Mn2P2O7F2 crystallizes in the orthorhombic Pbcn 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(3), and two equivalent F(1) atoms to form MnO4F2 octahedra that share corners with four equivalent P(1)O4 tetrahedra and edges with two equivalent Mn(2)O4F2 octahedra. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent F(1) atoms to form distorted MnO4F2 octahedra that share corners with four equivalent P(1)O4 tetrahedra and edges with two equivalent Mn(1)O4F2 octahedra. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O4F2 octahedra, corners with two equivalent Mn(2)O4F2 octahedra, and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 43-56°. There are four 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 P(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to two equivalent P(1) atoms. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Mn(2) and one P(1) atom. F(1) is bonded in a water-like geometry to one Mn(1) and one Mn(2) atom.
Mn2P2O7F2 crystallizes in the orthorhombic Pbcn 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(3), and two equivalent F(1) atoms to form MnO4F2 octahedra that share corners with four equivalent P(1)O4 tetrahedra and edges with two equivalent Mn(2)O4F2 octahedra. Both Mn(1)-O(1) bond lengths are 2.01 Å. Both Mn(1)-O(3) bond lengths are 1.94 Å. Both Mn(1)-F(1) bond lengths are 2.13 Å. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent F(1) atoms to form distorted MnO4F2 octahedra that share corners with four equivalent P(1)O4 tetrahedra and edges with two equivalent Mn(1)O4F2 octahedra. Both Mn(2)-O(1) bond lengths are 2.23 Å. Both Mn(2)-O(4) bond lengths are 2.04 Å. Both Mn(2)-F(1) bond lengths are 1.85 Å. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O4F2 octahedra, corners with two equivalent Mn(2)O4F2 octahedra, and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 43-56°. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(2) bond length is 1.61 Å. The P(1)-O(3) bond length is 1.53 Å. The P(1)-O(4) bond length is 1.51 Å. There are four 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 P(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to two equivalent P(1) atoms. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Mn(2) and one P(1) atom. F(1) is bonded in a water-like geometry to one Mn(1) and one Mn(2) atom.