MgMn6(OF)6 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(2), one O(3), one O(4), one F(2), one F(4), and one F(5) atom to form MgO3F3 octahedra that share  an edgeedge with one Mn(6)O2F4 octahedra,  an edgeedge with one Mn(5)O3F3 octahedra, and edges with two equivalent Mn(4)O3F3 octahedra. There are six inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(5), one F(3), and one F(6) atom. In the second Mn site, Mn(2) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), one O(6), one F(1), and one F(4) atom. In the third Mn site, Mn(3) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(4), one O(5), one F(3), and one F(6) atom. In the fourth Mn site, Mn(4) is bonded to one O(2), one O(4), one O(6), one F(1), one F(2), and one F(5) atom to form MnO3F3 octahedra that share  an edgeedge with one Mn(6)O2F4 octahedra,  an edgeedge with one Mn(5)O3F3 octahedra, and edges with two equivalent Mg(1)O3F3 octahedra. In the fifth Mn site, Mn(5) is bonded to one O(1), one O(3), one O(5), one F(1), one F(5), and one F(6) atom to form distorted MnO3F3 octahedra that share  an edgeedge with one Mg(1)O3F3 octahedra,  an edgeedge with one Mn(6)O2F4 octahedra, and  an edgeedge with one Mn(4)O3F3 octahedra. In the sixth Mn site, Mn(6) is bonded to one O(1), one O(6), one F(2), one F(3), one F(4), and one F(6) atom to form MnO2F4 octahedra that share  an edgeedge with one Mg(1)O3F3 octahedra,  an edgeedge with one Mn(4)O3F3 octahedra, and  an edgeedge with one Mn(5)O3F3 octahedra. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Mn(1), one Mn(3), one Mn(5), and one Mn(6) atom to form OMn4 tetrahedra that share  a cornercorner with one O(2)MgMn3 tetrahedra,  a cornercorner with one O(4)MgMn3 tetrahedra, and edges with two equivalent F(6)Mn4 trigonal pyramids. In the second O site, O(2) is bonded to one Mg(1), one Mn(1), one Mn(2), and one Mn(4) atom to form distorted OMgMn3 tetrahedra that share  a cornercorner with one O(1)Mn4 tetrahedra, corners with three equivalent O(4)MgMn3 tetrahedra, and  a cornercorner with one F(6)Mn4 trigonal pyramid. In the third O site, O(3) is bonded in a distorted see-saw-like geometry to one Mg(1), one Mn(2), one Mn(3), and one Mn(5) atom. In the fourth O site, O(4) is bonded to one Mg(1), one Mn(2), one Mn(3), and one Mn(4) atom to form OMgMn3 tetrahedra that share  a cornercorner with one O(1)Mn4 tetrahedra, corners with three equivalent O(2)MgMn3 tetrahedra, and  a cornercorner with one F(6)Mn4 trigonal pyramid. In the fifth O site, O(5) is bonded in a trigonal non-coplanar geometry to one Mn(1), one Mn(3), and one Mn(5) atom. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Mn(2), one Mn(4), and one Mn(6) atom. There are six inequivalent F sites. In the first F site, F(1) is bonded in a distorted water-like geometry to one Mn(2), one Mn(4), and one Mn(5) atom. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Mg(1), one Mn(4), and one Mn(6) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(3), and one Mn(6) atom. In the fourth F site, F(4) is bonded in a distorted trigonal non-coplanar geometry to one Mg(1), one Mn(2), and one Mn(6) atom. In the fifth F site, F(5) is bonded in a 3-coordinate geometry to one Mg(1), one Mn(4), and one Mn(5) atom. In the sixth F site, F(6) is bonded to one Mn(1), one Mn(3), one Mn(5), and one Mn(6) atom to form distorted FMn4 trigonal pyramids that share  a cornercorner with one O(2)MgMn3 tetrahedra,  a cornercorner with one O(4)MgMn3 tetrahedra, and edges with two equivalent O(1)Mn4 tetrahedra.
MgMn6(OF)6 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(2), one O(3), one O(4), one F(2), one F(4), and one F(5) atom to form MgO3F3 octahedra that share  an edgeedge with one Mn(6)O2F4 octahedra,  an edgeedge with one Mn(5)O3F3 octahedra, and edges with two equivalent Mn(4)O3F3 octahedra. The Mg(1)-O(2) bond length is 2.11 Å. The Mg(1)-O(3) bond length is 2.07 Å. The Mg(1)-O(4) bond length is 2.08 Å. The Mg(1)-F(2) bond length is 1.99 Å. The Mg(1)-F(4) bond length is 2.09 Å. The Mg(1)-F(5) bond length is 1.99 Å. There are six inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(5), one F(3), and one F(6) atom. The Mn(1)-O(1) bond length is 2.29 Å. The Mn(1)-O(2) bond length is 2.14 Å. The Mn(1)-O(5) bond length is 2.20 Å. The Mn(1)-F(3) bond length is 2.06 Å. The Mn(1)-F(6) bond length is 2.13 Å. In the second Mn site, Mn(2) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), one O(6), one F(1), and one F(4) atom. The Mn(2)-O(2) bond length is 1.97 Å. The Mn(2)-O(3) bond length is 1.89 Å. The Mn(2)-O(4) bond length is 1.96 Å. The Mn(2)-O(6) bond length is 2.29 Å. The Mn(2)-F(1) bond length is 2.66 Å. The Mn(2)-F(4) bond length is 2.03 Å. In the third Mn site, Mn(3) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(4), one O(5), one F(3), and one F(6) atom. The Mn(3)-O(1) bond length is 2.19 Å. The Mn(3)-O(3) bond length is 2.45 Å. The Mn(3)-O(4) bond length is 2.16 Å. The Mn(3)-O(5) bond length is 2.04 Å. The Mn(3)-F(3) bond length is 2.43 Å. The Mn(3)-F(6) bond length is 2.45 Å. In the fourth Mn site, Mn(4) is bonded to one O(2), one O(4), one O(6), one F(1), one F(2), and one F(5) atom to form MnO3F3 octahedra that share  an edgeedge with one Mn(6)O2F4 octahedra,  an edgeedge with one Mn(5)O3F3 octahedra, and edges with two equivalent Mg(1)O3F3 octahedra. The Mn(4)-O(2) bond length is 2.05 Å. The Mn(4)-O(4) bond length is 1.99 Å. The Mn(4)-O(6) bond length is 1.91 Å. The Mn(4)-F(1) bond length is 1.95 Å. The Mn(4)-F(2) bond length is 2.21 Å. The Mn(4)-F(5) bond length is 2.22 Å. In the fifth Mn site, Mn(5) is bonded to one O(1), one O(3), one O(5), one F(1), one F(5), and one F(6) atom to form distorted MnO3F3 octahedra that share  an edgeedge with one Mg(1)O3F3 octahedra,  an edgeedge with one Mn(6)O2F4 octahedra, and  an edgeedge with one Mn(4)O3F3 octahedra. The Mn(5)-O(1) bond length is 1.98 Å. The Mn(5)-O(3) bond length is 1.99 Å. The Mn(5)-O(5) bond length is 1.85 Å. The Mn(5)-F(1) bond length is 2.17 Å. The Mn(5)-F(5) bond length is 2.07 Å. The Mn(5)-F(6) bond length is 2.44 Å. In the sixth Mn site, Mn(6) is bonded to one O(1), one O(6), one F(2), one F(3), one F(4), and one F(6) atom to form MnO2F4 octahedra that share  an edgeedge with one Mg(1)O3F3 octahedra,  an edgeedge with one Mn(4)O3F3 octahedra, and  an edgeedge with one Mn(5)O3F3 octahedra. The Mn(6)-O(1) bond length is 1.95 Å. The Mn(6)-O(6) bond length is 1.88 Å. The Mn(6)-F(2) bond length is 2.15 Å. The Mn(6)-F(3) bond length is 1.96 Å. The Mn(6)-F(4) bond length is 2.08 Å. The Mn(6)-F(6) bond length is 2.19 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Mn(1), one Mn(3), one Mn(5), and one Mn(6) atom to form OMn4 tetrahedra that share  a cornercorner with one O(2)MgMn3 tetrahedra,  a cornercorner with one O(4)MgMn3 tetrahedra, and edges with two equivalent F(6)Mn4 trigonal pyramids. In the second O site, O(2) is bonded to one Mg(1), one Mn(1), one Mn(2), and one Mn(4) atom to form distorted OMgMn3 tetrahedra that share  a cornercorner with one O(1)Mn4 tetrahedra, corners with three equivalent O(4)MgMn3 tetrahedra, and  a cornercorner with one F(6)Mn4 trigonal pyramid. In the third O site, O(3) is bonded in a distorted see-saw-like geometry to one Mg(1), one Mn(2), one Mn(3), and one Mn(5) atom. In the fourth O site, O(4) is bonded to one Mg(1), one Mn(2), one Mn(3), and one Mn(4) atom to form OMgMn3 tetrahedra that share  a cornercorner with one O(1)Mn4 tetrahedra, corners with three equivalent O(2)MgMn3 tetrahedra, and  a cornercorner with one F(6)Mn4 trigonal pyramid. In the fifth O site, O(5) is bonded in a trigonal non-coplanar geometry to one Mn(1), one Mn(3), and one Mn(5) atom. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Mn(2), one Mn(4), and one Mn(6) atom. There are six inequivalent F sites. In the first F site, F(1) is bonded in a distorted water-like geometry to one Mn(2), one Mn(4), and one Mn(5) atom. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Mg(1), one Mn(4), and one Mn(6) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(3), and one Mn(6) atom. In the fourth F site, F(4) is bonded in a distorted trigonal non-coplanar geometry to one Mg(1), one Mn(2), and one Mn(6) atom. In the fifth F site, F(5) is bonded in a 3-coordinate geometry to one Mg(1), one Mn(4), and one Mn(5) atom. In the sixth F site, F(6) is bonded to one Mn(1), one Mn(3), one Mn(5), and one Mn(6) atom to form distorted FMn4 trigonal pyramids that share  a cornercorner with one O(2)MgMn3 tetrahedra,  a cornercorner with one O(4)MgMn3 tetrahedra, and edges with two equivalent O(1)Mn4 tetrahedra.