Fe3(OF2)2 is Hydrophilite-derived structured and crystallizes in the monoclinic C2 space group. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), one O(3), one F(1), one F(3), and one F(4) atom to form FeO3F3 octahedra that share corners with three equivalent Fe(4)O2F4 octahedra, corners with five equivalent Fe(2)OF5 octahedra,  an edgeedge with one Fe(3)O2F4 octahedra, and  an edgeedge with one Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 43-55°. In the second Fe site, Fe(2) is bonded to one O(1), one F(1), one F(2), one F(3), and two equivalent F(4) atoms to form FeOF5 octahedra that share corners with three equivalent Fe(3)O2F4 octahedra, corners with five equivalent Fe(1)O3F3 octahedra,  an edgeedge with one Fe(4)O2F4 octahedra, and  an edgeedge with one Fe(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 45-57°. In the third Fe site, Fe(3) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form FeO2F4 octahedra that share corners with two equivalent Fe(4)O2F4 octahedra, corners with six equivalent Fe(2)OF5 octahedra, and edges with two equivalent Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 45-57°. In the fourth Fe site, Fe(4) is bonded to one O(2), one O(3), two equivalent F(2), and two equivalent F(3) atoms to form FeO2F4 octahedra that share corners with two equivalent Fe(3)O2F4 octahedra, corners with six equivalent Fe(1)O3F3 octahedra, and edges with two equivalent Fe(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 43-48°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Fe(1), one Fe(2), and one Fe(3) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Fe(4) and two equivalent Fe(1) atoms. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Fe(4) and two equivalent Fe(1) atoms. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar 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(2), one Fe(3), and one Fe(4) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(2), and one Fe(4) atom. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Fe(1) and two equivalent Fe(2) atoms.
Fe3(OF2)2 is Hydrophilite-derived structured and crystallizes in the monoclinic C2 space group. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), one O(3), one F(1), one F(3), and one F(4) atom to form FeO3F3 octahedra that share corners with three equivalent Fe(4)O2F4 octahedra, corners with five equivalent Fe(2)OF5 octahedra,  an edgeedge with one Fe(3)O2F4 octahedra, and  an edgeedge with one Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 43-55°. The Fe(1)-O(1) bond length is 1.95 Å. The Fe(1)-O(2) bond length is 1.97 Å. The Fe(1)-O(3) bond length is 2.00 Å. The Fe(1)-F(1) bond length is 2.21 Å. The Fe(1)-F(3) bond length is 2.12 Å. The Fe(1)-F(4) bond length is 2.03 Å. In the second Fe site, Fe(2) is bonded to one O(1), one F(1), one F(2), one F(3), and two equivalent F(4) atoms to form FeOF5 octahedra that share corners with three equivalent Fe(3)O2F4 octahedra, corners with five equivalent Fe(1)O3F3 octahedra,  an edgeedge with one Fe(4)O2F4 octahedra, and  an edgeedge with one Fe(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 45-57°. The Fe(2)-O(1) bond length is 1.98 Å. The Fe(2)-F(1) bond length is 2.07 Å. The Fe(2)-F(2) bond length is 2.16 Å. The Fe(2)-F(3) bond length is 2.15 Å. There is one shorter (2.12 Å) and one longer (2.13 Å) Fe(2)-F(4) bond length. In the third Fe site, Fe(3) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form FeO2F4 octahedra that share corners with two equivalent Fe(4)O2F4 octahedra, corners with six equivalent Fe(2)OF5 octahedra, and edges with two equivalent Fe(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 45-57°. Both Fe(3)-O(1) bond lengths are 1.90 Å. Both Fe(3)-F(1) bond lengths are 2.13 Å. Both Fe(3)-F(2) bond lengths are 2.08 Å. In the fourth Fe site, Fe(4) is bonded to one O(2), one O(3), two equivalent F(2), and two equivalent F(3) atoms to form FeO2F4 octahedra that share corners with two equivalent Fe(3)O2F4 octahedra, corners with six equivalent Fe(1)O3F3 octahedra, and edges with two equivalent Fe(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 43-48°. The Fe(4)-O(2) bond length is 1.98 Å. The Fe(4)-O(3) bond length is 1.94 Å. Both Fe(4)-F(2) bond lengths are 2.07 Å. Both Fe(4)-F(3) bond lengths are 2.06 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Fe(1), one Fe(2), and one Fe(3) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Fe(4) and two equivalent Fe(1) atoms. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Fe(4) and two equivalent Fe(1) atoms. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar 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(2), one Fe(3), and one Fe(4) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Fe(1), one Fe(2), and one Fe(4) atom. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Fe(1) and two equivalent Fe(2) atoms.