded to one Mn(2), one Mn(5), and two equivalent Mn(6) atoms to form a mixture of distorted edge and corner-sharing OMn4 trigonal pyramids. There are six inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Mn(2) and three equivalent Mn(3) atoms. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Mn(1) and three equivalent Mn(6) atoms. In the third F site, F(3) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Mn(6) atoms. In the fourth F site, F(4) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Mn(3) atoms. In the fifth F site, F(5) is bonded in a trigonal non-coplanar geometry to one Mn(4) and two equivalent Mn(6) atoms. In the sixth F site, F(6) is bonded in a distorted trigonal non-coplanar geometry to one Mn(5) and two equivalent Mn(3) atoms.