Fe3C36O13F24 crystallizes in the hexagonal P6_3/mmc space group. Fe(1) is bonded to one O(2) and four equivalent O(1) atoms to form distorted corner-sharing FeO5 square pyramids. The Fe(1)-O(2) bond length is 1.89 Å. All Fe(1)-O(1) bond lengths are 2.02 Å. There are four inequivalent C sites. In the first C site, C(1) is bonded in a distorted water-like geometry to one C(1), one C(2), one C(4), and one F(1) atom. The C(1)-C(1) bond length is 0.80 Å. The C(1)-C(2) bond length is 1.38 Å. The C(1)-C(4) bond length is 1.34 Å. The C(1)-F(1) bond length is 1.41 Å. In the second C site, C(2) is bonded in a 4-coordinate geometry to one C(1), one C(2), one C(4), and one F(2) atom. The C(2)-C(2) bond length is 1.10 Å. The C(2)-C(4) bond length is 1.32 Å. The C(2)-F(2) bond length is 1.35 Å. In the third C site, C(3) is bonded in a distorted bent 120 degrees geometry to one C(4) and two equivalent O(1) atoms. The C(3)-C(4) bond length is 1.51 Å. Both C(3)-O(1) bond lengths are 1.22 Å. In the fourth C site, C(4) is bonded in a 5-coordinate geometry to one C(3), two equivalent C(1), and two equivalent C(2) atoms. There are two inequivalent O sites. In the first O site, O(2) is bonded in a trigonal planar geometry to three equivalent Fe(1) atoms. In the second O site, O(1) is bonded in a distorted single-bond geometry to one Fe(1) and one C(3) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a single-bond geometry to one C(1) atom. In the second F site, F(2) is bonded in a single-bond geometry to one C(2) atom. Linkers: 2 F[C]1[C@@]2(F)[C]3[C@]4(F)[C](F)[C@]5(F)[C]([C@]1(F)[C@]32F)[C@]45F.[O][C]=O.[O][C]=O ,2 F[C]1[C@@]2(F)[C]3[C@@]4(F)[C](F)[C@@]5(F)[C]([C@]1(F)[C@]32F)[C@]54F.[O][C]=O.[O][C]=O ,2 F[C]1[C@@]2(F)[C]3[C@@]4(F)[C](F)[C@@](F)([C]5[C@]1(F)[C@]52F)[C@@]34F.[O][C]=O.[O][C]=O. Metal clusters: 2 [C]1O[Fe]23O[C]O[Fe]45(O1)O[C]O[Fe](O[C]O2)(O[C]O3)(O[C]O4)O5. RCSR code: acs. The MOF has largest included sphere 11.48 A, density 1.21 g/cm3, surface area 2771.02 m2/g, accessible volume 0.46 cm3/g