Mn2OF2 is Ilmenite-like structured and crystallizes in the monoclinic C2/c space group. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one F(2), one F(3), and two equivalent F(1) atoms to form a mixture of distorted face, corner, and edge-sharing MnO2F4 octahedra. The corner-sharing octahedral tilt angles range from 44-68°. In the second Mn site, Mn(2) is bonded to one O(1), one O(2), one F(2), one F(3), and two equivalent F(1) atoms to form a mixture of distorted face, corner, and edge-sharing MnO2F4 octahedra. The corner-sharing octahedral tilt angles range from 45-74°. In the third Mn site, Mn(3) is bonded to two equivalent O(1), two equivalent F(2), and two equivalent F(3) atoms to form a mixture of distorted face, corner, and edge-sharing MnO2F4 octahedra. The corner-sharing octahedral tilt angles range from 44-68°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Mn(1), one Mn(2), and two equivalent Mn(3) atoms to form OMn4 trigonal pyramids that share corners with two equivalent O(2)Mn4 trigonal pyramids, corners with two equivalent F(1)Mn4 trigonal pyramids, corners with four equivalent F(2)Mn4 trigonal pyramids,  an edgeedge with one O(1)Mn4 trigonal pyramid,  an edgeedge with one F(1)Mn4 trigonal pyramid, and  an edgeedge with one F(2)Mn4 trigonal pyramid. In the second O site, O(2) is bonded to two equivalent Mn(1) and two equivalent Mn(2) atoms to form distorted OMn4 trigonal pyramids that share corners with four equivalent O(1)Mn4 trigonal pyramids, corners with four equivalent F(1)Mn4 trigonal pyramids, edges with two equivalent F(1)Mn4 trigonal pyramids, and edges with two equivalent F(2)Mn4 trigonal pyramids. There are three inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Mn(1) and two equivalent Mn(2) atoms to form distorted FMn4 trigonal pyramids that share corners with two equivalent O(1)Mn4 trigonal pyramids, corners with two equivalent O(2)Mn4 trigonal pyramids, corners with two equivalent F(1)Mn4 trigonal pyramids, corners with four equivalent F(2)Mn4 trigonal pyramids,  an edgeedge with one O(1)Mn4 trigonal pyramid,  an edgeedge with one O(2)Mn4 trigonal pyramid, and  an edgeedge with one F(1)Mn4 trigonal pyramid. 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 four equivalent O(1)Mn4 trigonal pyramids, corners with four equivalent F(1)Mn4 trigonal pyramids,  an edgeedge with one O(1)Mn4 trigonal pyramid,  an edgeedge with one O(2)Mn4 trigonal pyramid, and  an edgeedge with one F(2)Mn4 trigonal pyramid. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Mn(1), one Mn(2), and two equivalent Mn(3) atoms.
Mn2OF2 is Ilmenite-like structured and crystallizes in the monoclinic C2/c space group. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one F(2), one F(3), and two equivalent F(1) atoms to form a mixture of distorted face, corner, and edge-sharing MnO2F4 octahedra. The corner-sharing octahedral tilt angles range from 44-68°. The Mn(1)-O(1) bond length is 2.06 Å. The Mn(1)-O(2) bond length is 2.13 Å. The Mn(1)-F(2) bond length is 2.24 Å. The Mn(1)-F(3) bond length is 2.18 Å. There is one shorter (2.32 Å) and one longer (2.48 Å) Mn(1)-F(1) bond length. In the second Mn site, Mn(2) is bonded to one O(1), one O(2), one F(2), one F(3), and two equivalent F(1) atoms to form a mixture of distorted face, corner, and edge-sharing MnO2F4 octahedra. The corner-sharing octahedral tilt angles range from 45-74°. The Mn(2)-O(1) bond length is 2.14 Å. The Mn(2)-O(2) bond length is 2.08 Å. The Mn(2)-F(2) bond length is 2.31 Å. The Mn(2)-F(3) bond length is 2.45 Å. There is one shorter (2.16 Å) and one longer (2.20 Å) Mn(2)-F(1) bond length. In the third Mn site, Mn(3) is bonded to two equivalent O(1), two equivalent F(2), and two equivalent F(3) atoms to form a mixture of distorted face, corner, and edge-sharing MnO2F4 octahedra. The corner-sharing octahedral tilt angles range from 44-68°. There is one shorter (2.08 Å) and one longer (2.16 Å) Mn(3)-O(1) bond length. There is one shorter (2.19 Å) and one longer (2.35 Å) Mn(3)-F(2) bond length. There is one shorter (2.17 Å) and one longer (2.35 Å) Mn(3)-F(3) bond length. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Mn(1), one Mn(2), and two equivalent Mn(3) atoms to form OMn4 trigonal pyramids that share corners with two equivalent O(2)Mn4 trigonal pyramids, corners with two equivalent F(1)Mn4 trigonal pyramids, corners with four equivalent F(2)Mn4 trigonal pyramids,  an edgeedge with one O(1)Mn4 trigonal pyramid,  an edgeedge with one F(1)Mn4 trigonal pyramid, and  an edgeedge with one F(2)Mn4 trigonal pyramid. In the second O site, O(2) is bonded to two equivalent Mn(1) and two equivalent Mn(2) atoms to form distorted OMn4 trigonal pyramids that share corners with four equivalent O(1)Mn4 trigonal pyramids, corners with four equivalent F(1)Mn4 trigonal pyramids, edges with two equivalent F(1)Mn4 trigonal pyramids, and edges with two equivalent F(2)Mn4 trigonal pyramids. There are three inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Mn(1) and two equivalent Mn(2) atoms to form distorted FMn4 trigonal pyramids that share corners with two equivalent O(1)Mn4 trigonal pyramids, corners with two equivalent O(2)Mn4 trigonal pyramids, corners with two equivalent F(1)Mn4 trigonal pyramids, corners with four equivalent F(2)Mn4 trigonal pyramids,  an edgeedge with one O(1)Mn4 trigonal pyramid,  an edgeedge with one O(2)Mn4 trigonal pyramid, and  an edgeedge with one F(1)Mn4 trigonal pyramid. 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 four equivalent O(1)Mn4 trigonal pyramids, corners with four equivalent F(1)Mn4 trigonal pyramids,  an edgeedge with one O(1)Mn4 trigonal pyramid,  an edgeedge with one O(2)Mn4 trigonal pyramid, and  an edgeedge with one F(2)Mn4 trigonal pyramid. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Mn(1), one Mn(2), and two equivalent Mn(3) atoms.