Mn3(O2F)2 is Hydrophilite-derived structured and crystallizes in the monoclinic C2/m space group. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), two equivalent O(2), one F(1), and two equivalent F(2) atoms to form MnO3F3 octahedra that share corners with four equivalent Mn(3)O4F2 octahedra, corners with four equivalent Mn(4)O5F octahedra,  an edgeedge with one Mn(1)O3F3 octahedra, and  an edgeedge with one Mn(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 42-58°. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent F(1) atoms to form MnO4F2 octahedra that share corners with eight equivalent Mn(4)O5F octahedra and edges with two equivalent Mn(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 45-51°. In the third Mn site, Mn(3) is bonded to four equivalent O(2) and two equivalent F(2) atoms to form MnO4F2 octahedra that share corners with eight equivalent Mn(1)O3F3 octahedra and edges with two equivalent Mn(4)O5F octahedra. The corner-sharing octahedral tilt angles range from 45-58°. In the fourth Mn site, Mn(4) is bonded to one O(1), two equivalent O(2), two equivalent O(3), and one F(1) atom to form MnO5F octahedra that share corners with four equivalent Mn(1)O3F3 octahedra, corners with four equivalent Mn(2)O4F2 octahedra,  an edgeedge with one Mn(3)O4F2 octahedra, and  an edgeedge with one Mn(4)O5F octahedra. The corner-sharing octahedral tilt angles range from 42-52°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one Mn(4) 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(4) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Mn(2) and two equivalent Mn(4) atoms. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Mn(1), one Mn(2), and one Mn(4) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Mn(3) and two equivalent Mn(1) atoms.
Mn3(O2F)2 is Hydrophilite-derived structured and crystallizes in the monoclinic C2/m space group. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), two equivalent O(2), one F(1), and two equivalent F(2) atoms to form MnO3F3 octahedra that share corners with four equivalent Mn(3)O4F2 octahedra, corners with four equivalent Mn(4)O5F octahedra,  an edgeedge with one Mn(1)O3F3 octahedra, and  an edgeedge with one Mn(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 42-58°. The Mn(1)-O(1) bond length is 1.91 Å. Both Mn(1)-O(2) bond lengths are 1.93 Å. The Mn(1)-F(1) bond length is 2.15 Å. There is one shorter (1.99 Å) and one longer (2.09 Å) Mn(1)-F(2) bond length. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent F(1) atoms to form MnO4F2 octahedra that share corners with eight equivalent Mn(4)O5F octahedra and edges with two equivalent Mn(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 45-51°. Both Mn(2)-O(1) bond lengths are 1.96 Å. Both Mn(2)-O(3) bond lengths are 1.94 Å. Both Mn(2)-F(1) bond lengths are 2.13 Å. In the third Mn site, Mn(3) is bonded to four equivalent O(2) and two equivalent F(2) atoms to form MnO4F2 octahedra that share corners with eight equivalent Mn(1)O3F3 octahedra and edges with two equivalent Mn(4)O5F octahedra. The corner-sharing octahedral tilt angles range from 45-58°. All Mn(3)-O(2) bond lengths are 1.97 Å. Both Mn(3)-F(2) bond lengths are 2.11 Å. In the fourth Mn site, Mn(4) is bonded to one O(1), two equivalent O(2), two equivalent O(3), and one F(1) atom to form MnO5F octahedra that share corners with four equivalent Mn(1)O3F3 octahedra, corners with four equivalent Mn(2)O4F2 octahedra,  an edgeedge with one Mn(3)O4F2 octahedra, and  an edgeedge with one Mn(4)O5F octahedra. The corner-sharing octahedral tilt angles range from 42-52°. The Mn(4)-O(1) bond length is 1.94 Å. Both Mn(4)-O(2) bond lengths are 1.94 Å. Both Mn(4)-O(3) bond lengths are 1.94 Å. The Mn(4)-F(1) bond length is 2.01 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one Mn(4) 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(4) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Mn(2) and two equivalent Mn(4) atoms. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Mn(1), one Mn(2), and one Mn(4) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Mn(3) and two equivalent Mn(1) atoms.