Fe3(OF2)2 is Hydrophilite-derived structured and crystallizes in the orthorhombic Cmmm space group. There are four 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(2) atoms to form FeO2F4 octahedra that share corners with two equivalent Fe(3)O4F2 octahedra, corners with six equivalent Fe(2)OF5 octahedra, and edges with two equivalent Fe(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 47-54°. In the second Fe site, Fe(2) is bonded to one O(1), one F(3), and four equivalent F(1) atoms to form FeOF5 octahedra that share corners with two equivalent Fe(4)O2F4 octahedra, corners with six equivalent Fe(1)O2F4 octahedra, and edges with two equivalent Fe(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 49-54°. In the third Fe site, Fe(3) is bonded to four equivalent O(2) and two equivalent F(2) atoms to form FeO4F2 octahedra that share corners with four equivalent Fe(1)O2F4 octahedra, corners with four equivalent Fe(4)O2F4 octahedra, and edges with two equivalent Fe(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 47-49°. In the fourth Fe site, Fe(4) is bonded to two equivalent O(2) and four equivalent F(3) atoms to form FeO2F4 octahedra that share corners with four equivalent Fe(3)O4F2 octahedra, corners with four equivalent Fe(2)OF5 octahedra, and edges with two equivalent Fe(4)O2F4 octahedra. The corner-sharing octahedral tilt angles are 49°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Fe(2) and two equivalent Fe(1) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Fe(4) and two equivalent Fe(3) atoms. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Fe(1) and two equivalent Fe(2) atoms. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Fe(3) and two equivalent Fe(1) atoms. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Fe(2) and two equivalent Fe(4) atoms.
Fe3(OF2)2 is Hydrophilite-derived structured and crystallizes in the orthorhombic Cmmm space group. There are four 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(2) atoms to form FeO2F4 octahedra that share corners with two equivalent Fe(3)O4F2 octahedra, corners with six equivalent Fe(2)OF5 octahedra, and edges with two equivalent Fe(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 47-54°. Both Fe(1)-O(1) bond lengths are 1.92 Å. Both Fe(1)-F(1) bond lengths are 1.99 Å. Both Fe(1)-F(2) bond lengths are 2.13 Å. In the second Fe site, Fe(2) is bonded to one O(1), one F(3), and four equivalent F(1) atoms to form FeOF5 octahedra that share corners with two equivalent Fe(4)O2F4 octahedra, corners with six equivalent Fe(1)O2F4 octahedra, and edges with two equivalent Fe(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 49-54°. The Fe(2)-O(1) bond length is 2.04 Å. The Fe(2)-F(3) bond length is 2.20 Å. All Fe(2)-F(1) bond lengths are 2.08 Å. In the third Fe site, Fe(3) is bonded to four equivalent O(2) and two equivalent F(2) atoms to form FeO4F2 octahedra that share corners with four equivalent Fe(1)O2F4 octahedra, corners with four equivalent Fe(4)O2F4 octahedra, and edges with two equivalent Fe(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 47-49°. All Fe(3)-O(2) bond lengths are 2.05 Å. Both Fe(3)-F(2) bond lengths are 2.17 Å. In the fourth Fe site, Fe(4) is bonded to two equivalent O(2) and four equivalent F(3) atoms to form FeO2F4 octahedra that share corners with four equivalent Fe(3)O4F2 octahedra, corners with four equivalent Fe(2)OF5 octahedra, and edges with two equivalent Fe(4)O2F4 octahedra. The corner-sharing octahedral tilt angles are 49°. Both Fe(4)-O(2) bond lengths are 1.99 Å. All Fe(4)-F(3) bond lengths are 2.06 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Fe(2) and two equivalent Fe(1) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Fe(4) and two equivalent Fe(3) atoms. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Fe(1) and two equivalent Fe(2) atoms. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Fe(3) and two equivalent Fe(1) atoms. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Fe(2) and two equivalent Fe(4) atoms.