MgMn6(O2F)4 crystallizes in the monoclinic Pm space group. Mg(1) is bonded to one O(1), one O(6), two equivalent O(3), and two equivalent F(3) atoms to form MgO4F2 octahedra that share corners with two equivalent Mn(2)O2F4 octahedra, corners with two equivalent Mn(3)O5F octahedra, corners with two equivalent Mn(1)O3F2 square pyramids, edges with two equivalent Mg(1)O4F2 octahedra,  a faceface with one Mn(2)O2F4 octahedra, and  a faceface with one Mn(3)O5F octahedra. The corner-sharing octahedral tilt angles range from 33-38°. There are six inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), two equivalent O(1), and two equivalent F(4) atoms to form MnO3F2 square pyramids that share corners with two equivalent Mg(1)O4F2 octahedra, corners with two equivalent Mn(2)O2F4 octahedra, corners with two equivalent Mn(3)O5F octahedra, corners with two equivalent Mn(6)O5F octahedra, and edges with two equivalent Mn(1)O3F2 square pyramids. The corner-sharing octahedral tilt angles range from 47-71°. In the second Mn site, Mn(2) is bonded to one O(1), one O(5), two equivalent F(1), and two equivalent F(3) atoms to form MnO2F4 octahedra that share corners with two equivalent Mg(1)O4F2 octahedra, corners with two equivalent Mn(1)O3F2 square pyramids, corners with two equivalent Mn(4)O3F2 square pyramids, edges with two equivalent Mn(2)O2F4 octahedra, and  a faceface with one Mg(1)O4F2 octahedra. The corner-sharing octahedral tilt angles are 38°. In the third Mn site, Mn(3) is bonded to one O(6), two equivalent O(2), two equivalent O(3), and one F(2) atom to form distorted MnO5F octahedra that share corners with two equivalent Mg(1)O4F2 octahedra, corners with two equivalent Mn(1)O3F2 square pyramids, corners with two equivalent Mn(4)O3F2 square pyramids, edges with two equivalent Mn(3)O5F octahedra, and  a faceface with one Mg(1)O4F2 octahedra. The corner-sharing octahedral tilt angles are 33°. In the fourth Mn site, Mn(4) is bonded to one O(4), two equivalent O(5), and two equivalent F(2) atoms to form MnO3F2 square pyramids that share corners with two equivalent Mn(2)O2F4 octahedra, corners with two equivalent Mn(3)O5F octahedra, corners with two equivalent Mn(6)O5F octahedra, and edges with two equivalent Mn(4)O3F2 square pyramids. The corner-sharing octahedral tilt angles range from 50-51°. In the fifth Mn site, Mn(5) is bonded in a 6-coordinate geometry to two equivalent O(6), two equivalent O(7), one F(1), and one F(3) atom. In the sixth Mn site, Mn(6) is bonded to one O(7), two equivalent O(4), two equivalent O(8), and one F(4) atom to form MnO5F octahedra that share corners with two equivalent Mn(1)O3F2 square pyramids, corners with two equivalent Mn(4)O3F2 square pyramids, and edges with two equivalent Mn(6)O5F octahedra. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Mg(1), one Mn(2), and two equivalent Mn(1) atoms to form distorted corner-sharing OMgMn3 tetrahedra. In the second O site, O(2) is bonded in a trigonal planar geometry to one Mn(1) and two equivalent Mn(3) atoms. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Mg(1) and two equivalent Mn(3) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Mn(4) and two equivalent Mn(6) atoms. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Mn(2) and two equivalent Mn(4) atoms. In the sixth O site, O(6) is bonded to one Mg(1), one Mn(3), and two equivalent Mn(5) atoms to form distorted corner-sharing OMgMn3 tetrahedra. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Mn(6) and two equivalent Mn(5) atoms. In the eighth O site, O(8) is bonded in a water-like geometry to two equivalent Mn(6) atoms. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Mn(5) and two equivalent Mn(2) atoms. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Mn(3) and two equivalent Mn(4) atoms. In the third F site, F(3) is bonded in a 5-coordinate geometry to two equivalent Mg(1), one Mn(5), and two equivalent Mn(2) atoms. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Mn(6) and two equivalent Mn(1) atoms.
MgMn6(O2F)4 crystallizes in the monoclinic Pm space group. Mg(1) is bonded to one O(1), one O(6), two equivalent O(3), and two equivalent F(3) atoms to form MgO4F2 octahedra that share corners with two equivalent Mn(2)O2F4 octahedra, corners with two equivalent Mn(3)O5F octahedra, corners with two equivalent Mn(1)O3F2 square pyramids, edges with two equivalent Mg(1)O4F2 octahedra,  a faceface with one Mn(2)O2F4 octahedra, and  a faceface with one Mn(3)O5F octahedra. The corner-sharing octahedral tilt angles range from 33-38°. The Mg(1)-O(1) bond length is 2.05 Å. The Mg(1)-O(6) bond length is 2.04 Å. Both Mg(1)-O(3) bond lengths are 2.07 Å. Both Mg(1)-F(3) bond lengths are 2.13 Å. There are six inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), two equivalent O(1), and two equivalent F(4) atoms to form MnO3F2 square pyramids that share corners with two equivalent Mg(1)O4F2 octahedra, corners with two equivalent Mn(2)O2F4 octahedra, corners with two equivalent Mn(3)O5F octahedra, corners with two equivalent Mn(6)O5F octahedra, and edges with two equivalent Mn(1)O3F2 square pyramids. The corner-sharing octahedral tilt angles range from 47-71°. The Mn(1)-O(2) bond length is 2.02 Å. Both Mn(1)-O(1) bond lengths are 1.98 Å. Both Mn(1)-F(4) bond lengths are 2.06 Å. In the second Mn site, Mn(2) is bonded to one O(1), one O(5), two equivalent F(1), and two equivalent F(3) atoms to form MnO2F4 octahedra that share corners with two equivalent Mg(1)O4F2 octahedra, corners with two equivalent Mn(1)O3F2 square pyramids, corners with two equivalent Mn(4)O3F2 square pyramids, edges with two equivalent Mn(2)O2F4 octahedra, and  a faceface with one Mg(1)O4F2 octahedra. The corner-sharing octahedral tilt angles are 38°. The Mn(2)-O(1) bond length is 2.21 Å. The Mn(2)-O(5) bond length is 2.03 Å. Both Mn(2)-F(1) bond lengths are 2.05 Å. Both Mn(2)-F(3) bond lengths are 2.26 Å. In the third Mn site, Mn(3) is bonded to one O(6), two equivalent O(2), two equivalent O(3), and one F(2) atom to form distorted MnO5F octahedra that share corners with two equivalent Mg(1)O4F2 octahedra, corners with two equivalent Mn(1)O3F2 square pyramids, corners with two equivalent Mn(4)O3F2 square pyramids, edges with two equivalent Mn(3)O5F octahedra, and  a faceface with one Mg(1)O4F2 octahedra. The corner-sharing octahedral tilt angles are 33°. The Mn(3)-O(6) bond length is 2.35 Å. Both Mn(3)-O(2) bond lengths are 1.92 Å. Both Mn(3)-O(3) bond lengths are 2.04 Å. The Mn(3)-F(2) bond length is 2.39 Å. In the fourth Mn site, Mn(4) is bonded to one O(4), two equivalent O(5), and two equivalent F(2) atoms to form MnO3F2 square pyramids that share corners with two equivalent Mn(2)O2F4 octahedra, corners with two equivalent Mn(3)O5F octahedra, corners with two equivalent Mn(6)O5F octahedra, and edges with two equivalent Mn(4)O3F2 square pyramids. The corner-sharing octahedral tilt angles range from 50-51°. The Mn(4)-O(4) bond length is 2.00 Å. Both Mn(4)-O(5) bond lengths are 1.93 Å. Both Mn(4)-F(2) bond lengths are 2.02 Å. In the fifth Mn site, Mn(5) is bonded in a 6-coordinate geometry to two equivalent O(6), two equivalent O(7), one F(1), and one F(3) atom. Both Mn(5)-O(6) bond lengths are 1.95 Å. Both Mn(5)-O(7) bond lengths are 1.93 Å. The Mn(5)-F(1) bond length is 2.21 Å. The Mn(5)-F(3) bond length is 2.66 Å. In the sixth Mn site, Mn(6) is bonded to one O(7), two equivalent O(4), two equivalent O(8), and one F(4) atom to form MnO5F octahedra that share corners with two equivalent Mn(1)O3F2 square pyramids, corners with two equivalent Mn(4)O3F2 square pyramids, and edges with two equivalent Mn(6)O5F octahedra. The Mn(6)-O(7) bond length is 1.89 Å. Both Mn(6)-O(4) bond lengths are 1.97 Å. Both Mn(6)-O(8) bond lengths are 1.89 Å. The Mn(6)-F(4) bond length is 2.13 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Mg(1), one Mn(2), and two equivalent Mn(1) atoms to form distorted corner-sharing OMgMn3 tetrahedra. In the second O site, O(2) is bonded in a trigonal planar geometry to one Mn(1) and two equivalent Mn(3) atoms. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Mg(1) and two equivalent Mn(3) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Mn(4) and two equivalent Mn(6) atoms. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Mn(2) and two equivalent Mn(4) atoms. In the sixth O site, O(6) is bonded to one Mg(1), one Mn(3), and two equivalent Mn(5) atoms to form distorted corner-sharing OMgMn3 tetrahedra. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Mn(6) and two equivalent Mn(5) atoms. In the eighth O site, O(8) is bonded in a water-like geometry to two equivalent Mn(6) atoms. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Mn(5) and two equivalent Mn(2) atoms. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Mn(3) and two equivalent Mn(4) atoms. In the third F site, F(3) is bonded in a 5-coordinate geometry to two equivalent Mg(1), one Mn(5), and two equivalent Mn(2) atoms. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to one Mn(6) and two equivalent Mn(1) atoms.