Fe5P8(O8F)4 crystallizes in the tetragonal P-42_1c space group. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(5), one O(6), one O(8), one O(9), one F(1), and one F(2) atom to form FeO4F2 octahedra that share corners with two equivalent 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 range from 46-48°. The Fe(1)-O(5) bond length is 1.97 Å. The Fe(1)-O(6) bond length is 1.97 Å. The Fe(1)-O(8) bond length is 1.98 Å. The Fe(1)-O(9) bond length is 1.98 Å. The Fe(1)-F(1) bond length is 2.00 Å. The Fe(1)-F(2) bond length is 1.98 Å. In the second Fe site, Fe(2) is bonded to one O(1), one O(11), one O(14), one O(4), one F(1), and one F(2) atom to form FeO4F2 octahedra that share corners with two equivalent Fe(1)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 range from 46-48°. The Fe(2)-O(1) bond length is 1.96 Å. The Fe(2)-O(11) bond length is 1.94 Å. The Fe(2)-O(14) bond length is 2.01 Å. The Fe(2)-O(4) bond length is 2.01 Å. The Fe(2)-F(1) bond length is 2.00 Å. The Fe(2)-F(2) bond length is 1.99 Å. In the third Fe site, Fe(3) is bonded in a rectangular see-saw-like geometry to four equivalent O(2) atoms. All Fe(3)-O(2) bond lengths are 2.02 Å. In the fourth Fe site, Fe(4) is bonded in a rectangular see-saw-like geometry to four equivalent O(3) atoms. All Fe(4)-O(3) bond lengths are 2.00 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(13), one O(2), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O4F2 octahedra and  a cornercorner with one Fe(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 45-47°. The P(1)-O(1) bond length is 1.52 Å. The P(1)-O(13) bond length is 1.59 Å. The P(1)-O(2) bond length is 1.51 Å. The P(1)-O(8) bond length is 1.52 Å. In the second P site, P(2) is bonded to one O(14), one O(15), one O(16), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O4F2 octahedra and  a cornercorner with one Fe(2)O4F2 octahedra. The corner-sharing octahedral tilt angles are 42°. The P(2)-O(14) bond length is 1.53 Å. The P(2)-O(15) bond length is 1.53 Å. The P(2)-O(16) bond length is 1.52 Å. The P(2)-O(9) bond length is 1.50 Å. In the third P site, P(3) is bonded to one O(10), one O(12), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O4F2 octahedra and  a cornercorner with one Fe(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 43-44°. The P(3)-O(10) bond length is 1.53 Å. The P(3)-O(12) bond length is 1.57 Å. The P(3)-O(4) bond length is 1.51 Å. The P(3)-O(6) bond length is 1.51 Å. In the fourth P site, P(4) is bonded to one O(11), one O(3), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O4F2 octahedra and  a cornercorner with one Fe(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 46-48°. The P(4)-O(11) bond length is 1.52 Å. The P(4)-O(3) bond length is 1.51 Å. The P(4)-O(5) bond length is 1.52 Å. The P(4)-O(7) bond length is 1.58 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Fe(2) and one P(1) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Fe(3) and one P(1) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Fe(4) and one P(4) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Fe(2) and one P(3) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one Fe(1) and one P(4) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Fe(1) and one P(3) atom. In the seventh O site, O(7) is bonded in a single-bond geometry to one P(4) atom. In the eighth O site, O(8) is bonded in a distorted bent 120 degrees geometry to one Fe(1) and one P(1) atom. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one Fe(1) and one P(2) atom. In the tenth O site, O(10) is bonded in a single-bond geometry to one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted bent 120 degrees geometry to one Fe(2) and one P(4) atom. In the twelfth O site, O(12) is bonded in a single-bond geometry to one P(3) atom. In the thirteenth O site, O(13) is bonded in a single-bond geometry to one P(1) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 150 degrees geometry to one Fe(2) and one P(2) atom. In the fifteenth O site, O(15) is bonded in a single-bond geometry to one P(2) atom. In the sixteenth O site, O(16) is bonded in a single-bond geometry to one P(2) 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(1) and one Fe(2) atom. In the second F site, F(2) is bonded in a bent 120 degrees geometry to one Fe(1) and one Fe(2) atom. Linkers: 32 [O]P([O])([O])=O. Metal clusters: 20 [Fe]. The MOF has largest included sphere 4.92 A, density 1.88 g/cm3, surface area 2802.09 m2/g, accessible volume 0.17 cm3/g