Fe2P2O8F crystallizes in the monoclinic P2_1/c space group. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(4) atom. The Fe(1)-O(1) bond length is 1.92 Å. The Fe(1)-O(2) bond length is 1.93 Å. The Fe(1)-O(3) bond length is 1.93 Å. The Fe(1)-O(4) bond length is 1.93 Å. In the second Fe site, Fe(2) is bonded to one O(5), one O(6), one O(7), one O(8), one F(1), and one F(2) atom to form FeO4F2 octahedra that share  a cornercorner with one Fe(3)O4F square pyramid,  a cornercorner with one Fe(4)O4F square pyramid,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The Fe(2)-O(5) bond length is 1.93 Å. The Fe(2)-O(6) bond length is 2.00 Å. The Fe(2)-O(7) bond length is 2.01 Å. The Fe(2)-O(8) bond length is 2.05 Å. The Fe(2)-F(1) bond length is 2.00 Å. The Fe(2)-F(2) bond length is 2.01 Å. In the third Fe site, Fe(3) is bonded to one O(10), one O(11), one O(12), one O(9), and one F(1) atom to form FeO4F square pyramids that share  a cornercorner with one Fe(2)O4F2 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 50°. The Fe(3)-O(10) bond length is 1.98 Å. The Fe(3)-O(11) bond length is 1.98 Å. The Fe(3)-O(12) bond length is 1.99 Å. The Fe(3)-O(9) bond length is 1.96 Å. The Fe(3)-F(1) bond length is 2.02 Å. In the fourth Fe site, Fe(4) is bonded to one O(13), one O(14), one O(15), one O(16), and one F(2) atom to form FeO4F square pyramids that share  a cornercorner with one Fe(2)O4F2 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 54°. The Fe(4)-O(13) bond length is 1.95 Å. The Fe(4)-O(14) bond length is 1.96 Å. The Fe(4)-O(15) bond length is 1.98 Å. The Fe(4)-O(16) bond length is 2.03 Å. The Fe(4)-F(2) bond length is 2.01 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(16), one O(2), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(2)O4F2 octahedra and  a cornercorner with one Fe(4)O4F square pyramid. The corner-sharing octahedral tilt angles are 53°. The P(1)-O(16) bond length is 1.53 Å. The P(1)-O(2) bond length is 1.52 Å. The P(1)-O(4) bond length is 1.54 Å. The P(1)-O(6) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(12), one O(13), one O(3), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(2)O4F2 octahedra,  a cornercorner with one Fe(3)O4F square pyramid, and  a cornercorner with one Fe(4)O4F square pyramid. The corner-sharing octahedral tilt angles are 51°. The P(2)-O(12) bond length is 1.53 Å. The P(2)-O(13) bond length is 1.52 Å. The P(2)-O(3) bond length is 1.54 Å. The P(2)-O(5) bond length is 1.54 Å. In the third P site, P(3) is bonded to one O(11), one O(14), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Fe(2)O4F2 octahedra,  a cornercorner with one Fe(3)O4F square pyramid, and  a cornercorner with one Fe(4)O4F square pyramid. The corner-sharing octahedral tilt angles range from 38-53°. The P(3)-O(11) bond length is 1.56 Å. The P(3)-O(14) bond length is 1.55 Å. The P(3)-O(7) bond length is 1.53 Å. The P(3)-O(8) bond length is 1.53 Å. In the fourth P site, P(4) is bonded to one O(1), one O(10), one O(15), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(4)O4F square pyramid and corners with two equivalent Fe(3)O4F square pyramids. The P(4)-O(1) bond length is 1.54 Å. The P(4)-O(10) bond length is 1.53 Å. The P(4)-O(15) bond length is 1.53 Å. The P(4)-O(9) bond length is 1.51 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(4) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(1) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Fe(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one Fe(2) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one Fe(2) and one P(1) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Fe(2) and one P(3) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one Fe(2) and one P(3) atom. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one Fe(3) and one P(4) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Fe(3) and one P(4) atom. In the eleventh O site, O(11) is bonded in a bent 120 degrees geometry to one Fe(3) and one P(3) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one Fe(3) and one P(2) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one Fe(4) and one P(2) atom. In the fourteenth O site, O(14) is bonded in a bent 120 degrees geometry to one Fe(4) and one P(3) atom. In the fifteenth O site, O(15) is bonded in a bent 150 degrees geometry to one Fe(4) and one P(4) atom. In the sixteenth O site, O(16) is bonded in a distorted bent 120 degrees geometry to one Fe(4) and one P(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a bent 120 degrees geometry to one Fe(2) and one Fe(3) atom. In the second F site, F(2) is bonded in a bent 120 degrees geometry to one Fe(2) and one Fe(4) atom. Linkers: 16 [O]P([O])([O])=O. Metal clusters: 16 [Fe]. The MOF has largest included sphere 5.23 A, density 2.05 g/cm3, surface area 2359.07 m2/g, accessible volume 0.24 cm3/g