Mn4OF6 crystallizes in the orthorhombic Cmc2_1 space group. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 4-coordinate geometry to one O(1), one F(2), one F(3), two equivalent F(1), and two equivalent F(4) atoms. In the second Mn site, Mn(2) is bonded in a 6-coordinate geometry to one O(1), one F(2), two equivalent F(1), and two equivalent F(4) atoms. In the third Mn site, Mn(3) is bonded in a 6-coordinate geometry to one O(1), one F(2), one F(3), one F(4), and two equivalent F(1) atoms. O(1) is bonded to one Mn(1), one Mn(2), and two equivalent Mn(3) atoms to form OMn4 tetrahedra that share corners with two equivalent F(2)Mn4 trigonal pyramids and  an edgeedge with one F(2)Mn4 trigonal pyramid. There are four inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Mn(1), one Mn(2), and two equivalent Mn(3) atoms. In the second F site, F(2) is bonded to one Mn(1), one Mn(2), and two equivalent Mn(3) atoms to form distorted FMn4 trigonal pyramids that share corners with two equivalent O(1)Mn4 tetrahedra and  an edgeedge with one O(1)Mn4 tetrahedra. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Mn(1) and two equivalent Mn(3) atoms. In the fourth F site, F(4) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(2), and one Mn(3) atom.
Mn4OF6 crystallizes in the orthorhombic Cmc2_1 space group. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 4-coordinate geometry to one O(1), one F(2), one F(3), two equivalent F(1), and two equivalent F(4) atoms. The Mn(1)-O(1) bond length is 1.97 Å. The Mn(1)-F(2) bond length is 2.66 Å. The Mn(1)-F(3) bond length is 2.12 Å. Both Mn(1)-F(1) bond lengths are 2.67 Å. Both Mn(1)-F(4) bond lengths are 2.12 Å. In the second Mn site, Mn(2) is bonded in a 6-coordinate geometry to one O(1), one F(2), two equivalent F(1), and two equivalent F(4) atoms. The Mn(2)-O(1) bond length is 2.05 Å. The Mn(2)-F(2) bond length is 2.29 Å. Both Mn(2)-F(1) bond lengths are 2.20 Å. Both Mn(2)-F(4) bond lengths are 2.36 Å. In the third Mn site, Mn(3) is bonded in a 6-coordinate geometry to one O(1), one F(2), one F(3), one F(4), and two equivalent F(1) atoms. The Mn(3)-O(1) bond length is 2.05 Å. The Mn(3)-F(2) bond length is 2.21 Å. The Mn(3)-F(3) bond length is 2.36 Å. The Mn(3)-F(4) bond length is 2.36 Å. There is one shorter (2.20 Å) and one longer (2.30 Å) Mn(3)-F(1) bond length. O(1) is bonded to one Mn(1), one Mn(2), and two equivalent Mn(3) atoms to form OMn4 tetrahedra that share corners with two equivalent F(2)Mn4 trigonal pyramids and  an edgeedge with one F(2)Mn4 trigonal pyramid. There are four inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Mn(1), one Mn(2), and two equivalent Mn(3) atoms. In the second F site, F(2) is bonded to one Mn(1), one Mn(2), and two equivalent Mn(3) atoms to form distorted FMn4 trigonal pyramids that share corners with two equivalent O(1)Mn4 tetrahedra and  an edgeedge with one O(1)Mn4 tetrahedra. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Mn(1) and two equivalent Mn(3) atoms. In the fourth F site, F(4) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(2), and one Mn(3) atom.