MgMn6(O2F)4 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one F(3) atom to form MgO5F octahedra that share  a cornercorner with one Mn(3)O4F square pyramid, corners with two equivalent Mn(1)O5 square pyramids, edges with two equivalent Mn(5)O3F3 octahedra, edges with two equivalent Mn(4)O4F2 octahedra, and  an edgeedge with one Mn(3)O4F square pyramid. There are six inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one O(3), one O(6), one O(7), and one O(8) atom to form distorted MnO5 square pyramids that share  a cornercorner with one Mn(5)O3F3 octahedra, corners with two equivalent Mg(1)O5F octahedra, corners with two equivalent Mn(4)O4F2 octahedra, corners with three equivalent Mn(6)O3F3 octahedra, and  an edgeedge with one Mn(3)O4F square pyramid. The corner-sharing octahedral tilt angles range from 41-61°. In the second Mn site, Mn(2) is bonded in a 5-coordinate geometry to one O(3), one O(4), one O(5), one O(7), and one F(1) atom. In the third Mn site, Mn(3) is bonded to one O(2), one O(4), one O(5), one O(6), and one F(4) atom to form distorted MnO4F square pyramids that share  a cornercorner with one Mg(1)O5F octahedra,  a cornercorner with one Mn(4)O4F2 octahedra, corners with two equivalent Mn(6)O3F3 octahedra, corners with three equivalent Mn(5)O3F3 octahedra,  an edgeedge with one Mg(1)O5F octahedra, and  an edgeedge with one Mn(1)O5 square pyramid. The corner-sharing octahedral tilt angles range from 42-56°. In the fourth Mn site, Mn(4) is bonded to one O(1), one O(3), one O(5), one O(8), one F(1), and one F(3) atom to form MnO4F2 octahedra that share  a cornercorner with one Mn(3)O4F square pyramid, corners with two equivalent Mn(1)O5 square pyramids,  an edgeedge with one Mn(5)O3F3 octahedra,  an edgeedge with one Mn(6)O3F3 octahedra, and edges with two equivalent Mg(1)O5F octahedra. In the fifth Mn site, Mn(5) is bonded to one O(1), one O(4), one O(6), one F(2), one F(3), and one F(4) atom to form MnO3F3 octahedra that share  a cornercorner with one Mn(1)O5 square pyramid, corners with three equivalent Mn(3)O4F square pyramids,  an edgeedge with one Mn(6)O3F3 octahedra,  an edgeedge with one Mn(4)O4F2 octahedra, and edges with two equivalent Mg(1)O5F octahedra. In the sixth Mn site, Mn(6) is bonded to one O(2), one O(7), one O(8), one F(1), one F(2), and one F(4) atom to form MnO3F3 octahedra that share corners with two equivalent Mn(3)O4F square pyramids, corners with three equivalent Mn(1)O5 square pyramids,  an edgeedge with one Mn(5)O3F3 octahedra, and  an edgeedge with one Mn(4)O4F2 octahedra. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to one Mg(1), one Mn(4), and one Mn(5) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Mn(1), one Mn(3), and one Mn(6) atom. In the third O site, O(3) is bonded to one Mg(1), one Mn(1), one Mn(2), and one Mn(4) atom to form a mixture of distorted corner and edge-sharing OMgMn3 trigonal pyramids. In the fourth O site, O(4) is bonded to one Mg(1), one Mn(2), one Mn(3), and one Mn(5) atom to form a mixture of distorted corner and edge-sharing OMgMn3 trigonal pyramids. In the fifth O site, O(5) is bonded to one Mg(1), one Mn(2), one Mn(3), and one Mn(4) atom to form a mixture of corner and edge-sharing OMgMn3 trigonal pyramids. In the sixth O site, O(6) is bonded in a distorted see-saw-like geometry to one Mg(1), one Mn(1), one Mn(3), and one Mn(5) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Mn(1), one Mn(2), and one Mn(6) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(4), and one Mn(6) atom. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Mn(2), one Mn(4), and one Mn(6) atom. In the second F site, F(2) is bonded in a water-like geometry to one Mn(5) and one Mn(6) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Mg(1), one Mn(4), and one Mn(5) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Mn(3), one Mn(5), and one Mn(6) atom.
MgMn6(O2F)4 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one F(3) atom to form MgO5F octahedra that share  a cornercorner with one Mn(3)O4F square pyramid, corners with two equivalent Mn(1)O5 square pyramids, edges with two equivalent Mn(5)O3F3 octahedra, edges with two equivalent Mn(4)O4F2 octahedra, and  an edgeedge with one Mn(3)O4F square pyramid. The Mg(1)-O(1) bond length is 1.96 Å. The Mg(1)-O(3) bond length is 2.15 Å. The Mg(1)-O(4) bond length is 2.12 Å. The Mg(1)-O(5) bond length is 2.08 Å. The Mg(1)-O(6) bond length is 2.23 Å. The Mg(1)-F(3) bond length is 1.94 Å. There are six inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one O(3), one O(6), one O(7), and one O(8) atom to form distorted MnO5 square pyramids that share  a cornercorner with one Mn(5)O3F3 octahedra, corners with two equivalent Mg(1)O5F octahedra, corners with two equivalent Mn(4)O4F2 octahedra, corners with three equivalent Mn(6)O3F3 octahedra, and  an edgeedge with one Mn(3)O4F square pyramid. The corner-sharing octahedral tilt angles range from 41-61°. The Mn(1)-O(2) bond length is 1.95 Å. The Mn(1)-O(3) bond length is 1.99 Å. The Mn(1)-O(6) bond length is 2.04 Å. The Mn(1)-O(7) bond length is 1.95 Å. The Mn(1)-O(8) bond length is 2.39 Å. In the second Mn site, Mn(2) is bonded in a 5-coordinate geometry to one O(3), one O(4), one O(5), one O(7), and one F(1) atom. The Mn(2)-O(3) bond length is 1.98 Å. The Mn(2)-O(4) bond length is 2.04 Å. The Mn(2)-O(5) bond length is 1.99 Å. The Mn(2)-O(7) bond length is 1.93 Å. The Mn(2)-F(1) bond length is 2.08 Å. In the third Mn site, Mn(3) is bonded to one O(2), one O(4), one O(5), one O(6), and one F(4) atom to form distorted MnO4F square pyramids that share  a cornercorner with one Mg(1)O5F octahedra,  a cornercorner with one Mn(4)O4F2 octahedra, corners with two equivalent Mn(6)O3F3 octahedra, corners with three equivalent Mn(5)O3F3 octahedra,  an edgeedge with one Mg(1)O5F octahedra, and  an edgeedge with one Mn(1)O5 square pyramid. The corner-sharing octahedral tilt angles range from 42-56°. The Mn(3)-O(2) bond length is 1.93 Å. The Mn(3)-O(4) bond length is 1.98 Å. The Mn(3)-O(5) bond length is 2.00 Å. The Mn(3)-O(6) bond length is 1.99 Å. The Mn(3)-F(4) bond length is 2.18 Å. In the fourth Mn site, Mn(4) is bonded to one O(1), one O(3), one O(5), one O(8), one F(1), and one F(3) atom to form MnO4F2 octahedra that share  a cornercorner with one Mn(3)O4F square pyramid, corners with two equivalent Mn(1)O5 square pyramids,  an edgeedge with one Mn(5)O3F3 octahedra,  an edgeedge with one Mn(6)O3F3 octahedra, and edges with two equivalent Mg(1)O5F octahedra. The Mn(4)-O(1) bond length is 1.94 Å. The Mn(4)-O(3) bond length is 2.04 Å. The Mn(4)-O(5) bond length is 2.06 Å. The Mn(4)-O(8) bond length is 1.89 Å. The Mn(4)-F(1) bond length is 2.12 Å. The Mn(4)-F(3) bond length is 2.18 Å. In the fifth Mn site, Mn(5) is bonded to one O(1), one O(4), one O(6), one F(2), one F(3), and one F(4) atom to form MnO3F3 octahedra that share  a cornercorner with one Mn(1)O5 square pyramid, corners with three equivalent Mn(3)O4F square pyramids,  an edgeedge with one Mn(6)O3F3 octahedra,  an edgeedge with one Mn(4)O4F2 octahedra, and edges with two equivalent Mg(1)O5F octahedra. The Mn(5)-O(1) bond length is 1.87 Å. The Mn(5)-O(4) bond length is 2.01 Å. The Mn(5)-O(6) bond length is 2.00 Å. The Mn(5)-F(2) bond length is 2.08 Å. The Mn(5)-F(3) bond length is 2.20 Å. The Mn(5)-F(4) bond length is 2.01 Å. In the sixth Mn site, Mn(6) is bonded to one O(2), one O(7), one O(8), one F(1), one F(2), and one F(4) atom to form MnO3F3 octahedra that share corners with two equivalent Mn(3)O4F square pyramids, corners with three equivalent Mn(1)O5 square pyramids,  an edgeedge with one Mn(5)O3F3 octahedra, and  an edgeedge with one Mn(4)O4F2 octahedra. The Mn(6)-O(2) bond length is 1.99 Å. The Mn(6)-O(7) bond length is 1.97 Å. The Mn(6)-O(8) bond length is 1.89 Å. The Mn(6)-F(1) bond length is 2.16 Å. The Mn(6)-F(2) bond length is 1.97 Å. The Mn(6)-F(4) bond length is 2.19 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to one Mg(1), one Mn(4), and one Mn(5) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Mn(1), one Mn(3), and one Mn(6) atom. In the third O site, O(3) is bonded to one Mg(1), one Mn(1), one Mn(2), and one Mn(4) atom to form a mixture of distorted corner and edge-sharing OMgMn3 trigonal pyramids. In the fourth O site, O(4) is bonded to one Mg(1), one Mn(2), one Mn(3), and one Mn(5) atom to form a mixture of distorted corner and edge-sharing OMgMn3 trigonal pyramids. In the fifth O site, O(5) is bonded to one Mg(1), one Mn(2), one Mn(3), and one Mn(4) atom to form a mixture of corner and edge-sharing OMgMn3 trigonal pyramids. In the sixth O site, O(6) is bonded in a distorted see-saw-like geometry to one Mg(1), one Mn(1), one Mn(3), and one Mn(5) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Mn(1), one Mn(2), and one Mn(6) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(4), and one Mn(6) atom. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Mn(2), one Mn(4), and one Mn(6) atom. In the second F site, F(2) is bonded in a water-like geometry to one Mn(5) and one Mn(6) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Mg(1), one Mn(4), and one Mn(5) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Mn(3), one Mn(5), and one Mn(6) atom.