Mn3(OF2)2 is Hydrophilite-derived structured and crystallizes in the orthorhombic Cmmm space group. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(3) atoms to form MnO2F4 octahedra that share corners with two equivalent Mn(4)O4F2 octahedra, corners with six equivalent Mn(2)OF5 octahedra, and edges with two equivalent Mn(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 50-52°. In the second Mn site, Mn(2) is bonded to one O(1), one F(2), and four equivalent F(1) atoms to form MnOF5 octahedra that share corners with two equivalent Mn(3)O2F4 octahedra, corners with six equivalent Mn(1)O2F4 octahedra, and edges with two equivalent Mn(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 47-52°. In the third Mn site, Mn(3) is bonded to two equivalent O(2) and four equivalent F(2) atoms to form MnO2F4 octahedra that share corners with four equivalent Mn(4)O4F2 octahedra, corners with four equivalent Mn(2)OF5 octahedra, and edges with two equivalent Mn(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 47-50°. In the fourth Mn site, Mn(4) is bonded to four equivalent O(2) and two equivalent F(3) atoms to form MnO4F2 octahedra that share corners with four equivalent Mn(1)O2F4 octahedra, corners with four equivalent Mn(3)O2F4 octahedra, and edges with two equivalent Mn(4)O4F2 octahedra. The corner-sharing octahedral tilt angles are 50°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Mn(2) and two equivalent Mn(1) atoms. In the second O site, O(2) is bonded in a trigonal planar geometry to one Mn(3) and two equivalent Mn(4) atoms. There are three inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Mn(1) and two equivalent Mn(2) atoms. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Mn(2) and two equivalent Mn(3) atoms. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Mn(4) and two equivalent Mn(1) atoms.
Mn3(OF2)2 is Hydrophilite-derived structured and crystallizes in the orthorhombic Cmmm space group. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(3) atoms to form MnO2F4 octahedra that share corners with two equivalent Mn(4)O4F2 octahedra, corners with six equivalent Mn(2)OF5 octahedra, and edges with two equivalent Mn(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 50-52°. Both Mn(1)-O(1) bond lengths are 1.98 Å. Both Mn(1)-F(1) bond lengths are 2.09 Å. Both Mn(1)-F(3) bond lengths are 2.06 Å. In the second Mn site, Mn(2) is bonded to one O(1), one F(2), and four equivalent F(1) atoms to form MnOF5 octahedra that share corners with two equivalent Mn(3)O2F4 octahedra, corners with six equivalent Mn(1)O2F4 octahedra, and edges with two equivalent Mn(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 47-52°. The Mn(2)-O(1) bond length is 1.95 Å. The Mn(2)-F(2) bond length is 2.08 Å. All Mn(2)-F(1) bond lengths are 2.06 Å. In the third Mn site, Mn(3) is bonded to two equivalent O(2) and four equivalent F(2) atoms to form MnO2F4 octahedra that share corners with four equivalent Mn(4)O4F2 octahedra, corners with four equivalent Mn(2)OF5 octahedra, and edges with two equivalent Mn(3)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 47-50°. Both Mn(3)-O(2) bond lengths are 2.12 Å. All Mn(3)-F(2) bond lengths are 2.14 Å. In the fourth Mn site, Mn(4) is bonded to four equivalent O(2) and two equivalent F(3) atoms to form MnO4F2 octahedra that share corners with four equivalent Mn(1)O2F4 octahedra, corners with four equivalent Mn(3)O2F4 octahedra, and edges with two equivalent Mn(4)O4F2 octahedra. The corner-sharing octahedral tilt angles are 50°. All Mn(4)-O(2) bond lengths are 2.03 Å. Both Mn(4)-F(3) bond lengths are 2.30 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Mn(2) and two equivalent Mn(1) atoms. In the second O site, O(2) is bonded in a trigonal planar geometry to one Mn(3) and two equivalent Mn(4) atoms. There are three inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Mn(1) and two equivalent Mn(2) atoms. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Mn(2) and two equivalent Mn(3) atoms. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Mn(4) and two equivalent Mn(1) atoms.