MgMn6(OF)6 crystallizes in the monoclinic Pm space group. Mg(1) is bonded to one O(2), two equivalent O(3), one F(6), and two equivalent F(4) atoms to form MgO3F3 octahedra that share corners with four equivalent Mn(6)O3F3 octahedra, corners with two equivalent Mn(1)O4F square pyramids, edges with two equivalent Mg(1)O3F3 octahedra, edges with two equivalent Mn(3)O2F4 octahedra, and faces with two equivalent Mn(6)O3F3 octahedra. The corner-sharing octahedral tilt angles are 40°. There are six inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(2), two equivalent O(6), and one F(2) atom to form MnO4F square pyramids that share corners with two equivalent Mg(1)O3F3 octahedra, corners with two equivalent Mn(6)O3F3 octahedra, corners with four equivalent Mn(4)O2F4 octahedra, and edges with two equivalent Mn(1)O4F square pyramids. The corner-sharing octahedral tilt angles range from 48-73°. In the second Mn site, Mn(2) is bonded to one O(4), two equivalent O(1), one F(3), and two equivalent F(5) atoms to form distorted MnO3F3 octahedra that share corners with four equivalent Mn(4)O2F4 octahedra, corners with four equivalent Mn(5)O4F2 octahedra, and edges with two equivalent Mn(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 48-52°. In the third Mn site, Mn(3) is bonded to one O(3), one O(5), two equivalent F(1), and two equivalent F(6) atoms to form distorted MnO2F4 octahedra that share corners with four equivalent Mn(6)O3F3 octahedra, corners with four equivalent Mn(5)O4F2 octahedra, edges with two equivalent Mg(1)O3F3 octahedra, and edges with two equivalent Mn(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 40-60°. In the fourth Mn site, Mn(4) is bonded to one O(1), one O(6), two equivalent F(2), and two equivalent F(3) atoms to form MnO2F4 octahedra that share corners with four equivalent Mn(2)O3F3 octahedra, corners with four equivalent Mn(1)O4F square pyramids, and edges with two equivalent Mn(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 49-52°. In the fifth Mn site, Mn(5) is bonded to two equivalent O(4), two equivalent O(5), one F(1), and one F(5) atom to form MnO4F2 octahedra that share corners with four equivalent Mn(3)O2F4 octahedra, corners with four equivalent Mn(2)O3F3 octahedra, and edges with two equivalent Mn(5)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 48-51°. In the sixth Mn site, Mn(6) is bonded to one O(2), two equivalent O(3), one F(6), and two equivalent F(4) atoms to form distorted MnO3F3 octahedra that share corners with four equivalent Mg(1)O3F3 octahedra, corners with four equivalent Mn(3)O2F4 octahedra, corners with two equivalent Mn(1)O4F square pyramids, edges with two equivalent Mn(6)O3F3 octahedra, and faces with two equivalent Mg(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 40-60°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Mn(4) and two equivalent Mn(2) atoms. In the second O site, O(2) is bonded to one Mg(1), one Mn(6), and two equivalent Mn(1) atoms to form distorted OMgMn3 tetrahedra that share corners with two equivalent O(2)MgMn3 tetrahedra and edges with two equivalent O(3)Mg2Mn3 trigonal bipyramids. In the third O site, O(3) is bonded to two equivalent Mg(1), one Mn(3), and two equivalent Mn(6) atoms to form distorted OMg2Mn3 trigonal bipyramids that share edges with two equivalent O(2)MgMn3 tetrahedra and edges with two equivalent O(3)Mg2Mn3 trigonal bipyramids. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Mn(2) and two equivalent Mn(5) atoms. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Mn(3) and two equivalent Mn(5) atoms. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Mn(4) and two equivalent Mn(1) atoms. There are six inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Mn(5) and two equivalent Mn(3) atoms. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Mn(1) and two equivalent Mn(4) atoms. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Mn(2) and two equivalent Mn(4) atoms. In the fourth F site, F(4) is bonded in a 4-coordinate geometry to two equivalent Mg(1) and two equivalent Mn(6) atoms. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Mn(5) and two equivalent Mn(2) atoms. In the sixth F site, F(6) is bonded in a rectangular see-saw-like geometry to one Mg(1), one Mn(6), and two equivalent Mn(3) atoms.
MgMn6(OF)6 crystallizes in the monoclinic Pm space group. Mg(1) is bonded to one O(2), two equivalent O(3), one F(6), and two equivalent F(4) atoms to form MgO3F3 octahedra that share corners with four equivalent Mn(6)O3F3 octahedra, corners with two equivalent Mn(1)O4F square pyramids, edges with two equivalent Mg(1)O3F3 octahedra, edges with two equivalent Mn(3)O2F4 octahedra, and faces with two equivalent Mn(6)O3F3 octahedra. The corner-sharing octahedral tilt angles are 40°. The Mg(1)-O(2) bond length is 2.02 Å. Both Mg(1)-O(3) bond lengths are 2.11 Å. The Mg(1)-F(6) bond length is 1.98 Å. Both Mg(1)-F(4) bond lengths are 2.06 Å. There are six inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(2), two equivalent O(6), and one F(2) atom to form MnO4F square pyramids that share corners with two equivalent Mg(1)O3F3 octahedra, corners with two equivalent Mn(6)O3F3 octahedra, corners with four equivalent Mn(4)O2F4 octahedra, and edges with two equivalent Mn(1)O4F square pyramids. The corner-sharing octahedral tilt angles range from 48-73°. Both Mn(1)-O(2) bond lengths are 2.01 Å. Both Mn(1)-O(6) bond lengths are 1.96 Å. The Mn(1)-F(2) bond length is 2.23 Å. In the second Mn site, Mn(2) is bonded to one O(4), two equivalent O(1), one F(3), and two equivalent F(5) atoms to form distorted MnO3F3 octahedra that share corners with four equivalent Mn(4)O2F4 octahedra, corners with four equivalent Mn(5)O4F2 octahedra, and edges with two equivalent Mn(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 48-52°. The Mn(2)-O(4) bond length is 2.01 Å. Both Mn(2)-O(1) bond lengths are 1.96 Å. The Mn(2)-F(3) bond length is 2.44 Å. Both Mn(2)-F(5) bond lengths are 2.04 Å. In the third Mn site, Mn(3) is bonded to one O(3), one O(5), two equivalent F(1), and two equivalent F(6) atoms to form distorted MnO2F4 octahedra that share corners with four equivalent Mn(6)O3F3 octahedra, corners with four equivalent Mn(5)O4F2 octahedra, edges with two equivalent Mg(1)O3F3 octahedra, and edges with two equivalent Mn(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 40-60°. The Mn(3)-O(3) bond length is 2.16 Å. The Mn(3)-O(5) bond length is 1.97 Å. Both Mn(3)-F(1) bond lengths are 2.06 Å. Both Mn(3)-F(6) bond lengths are 2.38 Å. In the fourth Mn site, Mn(4) is bonded to one O(1), one O(6), two equivalent F(2), and two equivalent F(3) atoms to form MnO2F4 octahedra that share corners with four equivalent Mn(2)O3F3 octahedra, corners with four equivalent Mn(1)O4F square pyramids, and edges with two equivalent Mn(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 49-52°. The Mn(4)-O(1) bond length is 1.96 Å. The Mn(4)-O(6) bond length is 1.96 Å. Both Mn(4)-F(2) bond lengths are 2.12 Å. Both Mn(4)-F(3) bond lengths are 2.06 Å. In the fifth Mn site, Mn(5) is bonded to two equivalent O(4), two equivalent O(5), one F(1), and one F(5) atom to form MnO4F2 octahedra that share corners with four equivalent Mn(3)O2F4 octahedra, corners with four equivalent Mn(2)O3F3 octahedra, and edges with two equivalent Mn(5)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 48-51°. Both Mn(5)-O(4) bond lengths are 1.96 Å. Both Mn(5)-O(5) bond lengths are 1.97 Å. The Mn(5)-F(1) bond length is 2.41 Å. The Mn(5)-F(5) bond length is 2.43 Å. In the sixth Mn site, Mn(6) is bonded to one O(2), two equivalent O(3), one F(6), and two equivalent F(4) atoms to form distorted MnO3F3 octahedra that share corners with four equivalent Mg(1)O3F3 octahedra, corners with four equivalent Mn(3)O2F4 octahedra, corners with two equivalent Mn(1)O4F square pyramids, edges with two equivalent Mn(6)O3F3 octahedra, and faces with two equivalent Mg(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 40-60°. The Mn(6)-O(2) bond length is 2.19 Å. Both Mn(6)-O(3) bond lengths are 2.12 Å. The Mn(6)-F(6) bond length is 2.13 Å. Both Mn(6)-F(4) bond lengths are 2.35 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Mn(4) and two equivalent Mn(2) atoms. In the second O site, O(2) is bonded to one Mg(1), one Mn(6), and two equivalent Mn(1) atoms to form distorted OMgMn3 tetrahedra that share corners with two equivalent O(2)MgMn3 tetrahedra and edges with two equivalent O(3)Mg2Mn3 trigonal bipyramids. In the third O site, O(3) is bonded to two equivalent Mg(1), one Mn(3), and two equivalent Mn(6) atoms to form distorted OMg2Mn3 trigonal bipyramids that share edges with two equivalent O(2)MgMn3 tetrahedra and edges with two equivalent O(3)Mg2Mn3 trigonal bipyramids. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Mn(2) and two equivalent Mn(5) atoms. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Mn(3) and two equivalent Mn(5) atoms. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Mn(4) and two equivalent Mn(1) atoms. There are six inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Mn(5) and two equivalent Mn(3) atoms. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Mn(1) and two equivalent Mn(4) atoms. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Mn(2) and two equivalent Mn(4) atoms. In the fourth F site, F(4) is bonded in a 4-coordinate geometry to two equivalent Mg(1) and two equivalent Mn(6) atoms. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Mn(5) and two equivalent Mn(2) atoms. In the sixth F site, F(6) is bonded in a rectangular see-saw-like geometry to one Mg(1), one Mn(6), and two equivalent Mn(3) atoms.