MgFe12(OF)12 crystallizes in the triclinic P1 space group. Mg(1) is bonded in a 7-coordinate geometry to one O(9), two equivalent F(3), two equivalent F(5), and two equivalent F(7) atoms. There are twelve inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(3), two equivalent O(12), two equivalent O(2), and one F(9) atom to form FeO5F octahedra that share corners with two equivalent Fe(12)O3F3 octahedra, corners with two equivalent Fe(6)O3F3 octahedra, edges with two equivalent Fe(1)O5F octahedra, and edges with two equivalent Fe(4)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles range from 45-54°. In the second Fe site, Fe(2) is bonded to one O(4), two equivalent O(1), one F(8), and two equivalent F(11) atoms to form FeO3F3 octahedra that share corners with two equivalent Fe(11)O3F3 octahedra, corners with two equivalent Fe(5)O3F3 octahedra, corners with two equivalent Fe(4)O4F trigonal bipyramids, and edges with two equivalent Fe(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 48-58°. In the third Fe site, Fe(3) is bonded to one F(10), one F(2), two equivalent F(1), and two equivalent F(12) atoms to form FeF6 octahedra that share corners with two equivalent Fe(11)O3F3 octahedra, corners with two equivalent Fe(12)O3F3 octahedra, corners with two equivalent Fe(5)O3F3 octahedra, corners with two equivalent Fe(6)O3F3 octahedra, and edges with two equivalent Fe(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-50°. In the fourth Fe site, Fe(4) is bonded to one O(1), one O(12), two equivalent O(3), and one F(3) atom to form FeO4F trigonal bipyramids that share corners with two equivalent Fe(2)O3F3 octahedra, corners with two equivalent Fe(4)O4F trigonal bipyramids, and edges with two equivalent Fe(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 42-63°. In the fifth Fe site, Fe(5) is bonded to one O(6), two equivalent O(4), one F(1), and two equivalent F(4) atoms to form FeO3F3 octahedra that share corners with two equivalent Fe(3)F6 octahedra, corners with two equivalent Fe(2)O3F3 octahedra, corners with two equivalent Fe(9)O3F3 octahedra, corners with two equivalent Fe(7)O3F tetrahedra, and edges with two equivalent Fe(5)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 45-58°. In the sixth Fe site, Fe(6) is bonded to one O(2), two equivalent O(5), one F(6), and two equivalent F(2) atoms to form distorted FeO3F3 octahedra that share corners with two equivalent Fe(3)F6 octahedra, corners with two equivalent Fe(9)O3F3 octahedra, corners with two equivalent Fe(8)O4F2 octahedra, corners with two equivalent Fe(1)O5F octahedra, and edges with two equivalent Fe(6)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 47-54°. In the seventh Fe site, Fe(7) is bonded to one O(10), two equivalent O(6), and one F(7) atom to form distorted FeO3F tetrahedra that share corners with two equivalent Fe(11)O3F3 octahedra, corners with two equivalent Fe(5)O3F3 octahedra, and corners with two equivalent Fe(7)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 52-67°. In the eighth Fe site, Fe(8) is bonded to one O(5), one O(9), two equivalent O(7), and two equivalent F(5) atoms to form distorted FeO4F2 octahedra that share corners with two equivalent Fe(12)O3F3 octahedra, corners with two equivalent Fe(6)O3F3 octahedra, and edges with two equivalent Fe(8)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 52-56°. In the ninth Fe site, Fe(9) is bonded to one O(11), two equivalent O(8), one F(4), and two equivalent F(6) atoms to form a mixture of edge and corner-sharing FeO3F3 octahedra. The corner-sharing octahedral tilt angles range from 45-54°. In the tenth Fe site, Fe(10) is bonded in a 6-coordinate geometry to one O(12), two equivalent O(9), one F(7), and two equivalent F(8) atoms. In the eleventh Fe site, Fe(11) is bonded to one O(8), two equivalent O(10), one F(11), and two equivalent F(10) atoms to form FeO3F3 octahedra that share corners with two equivalent Fe(3)F6 octahedra, corners with two equivalent Fe(2)O3F3 octahedra, corners with two equivalent Fe(9)O3F3 octahedra, corners with two equivalent Fe(7)O3F tetrahedra, and edges with two equivalent Fe(11)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 46-54°. In the twelfth Fe site, Fe(12) is bonded to one O(7), two equivalent O(11), one F(12), and two equivalent F(9) atoms to form FeO3F3 octahedra that share corners with two equivalent Fe(3)F6 octahedra, corners with two equivalent Fe(9)O3F3 octahedra, corners with two equivalent Fe(8)O4F2 octahedra, corners with two equivalent Fe(1)O5F octahedra, and edges with two equivalent Fe(12)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 45-56°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Fe(4) and two equivalent Fe(2) atoms. In the second O site, O(2) is bonded in a trigonal planar geometry to one Fe(6) and two equivalent Fe(1) atoms. In the third O site, O(3) is bonded in a trigonal non-coplanar geometry to one Fe(1) and two equivalent Fe(4) atoms. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Fe(2) and two equivalent Fe(5) atoms. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Fe(8) and two equivalent Fe(6) atoms. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Fe(5) and two equivalent Fe(7) atoms. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Fe(12) and two equivalent Fe(8) atoms. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Fe(11) and two equivalent Fe(9) atoms. In the ninth O site, O(9) is bonded to one Mg(1), one Fe(8), and two equivalent Fe(10) atoms to form corner-sharing OMgFe3 tetrahedra. In the tenth O site, O(10) is bonded in a trigonal non-coplanar geometry to one Fe(7) and two equivalent Fe(11) atoms. In the eleventh O site, O(11) is bonded in a trigonal planar geometry to one Fe(9) and two equivalent Fe(12) atoms. In the twelfth O site, O(12) is bonded in a rectangular see-saw-like geometry to one Fe(10), one Fe(4), and two equivalent Fe(1) atoms. There are twelve inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Fe(5) and two equivalent Fe(3) atoms. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Fe(3) and two equivalent Fe(6) atoms. In the third F site, F(3) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Mg(1) and one Fe(4) atom. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Fe(9) and two equivalent Fe(5) atoms. In the fifth F site, F(5) is bonded in a distorted square co-planar geometry to two equivalent Mg(1) and two equivalent Fe(8) atoms. In the sixth F site, F(6) is bonded in a distorted T-shaped geometry to one Fe(6) and two equivalent Fe(9) atoms. In the seventh F site, F(7) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Mg(1), one Fe(10), and one Fe(7) atom. In the eighth F site, F(8) is bonded in a distorted trigonal planar geometry to one Fe(2) and two equivalent Fe(10) atoms. In the ninth F site, F(9) is bonded in a distorted T-shaped geometry to one Fe(1) and two equivalent Fe(12) atoms. In the tenth F site, F(10) is bonded in a distorted T-shaped geometry to one Fe(3) and two equivalent Fe(11) atoms. In the eleventh F site, F(11) is bonded in a distorted trigonal planar geometry to one Fe(11) and two equivalent Fe(2) atoms. In the twelfth F site, F(12) is bonded in a distorted trigonal planar geometry to one Fe(12) and two equivalent Fe(3) atoms.
MgFe12(OF)12 crystallizes in the triclinic P1 space group. Mg(1) is bonded in a 7-coordinate geometry to one O(9), two equivalent F(3), two equivalent F(5), and two equivalent F(7) atoms. The Mg(1)-O(9) bond length is 2.21 Å. There is one shorter (2.04 Å) and one longer (2.24 Å) Mg(1)-F(3) bond length. There is one shorter (2.08 Å) and one longer (2.41 Å) Mg(1)-F(5) bond length. There is one shorter (2.07 Å) and one longer (2.20 Å) Mg(1)-F(7) bond length. There are twelve inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(3), two equivalent O(12), two equivalent O(2), and one F(9) atom to form FeO5F octahedra that share corners with two equivalent Fe(12)O3F3 octahedra, corners with two equivalent Fe(6)O3F3 octahedra, edges with two equivalent Fe(1)O5F octahedra, and edges with two equivalent Fe(4)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles range from 45-54°. The Fe(1)-O(3) bond length is 2.02 Å. There is one shorter (2.16 Å) and one longer (2.19 Å) Fe(1)-O(12) bond length. Both Fe(1)-O(2) bond lengths are 1.97 Å. The Fe(1)-F(9) bond length is 2.09 Å. In the second Fe site, Fe(2) is bonded to one O(4), two equivalent O(1), one F(8), and two equivalent F(11) atoms to form FeO3F3 octahedra that share corners with two equivalent Fe(11)O3F3 octahedra, corners with two equivalent Fe(5)O3F3 octahedra, corners with two equivalent Fe(4)O4F trigonal bipyramids, and edges with two equivalent Fe(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 48-58°. The Fe(2)-O(4) bond length is 1.90 Å. There is one shorter (1.96 Å) and one longer (1.98 Å) Fe(2)-O(1) bond length. The Fe(2)-F(8) bond length is 2.29 Å. There is one shorter (2.05 Å) and one longer (2.12 Å) Fe(2)-F(11) bond length. In the third Fe site, Fe(3) is bonded to one F(10), one F(2), two equivalent F(1), and two equivalent F(12) atoms to form FeF6 octahedra that share corners with two equivalent Fe(11)O3F3 octahedra, corners with two equivalent Fe(12)O3F3 octahedra, corners with two equivalent Fe(5)O3F3 octahedra, corners with two equivalent Fe(6)O3F3 octahedra, and edges with two equivalent Fe(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-50°. The Fe(3)-F(10) bond length is 2.13 Å. The Fe(3)-F(2) bond length is 2.13 Å. There is one shorter (2.06 Å) and one longer (2.08 Å) Fe(3)-F(1) bond length. There is one shorter (2.09 Å) and one longer (2.11 Å) Fe(3)-F(12) bond length. In the fourth Fe site, Fe(4) is bonded to one O(1), one O(12), two equivalent O(3), and one F(3) atom to form FeO4F trigonal bipyramids that share corners with two equivalent Fe(2)O3F3 octahedra, corners with two equivalent Fe(4)O4F trigonal bipyramids, and edges with two equivalent Fe(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 42-63°. The Fe(4)-O(1) bond length is 1.90 Å. The Fe(4)-O(12) bond length is 2.19 Å. There is one shorter (1.88 Å) and one longer (1.89 Å) Fe(4)-O(3) bond length. The Fe(4)-F(3) bond length is 2.08 Å. In the fifth Fe site, Fe(5) is bonded to one O(6), two equivalent O(4), one F(1), and two equivalent F(4) atoms to form FeO3F3 octahedra that share corners with two equivalent Fe(3)F6 octahedra, corners with two equivalent Fe(2)O3F3 octahedra, corners with two equivalent Fe(9)O3F3 octahedra, corners with two equivalent Fe(7)O3F tetrahedra, and edges with two equivalent Fe(5)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 45-58°. The Fe(5)-O(6) bond length is 1.88 Å. There is one shorter (1.96 Å) and one longer (1.98 Å) Fe(5)-O(4) bond length. The Fe(5)-F(1) bond length is 2.12 Å. There is one shorter (2.17 Å) and one longer (2.18 Å) Fe(5)-F(4) bond length. In the sixth Fe site, Fe(6) is bonded to one O(2), two equivalent O(5), one F(6), and two equivalent F(2) atoms to form distorted FeO3F3 octahedra that share corners with two equivalent Fe(3)F6 octahedra, corners with two equivalent Fe(9)O3F3 octahedra, corners with two equivalent Fe(8)O4F2 octahedra, corners with two equivalent Fe(1)O5F octahedra, and edges with two equivalent Fe(6)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 47-54°. The Fe(6)-O(2) bond length is 1.95 Å. Both Fe(6)-O(5) bond lengths are 1.95 Å. The Fe(6)-F(6) bond length is 2.27 Å. Both Fe(6)-F(2) bond lengths are 2.12 Å. In the seventh Fe site, Fe(7) is bonded to one O(10), two equivalent O(6), and one F(7) atom to form distorted FeO3F tetrahedra that share corners with two equivalent Fe(11)O3F3 octahedra, corners with two equivalent Fe(5)O3F3 octahedra, and corners with two equivalent Fe(7)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 52-67°. The Fe(7)-O(10) bond length is 1.96 Å. There is one shorter (1.94 Å) and one longer (1.95 Å) Fe(7)-O(6) bond length. The Fe(7)-F(7) bond length is 2.35 Å. In the eighth Fe site, Fe(8) is bonded to one O(5), one O(9), two equivalent O(7), and two equivalent F(5) atoms to form distorted FeO4F2 octahedra that share corners with two equivalent Fe(12)O3F3 octahedra, corners with two equivalent Fe(6)O3F3 octahedra, and edges with two equivalent Fe(8)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 52-56°. The Fe(8)-O(5) bond length is 1.95 Å. The Fe(8)-O(9) bond length is 2.09 Å. There is one shorter (1.91 Å) and one longer (1.92 Å) Fe(8)-O(7) bond length. There is one shorter (2.16 Å) and one longer (2.34 Å) Fe(8)-F(5) bond length. In the ninth Fe site, Fe(9) is bonded to one O(11), two equivalent O(8), one F(4), and two equivalent F(6) atoms to form a mixture of edge and corner-sharing FeO3F3 octahedra. The corner-sharing octahedral tilt angles range from 45-54°. The Fe(9)-O(11) bond length is 1.98 Å. There is one shorter (1.95 Å) and one longer (1.96 Å) Fe(9)-O(8) bond length. The Fe(9)-F(4) bond length is 2.14 Å. There is one shorter (2.12 Å) and one longer (2.15 Å) Fe(9)-F(6) bond length. In the tenth Fe site, Fe(10) is bonded in a 6-coordinate geometry to one O(12), two equivalent O(9), one F(7), and two equivalent F(8) atoms. The Fe(10)-O(12) bond length is 1.95 Å. There is one shorter (1.97 Å) and one longer (1.98 Å) Fe(10)-O(9) bond length. The Fe(10)-F(7) bond length is 2.44 Å. There is one shorter (2.05 Å) and one longer (2.21 Å) Fe(10)-F(8) bond length. In the eleventh Fe site, Fe(11) is bonded to one O(8), two equivalent O(10), one F(11), and two equivalent F(10) atoms to form FeO3F3 octahedra that share corners with two equivalent Fe(3)F6 octahedra, corners with two equivalent Fe(2)O3F3 octahedra, corners with two equivalent Fe(9)O3F3 octahedra, corners with two equivalent Fe(7)O3F tetrahedra, and edges with two equivalent Fe(11)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 46-54°. The Fe(11)-O(8) bond length is 1.96 Å. There is one shorter (1.92 Å) and one longer (1.93 Å) Fe(11)-O(10) bond length. The Fe(11)-F(11) bond length is 2.18 Å. There is one shorter (2.14 Å) and one longer (2.15 Å) Fe(11)-F(10) bond length. In the twelfth Fe site, Fe(12) is bonded to one O(7), two equivalent O(11), one F(12), and two equivalent F(9) atoms to form FeO3F3 octahedra that share corners with two equivalent Fe(3)F6 octahedra, corners with two equivalent Fe(9)O3F3 octahedra, corners with two equivalent Fe(8)O4F2 octahedra, corners with two equivalent Fe(1)O5F octahedra, and edges with two equivalent Fe(12)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 45-56°. The Fe(12)-O(7) bond length is 1.94 Å. Both Fe(12)-O(11) bond lengths are 1.93 Å. The Fe(12)-F(12) bond length is 2.07 Å. There is one shorter (2.15 Å) and one longer (2.18 Å) Fe(12)-F(9) bond length. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Fe(4) and two equivalent Fe(2) atoms. In the second O site, O(2) is bonded in a trigonal planar geometry to one Fe(6) and two equivalent Fe(1) atoms. In the third O site, O(3) is bonded in a trigonal non-coplanar geometry to one Fe(1) and two equivalent Fe(4) atoms. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Fe(2) and two equivalent Fe(5) atoms. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Fe(8) and two equivalent Fe(6) atoms. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Fe(5) and two equivalent Fe(7) atoms. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Fe(12) and two equivalent Fe(8) atoms. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Fe(11) and two equivalent Fe(9) atoms. In the ninth O site, O(9) is bonded to one Mg(1), one Fe(8), and two equivalent Fe(10) atoms to form corner-sharing OMgFe3 tetrahedra. In the tenth O site, O(10) is bonded in a trigonal non-coplanar geometry to one Fe(7) and two equivalent Fe(11) atoms. In the eleventh O site, O(11) is bonded in a trigonal planar geometry to one Fe(9) and two equivalent Fe(12) atoms. In the twelfth O site, O(12) is bonded in a rectangular see-saw-like geometry to one Fe(10), one Fe(4), and two equivalent Fe(1) atoms. There are twelve inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Fe(5) and two equivalent Fe(3) atoms. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Fe(3) and two equivalent Fe(6) atoms. In the third F site, F(3) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Mg(1) and one Fe(4) atom. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Fe(9) and two equivalent Fe(5) atoms. In the fifth F site, F(5) is bonded in a distorted square co-planar geometry to two equivalent Mg(1) and two equivalent Fe(8) atoms. In the sixth F site, F(6) is bonded in a distorted T-shaped geometry to one Fe(6) and two equivalent Fe(9) atoms. In the seventh F site, F(7) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Mg(1), one Fe(10), and one Fe(7) atom. In the eighth F site, F(8) is bonded in a distorted trigonal planar geometry to one Fe(2) and two equivalent Fe(10) atoms. In the ninth F site, F(9) is bonded in a distorted T-shaped geometry to one Fe(1) and two equivalent Fe(12) atoms. In the tenth F site, F(10) is bonded in a distorted T-shaped geometry to one Fe(3) and two equivalent Fe(11) atoms. In the eleventh F site, F(11) is bonded in a distorted trigonal planar geometry to one Fe(11) and two equivalent Fe(2) atoms. In the twelfth F site, F(12) is bonded in a distorted trigonal planar geometry to one Fe(12) and two equivalent Fe(3) atoms.