MgMn6(OF)6 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(4), one O(6), two equivalent F(2), and two equivalent F(5) atoms to form MgO2F4 octahedra that share  a cornercorner with one Mn(2)O2F2 tetrahedra,  a cornercorner with one Mn(3)O2F2 tetrahedra, edges with two equivalent Mg(1)O2F4 octahedra, and edges with four equivalent Mn(5)O4F2 octahedra. There are six inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), two equivalent O(1), one F(3), and two equivalent F(4) atoms to form MnO3F3 octahedra that share corners with four equivalent Mn(6)O3F3 octahedra, corners with four equivalent Mn(4)O4F2 octahedra, and edges with two equivalent Mn(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 46-52°. In the second Mn site, Mn(2) is bonded to one O(4), one O(5), and two equivalent F(1) atoms to form MnO2F2 tetrahedra that share  a cornercorner with one Mg(1)O2F4 octahedra, corners with two equivalent Mn(5)O4F2 octahedra, corners with four equivalent Mn(4)O4F2 octahedra, and corners with two equivalent Mn(2)O2F2 tetrahedra. The corner-sharing octahedral tilt angles range from 51-67°. In the third Mn site, Mn(3) is bonded to one O(3), one O(6), and two equivalent F(6) atoms to form MnO2F2 tetrahedra that share  a cornercorner with one Mg(1)O2F4 octahedra, corners with two equivalent Mn(5)O4F2 octahedra, corners with four equivalent Mn(6)O3F3 octahedra, and corners with two equivalent Mn(3)O2F2 tetrahedra. The corner-sharing octahedral tilt angles range from 49-68°. In the fourth Mn site, Mn(4) is bonded to two equivalent O(2), two equivalent O(5), one F(1), and one F(4) atom to form MnO4F2 octahedra that share corners with four equivalent Mn(1)O3F3 octahedra, corners with four equivalent Mn(2)O2F2 tetrahedra, and edges with two equivalent Mn(4)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 49-51°. In the fifth Mn site, Mn(5) is bonded to two equivalent O(4), two equivalent O(6), one F(2), and one F(5) atom to form MnO4F2 octahedra that share corners with two equivalent Mn(2)O2F2 tetrahedra, corners with two equivalent Mn(3)O2F2 tetrahedra, edges with two equivalent Mn(5)O4F2 octahedra, and edges with four equivalent Mg(1)O2F4 octahedra. In the sixth Mn site, Mn(6) is bonded to one O(1), two equivalent O(3), one F(6), and two equivalent F(3) atoms to form MnO3F3 octahedra that share corners with four equivalent Mn(1)O3F3 octahedra, corners with four equivalent Mn(3)O2F2 tetrahedra, and edges with two equivalent Mn(6)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 46-52°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Mn(6) 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(4) atoms. In the third O site, O(3) is bonded in a trigonal planar geometry to one Mn(3) and two equivalent Mn(6) atoms. In the fourth O site, O(4) is bonded to one Mg(1), one Mn(2), and two equivalent Mn(5) atoms to form a mixture of corner and edge-sharing OMgMn3 tetrahedra. 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 a mixture of corner and edge-sharing OMgMn3 tetrahedra. There are six 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 distorted T-shaped geometry to two equivalent Mg(1) and one Mn(5) atom. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one Mn(1) and two equivalent Mn(6) atoms. In the fourth F site, F(4) is bonded in a 3-coordinate geometry to one Mn(4) and two equivalent Mn(1) atoms. In the fifth F site, F(5) is bonded in a distorted T-shaped geometry to two equivalent Mg(1) and one Mn(5) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Mn(6) and two equivalent Mn(3) atoms.
MgMn6(OF)6 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one O(4), one O(6), two equivalent F(2), and two equivalent F(5) atoms to form MgO2F4 octahedra that share  a cornercorner with one Mn(2)O2F2 tetrahedra,  a cornercorner with one Mn(3)O2F2 tetrahedra, edges with two equivalent Mg(1)O2F4 octahedra, and edges with four equivalent Mn(5)O4F2 octahedra. The Mg(1)-O(4) bond length is 2.08 Å. The Mg(1)-O(6) bond length is 2.09 Å. Both Mg(1)-F(2) bond lengths are 2.02 Å. Both Mg(1)-F(5) bond lengths are 2.01 Å. There are six inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), two equivalent O(1), one F(3), and two equivalent F(4) atoms to form MnO3F3 octahedra that share corners with four equivalent Mn(6)O3F3 octahedra, corners with four equivalent Mn(4)O4F2 octahedra, and edges with two equivalent Mn(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 46-52°. The Mn(1)-O(2) bond length is 1.99 Å. Both Mn(1)-O(1) bond lengths are 1.96 Å. The Mn(1)-F(3) bond length is 2.31 Å. Both Mn(1)-F(4) bond lengths are 2.04 Å. In the second Mn site, Mn(2) is bonded to one O(4), one O(5), and two equivalent F(1) atoms to form MnO2F2 tetrahedra that share  a cornercorner with one Mg(1)O2F4 octahedra, corners with two equivalent Mn(5)O4F2 octahedra, corners with four equivalent Mn(4)O4F2 octahedra, and corners with two equivalent Mn(2)O2F2 tetrahedra. The corner-sharing octahedral tilt angles range from 51-67°. The Mn(2)-O(4) bond length is 2.08 Å. The Mn(2)-O(5) bond length is 1.95 Å. Both Mn(2)-F(1) bond lengths are 2.04 Å. In the third Mn site, Mn(3) is bonded to one O(3), one O(6), and two equivalent F(6) atoms to form MnO2F2 tetrahedra that share  a cornercorner with one Mg(1)O2F4 octahedra, corners with two equivalent Mn(5)O4F2 octahedra, corners with four equivalent Mn(6)O3F3 octahedra, and corners with two equivalent Mn(3)O2F2 tetrahedra. The corner-sharing octahedral tilt angles range from 49-68°. The Mn(3)-O(3) bond length is 1.97 Å. The Mn(3)-O(6) bond length is 2.05 Å. Both Mn(3)-F(6) bond lengths are 2.05 Å. In the fourth Mn site, Mn(4) is bonded to two equivalent O(2), two equivalent O(5), one F(1), and one F(4) atom to form MnO4F2 octahedra that share corners with four equivalent Mn(1)O3F3 octahedra, corners with four equivalent Mn(2)O2F2 tetrahedra, and edges with two equivalent Mn(4)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 49-51°. Both Mn(4)-O(2) bond lengths are 1.96 Å. Both Mn(4)-O(5) bond lengths are 1.98 Å. The Mn(4)-F(1) bond length is 2.33 Å. The Mn(4)-F(4) bond length is 2.57 Å. In the fifth Mn site, Mn(5) is bonded to two equivalent O(4), two equivalent O(6), one F(2), and one F(5) atom to form MnO4F2 octahedra that share corners with two equivalent Mn(2)O2F2 tetrahedra, corners with two equivalent Mn(3)O2F2 tetrahedra, edges with two equivalent Mn(5)O4F2 octahedra, and edges with four equivalent Mg(1)O2F4 octahedra. Both Mn(5)-O(4) bond lengths are 2.01 Å. Both Mn(5)-O(6) bond lengths are 2.02 Å. The Mn(5)-F(2) bond length is 2.23 Å. The Mn(5)-F(5) bond length is 2.22 Å. In the sixth Mn site, Mn(6) is bonded to one O(1), two equivalent O(3), one F(6), and two equivalent F(3) atoms to form MnO3F3 octahedra that share corners with four equivalent Mn(1)O3F3 octahedra, corners with four equivalent Mn(3)O2F2 tetrahedra, and edges with two equivalent Mn(6)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 46-52°. The Mn(6)-O(1) bond length is 2.02 Å. Both Mn(6)-O(3) bond lengths are 1.96 Å. The Mn(6)-F(6) bond length is 2.26 Å. Both Mn(6)-F(3) bond lengths are 2.11 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Mn(6) 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(4) atoms. In the third O site, O(3) is bonded in a trigonal planar geometry to one Mn(3) and two equivalent Mn(6) atoms. In the fourth O site, O(4) is bonded to one Mg(1), one Mn(2), and two equivalent Mn(5) atoms to form a mixture of corner and edge-sharing OMgMn3 tetrahedra. 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 a mixture of corner and edge-sharing OMgMn3 tetrahedra. There are six 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 distorted T-shaped geometry to two equivalent Mg(1) and one Mn(5) atom. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one Mn(1) and two equivalent Mn(6) atoms. In the fourth F site, F(4) is bonded in a 3-coordinate geometry to one Mn(4) and two equivalent Mn(1) atoms. In the fifth F site, F(5) is bonded in a distorted T-shaped geometry to two equivalent Mg(1) and one Mn(5) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Mn(6) and two equivalent Mn(3) atoms.