MgMn6(O2F)4 crystallizes in the monoclinic P2/m space group. Mg(1) is bonded to four equivalent O(3) and two equivalent F(2) atoms to form MgO4F2 octahedra that share corners with four equivalent Mn(1)O3F2 square pyramids, corners with four equivalent Mn(3)O5 square pyramids, edges with two equivalent Mg(1)O4F2 octahedra, and edges with two equivalent Mn(3)O5 square pyramids. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), two equivalent O(1), and two equivalent F(2) atoms to form distorted 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)O5 square pyramids, and edges with two equivalent Mn(1)O3F2 square pyramids. The corner-sharing octahedral tilt angles range from 53-68°. In the second Mn site, Mn(2) is bonded to two equivalent O(1) and four equivalent F(1) atoms to form MnO2F4 octahedra that share corners with four equivalent Mn(4)O4F2 octahedra, corners with four equivalent Mn(1)O3F2 square pyramids, and edges with two equivalent Mn(2)O2F4 octahedra. The corner-sharing octahedral tilt angles are 48°. In the third Mn site, Mn(3) is bonded to one O(4), two equivalent O(2), and two equivalent O(3) atoms to form distorted MnO5 square pyramids that share corners with two equivalent Mg(1)O4F2 octahedra, corners with two equivalent Mn(4)O4F2 octahedra, corners with two equivalent Mn(1)O3F2 square pyramids,  an edgeedge with one Mg(1)O4F2 octahedra, and edges with two equivalent Mn(3)O5 square pyramids. The corner-sharing octahedral tilt angles range from 27-51°. In the fourth Mn site, Mn(4) is bonded to four equivalent O(4) and two equivalent F(1) atoms to form MnO4F2 octahedra that share corners with four equivalent Mn(2)O2F4 octahedra, corners with four equivalent Mn(3)O5 square pyramids, and edges with two equivalent Mn(4)O4F2 octahedra. The corner-sharing octahedral tilt angles are 48°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Mn(2) and two equivalent Mn(1) atoms. 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 4-coordinate geometry to two equivalent Mg(1) and two equivalent Mn(3) atoms. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Mn(3) and two equivalent Mn(4) atoms. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Mn(4) and two equivalent Mn(2) atoms. In the second F site, F(2) is bonded in a trigonal non-coplanar geometry to one Mg(1) and two equivalent Mn(1) atoms.
MgMn6(O2F)4 crystallizes in the monoclinic P2/m space group. Mg(1) is bonded to four equivalent O(3) and two equivalent F(2) atoms to form MgO4F2 octahedra that share corners with four equivalent Mn(1)O3F2 square pyramids, corners with four equivalent Mn(3)O5 square pyramids, edges with two equivalent Mg(1)O4F2 octahedra, and edges with two equivalent Mn(3)O5 square pyramids. All Mg(1)-O(3) bond lengths are 2.13 Å. Both Mg(1)-F(2) bond lengths are 2.02 Å. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), two equivalent O(1), and two equivalent F(2) atoms to form distorted 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)O5 square pyramids, and edges with two equivalent Mn(1)O3F2 square pyramids. The corner-sharing octahedral tilt angles range from 53-68°. The Mn(1)-O(2) bond length is 2.05 Å. Both Mn(1)-O(1) bond lengths are 1.93 Å. Both Mn(1)-F(2) bond lengths are 2.11 Å. In the second Mn site, Mn(2) is bonded to two equivalent O(1) and four equivalent F(1) atoms to form MnO2F4 octahedra that share corners with four equivalent Mn(4)O4F2 octahedra, corners with four equivalent Mn(1)O3F2 square pyramids, and edges with two equivalent Mn(2)O2F4 octahedra. The corner-sharing octahedral tilt angles are 48°. Both Mn(2)-O(1) bond lengths are 1.92 Å. All Mn(2)-F(1) bond lengths are 2.03 Å. In the third Mn site, Mn(3) is bonded to one O(4), two equivalent O(2), and two equivalent O(3) atoms to form distorted MnO5 square pyramids that share corners with two equivalent Mg(1)O4F2 octahedra, corners with two equivalent Mn(4)O4F2 octahedra, corners with two equivalent Mn(1)O3F2 square pyramids,  an edgeedge with one Mg(1)O4F2 octahedra, and edges with two equivalent Mn(3)O5 square pyramids. The corner-sharing octahedral tilt angles range from 27-51°. The Mn(3)-O(4) bond length is 1.97 Å. Both Mn(3)-O(2) bond lengths are 1.94 Å. Both Mn(3)-O(3) bond lengths are 2.06 Å. In the fourth Mn site, Mn(4) is bonded to four equivalent O(4) and two equivalent F(1) atoms to form MnO4F2 octahedra that share corners with four equivalent Mn(2)O2F4 octahedra, corners with four equivalent Mn(3)O5 square pyramids, and edges with two equivalent Mn(4)O4F2 octahedra. The corner-sharing octahedral tilt angles are 48°. All Mn(4)-O(4) bond lengths are 1.96 Å. Both Mn(4)-F(1) bond lengths are 2.22 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Mn(2) and two equivalent Mn(1) atoms. 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 4-coordinate geometry to two equivalent Mg(1) and two equivalent Mn(3) atoms. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Mn(3) and two equivalent Mn(4) atoms. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Mn(4) and two equivalent Mn(2) atoms. In the second F site, F(2) is bonded in a trigonal non-coplanar geometry to one Mg(1) and two equivalent Mn(1) atoms.