Mn2O3F crystallizes in the orthorhombic Pnma space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form MnO4F2 octahedra that share edges with two equivalent Mn(1)O4F2 octahedra and edges with four equivalent Mn(2)O5F octahedra. In the second Mn site, Mn(2) is bonded to one O(2), four equivalent O(1), and one F(1) atom to form MnO5F octahedra that share edges with two equivalent Mn(2)O5F octahedra and edges with four equivalent Mn(1)O4F2 octahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1) and two equivalent Mn(2) atoms. In the second O site, O(2) is bonded in a trigonal non-coplanar geometry to one Mn(2) and two equivalent Mn(1) atoms. F(1) is bonded in a 3-coordinate geometry to one Mn(2) and two equivalent Mn(1) atoms.
Mn2O3F crystallizes in the orthorhombic Pnma space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form MnO4F2 octahedra that share edges with two equivalent Mn(1)O4F2 octahedra and edges with four equivalent Mn(2)O5F octahedra. Both Mn(1)-O(1) bond lengths are 1.96 Å. Both Mn(1)-O(2) bond lengths are 1.97 Å. Both Mn(1)-F(1) bond lengths are 2.28 Å. In the second Mn site, Mn(2) is bonded to one O(2), four equivalent O(1), and one F(1) atom to form MnO5F octahedra that share edges with two equivalent Mn(2)O5F octahedra and edges with four equivalent Mn(1)O4F2 octahedra. The Mn(2)-O(2) bond length is 1.91 Å. There are two shorter (1.93 Å) and two longer (1.95 Å) Mn(2)-O(1) bond lengths. The Mn(2)-F(1) bond length is 1.95 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1) and two equivalent Mn(2) atoms. In the second O site, O(2) is bonded in a trigonal non-coplanar geometry to one Mn(2) and two equivalent Mn(1) atoms. F(1) is bonded in a 3-coordinate geometry to one Mn(2) and two equivalent Mn(1) atoms.