Fe5P6H3(O6F)4 crystallizes in the monoclinic P2_1/c space group. There are five inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), and one F(2) atom to form FeO4F2 octahedra that share  a cornercorner with one Fe(2)O4F2 octahedra,  a cornercorner with one Fe(5)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(5)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-48°. The Fe(1)-O(1) bond length is 1.97 Å. The Fe(1)-O(2) bond length is 1.99 Å. The Fe(1)-O(3) bond length is 2.00 Å. The Fe(1)-O(4) bond length is 2.03 Å. The Fe(1)-F(1) bond length is 1.99 Å. The Fe(1)-F(2) bond length is 2.06 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(3) atom to form FeO4F2 octahedra that share  a cornercorner with one Fe(1)O4F2 octahedra,  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-57°. The Fe(2)-O(5) bond length is 1.97 Å. The Fe(2)-O(6) bond length is 1.99 Å. The Fe(2)-O(7) bond length is 2.01 Å. The Fe(2)-O(8) bond length is 2.13 Å. The Fe(2)-F(1) bond length is 2.00 Å. The Fe(2)-F(3) bond length is 1.93 Å. In the third Fe site, Fe(3) is bonded to one O(10), one O(11), one O(12), one O(13), one O(8), and one O(9) atom to form FeO6 octahedra that share  a cornercorner with one Fe(2)O4F2 octahedra,  a cornercorner with one Fe(4)O4F square pyramid,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 57°. The Fe(3)-O(10) bond length is 1.94 Å. The Fe(3)-O(11) bond length is 1.99 Å. The Fe(3)-O(12) bond length is 2.03 Å. The Fe(3)-O(13) bond length is 2.16 Å. The Fe(3)-O(8) bond length is 2.21 Å. The Fe(3)-O(9) bond length is 1.93 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(4) atom to form FeO4F square pyramids that share  a cornercorner with one Fe(5)O4F2 octahedra,  a cornercorner with one Fe(3)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-64°. The Fe(4)-O(13) bond length is 2.18 Å. The Fe(4)-O(14) bond length is 1.95 Å. The Fe(4)-O(15) bond length is 1.96 Å. The Fe(4)-O(16) bond length is 1.97 Å. The Fe(4)-F(4) bond length is 2.06 Å. In the fifth Fe site, Fe(5) is bonded to one O(17), one O(18), one O(19), one O(20), one F(2), and one F(4) atom to form FeO4F2 octahedra that share  a cornercorner with one Fe(1)O4F2 octahedra,  a cornercorner with one Fe(4)O4F square pyramid,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The corner-sharing octahedral tilt angles are 48°. The Fe(5)-O(17) bond length is 1.97 Å. The Fe(5)-O(18) bond length is 1.98 Å. The Fe(5)-O(19) bond length is 1.98 Å. The Fe(5)-O(20) bond length is 1.99 Å. The Fe(5)-F(2) bond length is 2.06 Å. The Fe(5)-F(4) bond length is 2.05 Å. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(18), one O(21), and one O(22) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O4F2 octahedra and  a cornercorner with one Fe(5)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 41-46°. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(18) bond length is 1.54 Å. The P(1)-O(21) bond length is 1.51 Å. The P(1)-O(22) bond length is 1.57 Å. In the second P site, P(2) is bonded to one O(12), one O(23), one O(3), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O4F2 octahedra,  a cornercorner with one Fe(2)O4F2 octahedra, and  a cornercorner with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-55°. The P(2)-O(12) bond length is 1.52 Å. The P(2)-O(23) bond length is 1.58 Å. The P(2)-O(3) bond length is 1.55 Å. The P(2)-O(6) bond length is 1.52 Å. In the third P site, P(3) is bonded to one O(13), one O(19), one O(4), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O4F2 octahedra,  a cornercorner with one Fe(2)O4F2 octahedra,  a cornercorner with one Fe(5)O4F2 octahedra,  a cornercorner with one Fe(4)O4F square pyramid, and  an edgeedge with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-44°. The P(3)-O(13) bond length is 1.56 Å. The P(3)-O(19) bond length is 1.52 Å. The P(3)-O(4) bond length is 1.52 Å. The P(3)-O(8) bond length is 1.56 Å. In the fourth P site, P(4) is bonded to one O(10), one O(15), one O(16), and one O(24) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(3)O6 octahedra and corners with two equivalent Fe(4)O4F square pyramids. The corner-sharing octahedral tilt angles are 48°. The P(4)-O(10) bond length is 1.57 Å. The P(4)-O(15) bond length is 1.54 Å. The P(4)-O(16) bond length is 1.54 Å. The P(4)-O(24) bond length is 1.53 Å. In the fifth P site, P(5) is bonded to one O(17), one O(2), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O4F2 octahedra,  a cornercorner with one Fe(2)O4F2 octahedra,  a cornercorner with one Fe(5)O4F2 octahedra, and  a cornercorner with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-46°. The P(5)-O(17) bond length is 1.53 Å. The P(5)-O(2) bond length is 1.55 Å. The P(5)-O(7) bond length is 1.55 Å. The P(5)-O(9) bond length is 1.53 Å. In the sixth P site, P(6) is bonded to one O(11), one O(14), one O(20), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(2)O4F2 octahedra,  a cornercorner with one Fe(5)O4F2 octahedra,  a cornercorner with one Fe(3)O6 octahedra, and  a cornercorner with one Fe(4)O4F square pyramid. The corner-sharing octahedral tilt angles range from 42-50°. The P(6)-O(11) bond length is 1.54 Å. The P(6)-O(14) bond length is 1.54 Å. The P(6)-O(20) bond length is 1.54 Å. The P(6)-O(5) bond length is 1.55 Å. There are three inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(22) atom. The H(1)-O(22) bond length is 0.82 Å. In the second H site, H(2) is bonded in a single-bond geometry to one O(23) atom. The H(2)-O(23) bond length is 0.82 Å. In the third H site, H(3) is bonded in a single-bond geometry to one O(24) atom. The H(3)-O(24) bond length is 0.82 Å. There are twenty-four 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(1) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Fe(1) and one P(5) 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 distorted bent 150 degrees geometry to one Fe(1) and one P(3) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Fe(2) and one P(6) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one Fe(2) and one P(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Fe(2) and one P(5) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Fe(2), one Fe(3), 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(5) atom. In the tenth O site, O(10) is bonded in a distorted bent 120 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(6) atom. In the twelfth O site, O(12) is bonded in a distorted bent 120 degrees geometry to one Fe(3) and one P(2) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Fe(3), one Fe(4), and one P(3) atom. In the fourteenth O site, O(14) is bonded in a bent 120 degrees geometry to one Fe(4) and one P(6) atom. In the fifteenth O site, O(15) is bonded in a distorted bent 150 degrees geometry to one Fe(4) and one P(4) atom. In the sixteenth O site, O(16) is bonded in a 2-coordinate geometry to one Fe(4) and one P(4) atom. In the seventeenth O site, O(17) is bonded in a bent 150 degrees geometry to one Fe(5) and one P(5) atom. In the eighteenth O site, O(18) is bonded in a distorted bent 120 degrees geometry to one Fe(5) and one P(1) atom. In the nineteenth O site, O(19) is bonded in a bent 150 degrees geometry to one Fe(5) and one P(3) atom. In the twentieth O site, O(20) is bonded in a distorted bent 150 degrees geometry to one Fe(5) and one P(6) atom. In the twenty-first O site, O(21) is bonded in a single-bond geometry to one P(1) atom. In the twenty-second O site, O(22) is bonded in a water-like geometry to one P(1) and one H(1) atom. In the twenty-third O site, O(23) is bonded in a water-like geometry to one P(2) and one H(2) atom. In the twenty-fourth O site, O(24) is bonded in a water-like geometry to one P(4) and one H(3) atom. There are four 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(5) atom. In the third F site, F(3) is bonded in a single-bond geometry to one Fe(2) atom. In the fourth F site, F(4) is bonded in a distorted bent 120 degrees geometry to one Fe(4) and one Fe(5) atom. Linkers: 12 [O]P([O])([O])=O ,12 [O]P([O])(=O)O. Metal clusters: 20 [Fe]. The MOF has largest included sphere 4.37 A, density 1.81 g/cm3, surface area 2458.36 m2/g, accessible volume 0.28 cm3/g