MgMn6(O2F)4 crystallizes in the triclinic P-1 space group. Mg(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent F(2) atoms to form MgO4F2 octahedra that share corners with two equivalent Mn(1)O4F2 octahedra, edges with two equivalent Mn(2)O4F2 octahedra, and edges with two equivalent Mn(3)O4F2 octahedra. The corner-sharing octahedral tilt angles are 49°. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent F(1) atoms to form MnO4F2 octahedra that share corners with two equivalent Mg(1)O4F2 octahedra, corners with two equivalent Mn(3)O4F2 octahedra, and corners with six equivalent Mn(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 47-64°. In the second Mn site, Mn(2) is bonded to one O(2), one O(4), two equivalent O(3), one F(1), and one F(2) atom to form MnO4F2 octahedra that share corners with three equivalent Mn(1)O4F2 octahedra,  an edgeedge with one Mg(1)O4F2 octahedra,  an edgeedge with one Mn(2)O4F2 octahedra, and  an edgeedge with one Mn(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 52-64°. In the third Mn site, Mn(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(2) atoms to form MnO4F2 octahedra that share corners with two equivalent Mn(1)O4F2 octahedra, edges with two equivalent Mg(1)O4F2 octahedra, and edges with two equivalent Mn(2)O4F2 octahedra. The corner-sharing octahedral tilt angles are 47°. In the fourth Mn site, Mn(4) is bonded in a 5-coordinate geometry to one O(3), one O(4), two equivalent O(1), and one F(1) atom. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Mg(1), one Mn(3), and two equivalent Mn(4) atoms to form a mixture of distorted edge and corner-sharing OMgMn3 trigonal pyramids. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one Mn(3) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Mn(4) and two equivalent Mn(2) atoms. In the fourth O site, O(4) is bonded to one Mg(1), one Mn(1), one Mn(2), and one Mn(4) atom to form a mixture of distorted edge and corner-sharing OMgMn3 trigonal pyramids. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one Mn(4) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to one Mg(1), one Mn(2), and one Mn(3) atom.
MgMn6(O2F)4 crystallizes in the triclinic P-1 space group. Mg(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent F(2) atoms to form MgO4F2 octahedra that share corners with two equivalent Mn(1)O4F2 octahedra, edges with two equivalent Mn(2)O4F2 octahedra, and edges with two equivalent Mn(3)O4F2 octahedra. The corner-sharing octahedral tilt angles are 49°. Both Mg(1)-O(1) bond lengths are 2.06 Å. Both Mg(1)-O(4) bond lengths are 2.12 Å. Both Mg(1)-F(2) bond lengths are 1.96 Å. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent F(1) atoms to form MnO4F2 octahedra that share corners with two equivalent Mg(1)O4F2 octahedra, corners with two equivalent Mn(3)O4F2 octahedra, and corners with six equivalent Mn(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 47-64°. Both Mn(1)-O(2) bond lengths are 2.15 Å. Both Mn(1)-O(4) bond lengths are 2.03 Å. Both Mn(1)-F(1) bond lengths are 2.20 Å. In the second Mn site, Mn(2) is bonded to one O(2), one O(4), two equivalent O(3), one F(1), and one F(2) atom to form MnO4F2 octahedra that share corners with three equivalent Mn(1)O4F2 octahedra,  an edgeedge with one Mg(1)O4F2 octahedra,  an edgeedge with one Mn(2)O4F2 octahedra, and  an edgeedge with one Mn(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 52-64°. The Mn(2)-O(2) bond length is 1.97 Å. The Mn(2)-O(4) bond length is 2.18 Å. There is one shorter (1.91 Å) and one longer (1.95 Å) Mn(2)-O(3) bond length. The Mn(2)-F(1) bond length is 2.19 Å. The Mn(2)-F(2) bond length is 2.11 Å. In the third Mn site, Mn(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(2) atoms to form MnO4F2 octahedra that share corners with two equivalent Mn(1)O4F2 octahedra, edges with two equivalent Mg(1)O4F2 octahedra, and edges with two equivalent Mn(2)O4F2 octahedra. The corner-sharing octahedral tilt angles are 47°. Both Mn(3)-O(1) bond lengths are 2.15 Å. Both Mn(3)-O(2) bond lengths are 2.02 Å. Both Mn(3)-F(2) bond lengths are 2.11 Å. In the fourth Mn site, Mn(4) is bonded in a 5-coordinate geometry to one O(3), one O(4), two equivalent O(1), and one F(1) atom. The Mn(4)-O(3) bond length is 1.95 Å. The Mn(4)-O(4) bond length is 1.95 Å. There is one shorter (1.98 Å) and one longer (1.99 Å) Mn(4)-O(1) bond length. The Mn(4)-F(1) bond length is 1.97 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Mg(1), one Mn(3), and two equivalent Mn(4) atoms to form a mixture of distorted edge and corner-sharing OMgMn3 trigonal pyramids. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one Mn(3) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Mn(4) and two equivalent Mn(2) atoms. In the fourth O site, O(4) is bonded to one Mg(1), one Mn(1), one Mn(2), and one Mn(4) atom to form a mixture of distorted edge and corner-sharing OMgMn3 trigonal pyramids. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one Mn(4) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to one Mg(1), one Mn(2), and one Mn(3) atom.