Fe5(OF4)2 is Hydrophilite-derived structured and crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(3) atoms to form a mixture of corner and edge-sharing FeO2F4 octahedra. The corner-sharing octahedral tilt angles range from 50-57°. In the second Fe site, Fe(2) is bonded to one O(1), one F(1), two equivalent F(2), and two equivalent F(4) atoms to form FeOF5 octahedra that share corners with four equivalent Fe(2)OF5 octahedra, corners with four equivalent Fe(3)OF5 octahedra,  an edgeedge with one Fe(1)O2F4 octahedra, and  an edgeedge with one Fe(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 37-61°. In the third Fe site, Fe(3) is bonded to one O(1), one F(1), one F(2), one F(4), and two equivalent F(3) atoms to form FeOF5 octahedra that share corners with four equivalent Fe(1)O2F4 octahedra, corners with four equivalent Fe(2)OF5 octahedra,  an edgeedge with one Fe(2)OF5 octahedra, and  an edgeedge with one Fe(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 37-61°. O(1) is bonded in a trigonal planar geometry to one Fe(1), one Fe(2), and one Fe(3) atom. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Fe(1), one Fe(2), and one Fe(3) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Fe(3) and two equivalent Fe(2) atoms. In the third F site, F(3) is bonded in a trigonal planar geometry to one Fe(1) and two equivalent Fe(3) atoms. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Fe(3) and two equivalent Fe(2) atoms.
Fe5(OF4)2 is Hydrophilite-derived structured and crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(3) atoms to form a mixture of corner and edge-sharing FeO2F4 octahedra. The corner-sharing octahedral tilt angles range from 50-57°. Both Fe(1)-O(1) bond lengths are 2.06 Å. Both Fe(1)-F(1) bond lengths are 2.31 Å. Both Fe(1)-F(3) bond lengths are 2.08 Å. In the second Fe site, Fe(2) is bonded to one O(1), one F(1), two equivalent F(2), and two equivalent F(4) atoms to form FeOF5 octahedra that share corners with four equivalent Fe(2)OF5 octahedra, corners with four equivalent Fe(3)OF5 octahedra,  an edgeedge with one Fe(1)O2F4 octahedra, and  an edgeedge with one Fe(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 37-61°. The Fe(2)-O(1) bond length is 1.81 Å. The Fe(2)-F(1) bond length is 2.01 Å. There is one shorter (2.05 Å) and one longer (2.12 Å) Fe(2)-F(2) bond length. There is one shorter (2.06 Å) and one longer (2.09 Å) Fe(2)-F(4) bond length. In the third Fe site, Fe(3) is bonded to one O(1), one F(1), one F(2), one F(4), and two equivalent F(3) atoms to form FeOF5 octahedra that share corners with four equivalent Fe(1)O2F4 octahedra, corners with four equivalent Fe(2)OF5 octahedra,  an edgeedge with one Fe(2)OF5 octahedra, and  an edgeedge with one Fe(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 37-61°. The Fe(3)-O(1) bond length is 2.03 Å. The Fe(3)-F(1) bond length is 2.13 Å. The Fe(3)-F(2) bond length is 2.21 Å. The Fe(3)-F(4) bond length is 2.21 Å. There is one shorter (2.10 Å) and one longer (2.12 Å) Fe(3)-F(3) bond length. O(1) is bonded in a trigonal planar geometry to one Fe(1), one Fe(2), and one Fe(3) atom. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Fe(1), one Fe(2), and one Fe(3) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Fe(3) and two equivalent Fe(2) atoms. In the third F site, F(3) is bonded in a trigonal planar geometry to one Fe(1) and two equivalent Fe(3) atoms. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Fe(3) and two equivalent Fe(2) atoms.