MgFe6(OF)6 crystallizes in the triclinic P1 space group. Mg(1) is bonded in a 5-coordinate geometry to one O(6), two equivalent O(5), one F(5), and two equivalent F(6) atoms. There are six inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(2), two equivalent O(1), and one F(6) atom to form distorted FeO3F tetrahedra that share corners with four equivalent Fe(2)O3F2 square pyramids and corners with two equivalent Fe(1)O3F tetrahedra. In the second Fe site, Fe(2) is bonded to one O(1), two equivalent O(2), and two equivalent F(1) atoms to form distorted FeO3F2 square pyramids that share corners with two equivalent Fe(3)O2F4 octahedra, corners with four equivalent Fe(1)O3F tetrahedra, and edges with two equivalent Fe(2)O3F2 square pyramids. The corner-sharing octahedral tilt angles range from 44-45°. In the third Fe site, Fe(3) is bonded to two equivalent O(3), one F(1), one F(3), and two equivalent F(2) atoms to form FeO2F4 octahedra that share corners with four equivalent Fe(4)O3F3 octahedra, corners with two equivalent Fe(2)O3F2 square pyramids, and edges with two equivalent Fe(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 46-53°. In the fourth Fe site, Fe(4) is bonded to one O(3), two equivalent O(4), one F(4), and two equivalent F(3) atoms to form FeO3F3 octahedra that share corners with four equivalent Fe(3)O2F4 octahedra, corners with four equivalent Fe(5)O4F2 octahedra, and edges with two equivalent Fe(4)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 46-55°. In the fifth Fe site, Fe(5) is bonded to one O(4), one O(6), two equivalent O(5), and two equivalent F(4) atoms to form FeO4F2 octahedra that share corners with four equivalent Fe(4)O3F3 octahedra, corners with four equivalent Fe(6)O3F2 square pyramids, and edges with two equivalent Fe(5)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. In the sixth Fe site, Fe(6) is bonded to one O(5), two equivalent O(6), and two equivalent F(5) atoms to form distorted FeO3F2 square pyramids that share corners with four equivalent Fe(5)O4F2 octahedra and edges with two equivalent Fe(6)O3F2 square pyramids. The corner-sharing octahedral tilt angles range from 54-59°. There are six 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 trigonal planar geometry to one Fe(1) and two equivalent Fe(2) atoms. In the third O site, O(3) is bonded in a trigonal planar geometry to one Fe(4) and two equivalent Fe(3) atoms. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Fe(5) and two equivalent Fe(4) atoms. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to two equivalent Mg(1), one Fe(6), and two equivalent Fe(5) atoms. In the sixth O site, O(6) is bonded to one Mg(1), one Fe(5), and two equivalent Fe(6) atoms to form distorted corner-sharing OMgFe3 tetrahedra. There are six inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Fe(3) and two equivalent Fe(2) atoms. In the second F site, F(2) is bonded in a water-like geometry to two equivalent Fe(3) atoms. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one Fe(3) and two equivalent Fe(4) atoms. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Fe(4) and two equivalent Fe(5) atoms. In the fifth F site, F(5) is bonded in a distorted trigonal non-coplanar geometry to one Mg(1) and two equivalent Fe(6) atoms. In the sixth F site, F(6) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Mg(1) and one Fe(1) atom.
MgFe6(OF)6 crystallizes in the triclinic P1 space group. Mg(1) is bonded in a 5-coordinate geometry to one O(6), two equivalent O(5), one F(5), and two equivalent F(6) atoms. The Mg(1)-O(6) bond length is 1.99 Å. There is one shorter (2.22 Å) and one longer (2.64 Å) Mg(1)-O(5) bond length. The Mg(1)-F(5) bond length is 1.92 Å. There is one shorter (1.96 Å) and one longer (1.99 Å) Mg(1)-F(6) bond length. There are six inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(2), two equivalent O(1), and one F(6) atom to form distorted FeO3F tetrahedra that share corners with four equivalent Fe(2)O3F2 square pyramids and corners with two equivalent Fe(1)O3F tetrahedra. The Fe(1)-O(2) bond length is 1.96 Å. There is one shorter (1.94 Å) and one longer (1.96 Å) Fe(1)-O(1) bond length. The Fe(1)-F(6) bond length is 2.28 Å. In the second Fe site, Fe(2) is bonded to one O(1), two equivalent O(2), and two equivalent F(1) atoms to form distorted FeO3F2 square pyramids that share corners with two equivalent Fe(3)O2F4 octahedra, corners with four equivalent Fe(1)O3F tetrahedra, and edges with two equivalent Fe(2)O3F2 square pyramids. The corner-sharing octahedral tilt angles range from 44-45°. The Fe(2)-O(1) bond length is 1.85 Å. There is one shorter (1.91 Å) and one longer (1.92 Å) Fe(2)-O(2) bond length. There is one shorter (2.20 Å) and one longer (2.23 Å) Fe(2)-F(1) bond length. In the third Fe site, Fe(3) is bonded to two equivalent O(3), one F(1), one F(3), and two equivalent F(2) atoms to form FeO2F4 octahedra that share corners with four equivalent Fe(4)O3F3 octahedra, corners with two equivalent Fe(2)O3F2 square pyramids, and edges with two equivalent Fe(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 46-53°. There is one shorter (1.96 Å) and one longer (1.97 Å) Fe(3)-O(3) bond length. The Fe(3)-F(1) bond length is 2.05 Å. The Fe(3)-F(3) bond length is 2.16 Å. There is one shorter (2.04 Å) and one longer (2.06 Å) Fe(3)-F(2) bond length. In the fourth Fe site, Fe(4) is bonded to one O(3), two equivalent O(4), one F(4), and two equivalent F(3) atoms to form FeO3F3 octahedra that share corners with four equivalent Fe(3)O2F4 octahedra, corners with four equivalent Fe(5)O4F2 octahedra, and edges with two equivalent Fe(4)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 46-55°. The Fe(4)-O(3) bond length is 1.97 Å. Both Fe(4)-O(4) bond lengths are 1.94 Å. The Fe(4)-F(4) bond length is 2.29 Å. Both Fe(4)-F(3) bond lengths are 2.17 Å. In the fifth Fe site, Fe(5) is bonded to one O(4), one O(6), two equivalent O(5), and two equivalent F(4) atoms to form FeO4F2 octahedra that share corners with four equivalent Fe(4)O3F3 octahedra, corners with four equivalent Fe(6)O3F2 square pyramids, and edges with two equivalent Fe(5)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. The Fe(5)-O(4) bond length is 2.03 Å. The Fe(5)-O(6) bond length is 1.97 Å. There is one shorter (2.03 Å) and one longer (2.04 Å) Fe(5)-O(5) bond length. There is one shorter (2.10 Å) and one longer (2.17 Å) Fe(5)-F(4) bond length. In the sixth Fe site, Fe(6) is bonded to one O(5), two equivalent O(6), and two equivalent F(5) atoms to form distorted FeO3F2 square pyramids that share corners with four equivalent Fe(5)O4F2 octahedra and edges with two equivalent Fe(6)O3F2 square pyramids. The corner-sharing octahedral tilt angles range from 54-59°. The Fe(6)-O(5) bond length is 2.01 Å. There is one shorter (2.00 Å) and one longer (2.04 Å) Fe(6)-O(6) bond length. There is one shorter (2.17 Å) and one longer (2.23 Å) Fe(6)-F(5) bond length. There are six 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 trigonal planar geometry to one Fe(1) and two equivalent Fe(2) atoms. In the third O site, O(3) is bonded in a trigonal planar geometry to one Fe(4) and two equivalent Fe(3) atoms. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Fe(5) and two equivalent Fe(4) atoms. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to two equivalent Mg(1), one Fe(6), and two equivalent Fe(5) atoms. In the sixth O site, O(6) is bonded to one Mg(1), one Fe(5), and two equivalent Fe(6) atoms to form distorted corner-sharing OMgFe3 tetrahedra. There are six inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Fe(3) and two equivalent Fe(2) atoms. In the second F site, F(2) is bonded in a water-like geometry to two equivalent Fe(3) atoms. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one Fe(3) and two equivalent Fe(4) atoms. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Fe(4) and two equivalent Fe(5) atoms. In the fifth F site, F(5) is bonded in a distorted trigonal non-coplanar geometry to one Mg(1) and two equivalent Fe(6) atoms. In the sixth F site, F(6) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Mg(1) and one Fe(1) atom.