Fe3(OF3)2 crystallizes in the monoclinic P2_1/c space group. There are two 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 a mixture of corner and edge-sharing FeO2F4 octahedra. The corner-sharing octahedral tilt angles range from 42-51°. In the second Fe site, Fe(2) is bonded to two equivalent O(1), one F(1), one F(2), 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 37-51°. O(1) is bonded in a trigonal planar geometry to one Fe(1) and two equivalent Fe(2) atoms. There are three inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Fe(1) and one Fe(2) atom. In the second F site, F(2) is bonded in a water-like geometry to one Fe(1) and one Fe(2) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to two equivalent Fe(2) atoms.
Fe3(OF3)2 crystallizes in the monoclinic P2_1/c space group. There are two 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 a mixture of corner and edge-sharing FeO2F4 octahedra. The corner-sharing octahedral tilt angles range from 42-51°. Both Fe(1)-O(1) bond lengths are 1.90 Å. Both Fe(1)-F(1) bond lengths are 1.98 Å. Both Fe(1)-F(2) bond lengths are 1.93 Å. In the second Fe site, Fe(2) is bonded to two equivalent O(1), one F(1), one F(2), 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 37-51°. There is one shorter (2.00 Å) and one longer (2.03 Å) Fe(2)-O(1) bond length. The Fe(2)-F(1) bond length is 1.94 Å. The Fe(2)-F(2) bond length is 2.01 Å. There is one shorter (1.95 Å) and one longer (1.98 Å) Fe(2)-F(3) bond length. O(1) is bonded in a trigonal planar geometry to one Fe(1) and two equivalent Fe(2) atoms. There are three inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Fe(1) and one Fe(2) atom. In the second F site, F(2) is bonded in a water-like geometry to one Fe(1) and one Fe(2) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to two equivalent Fe(2) atoms.