Fe5(OF2)4 crystallizes in the orthorhombic F222 space group. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded in a 6-coordinate geometry to four equivalent O(1) and two equivalent F(3) atoms. In the second Fe site, Fe(2) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form a mixture of edge and corner-sharing FeO2F4 octahedra. The corner-sharing octahedral tilt angles are 1°. In the third Fe site, Fe(3) is bonded to two equivalent O(1), two equivalent F(2), and two equivalent F(3) atoms to form a mixture of distorted edge and corner-sharing FeO2F4 octahedra. The corner-sharing octahedral tilt angles are 13°. O(1) is bonded in a distorted trigonal non-coplanar geometry to one Fe(1), one Fe(2), and one Fe(3) atom. There are three inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to two equivalent Fe(2) atoms. In the second F site, F(2) is bonded in a water-like geometry to one Fe(2) and one Fe(3) atom. In the third F site, F(3) is bonded in a T-shaped geometry to one Fe(1) and two equivalent Fe(3) atoms.
Fe5(OF2)4 crystallizes in the orthorhombic F222 space group. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded in a 6-coordinate geometry to four equivalent O(1) and two equivalent F(3) atoms. All Fe(1)-O(1) bond lengths are 1.91 Å. Both Fe(1)-F(3) bond lengths are 2.25 Å. In the second Fe site, Fe(2) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form a mixture of edge and corner-sharing FeO2F4 octahedra. The corner-sharing octahedral tilt angles are 1°. Both Fe(2)-O(1) bond lengths are 2.01 Å. Both Fe(2)-F(1) bond lengths are 1.97 Å. Both Fe(2)-F(2) bond lengths are 2.00 Å. In the third Fe site, Fe(3) is bonded to two equivalent O(1), two equivalent F(2), and two equivalent F(3) atoms to form a mixture of distorted edge and corner-sharing FeO2F4 octahedra. The corner-sharing octahedral tilt angles are 13°. Both Fe(3)-O(1) bond lengths are 1.99 Å. Both Fe(3)-F(2) bond lengths are 1.94 Å. Both Fe(3)-F(3) bond lengths are 2.02 Å. O(1) is bonded in a distorted trigonal non-coplanar geometry to one Fe(1), one Fe(2), and one Fe(3) atom. There are three inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to two equivalent Fe(2) atoms. In the second F site, F(2) is bonded in a water-like geometry to one Fe(2) and one Fe(3) atom. In the third F site, F(3) is bonded in a T-shaped geometry to one Fe(1) and two equivalent Fe(3) atoms.