Hf3C20H4(SO2)6 crystallizes in the cubic Fm-3m space group. There are two inequivalent Hf sites. In the first Hf site, Hf(1) is bonded in a 8-coordinate geometry to two equivalent O(3), two equivalent O(4), and four equivalent O(1) atoms. Both Hf(1)-O(3) bond lengths are 2.15 Å. Both Hf(1)-O(4) bond lengths are 2.14 Å. All Hf(1)-O(1) bond lengths are 2.19 Å. In the second Hf site, Hf(2) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms. Both Hf(2)-O(2) bond lengths are 2.26 Å. Both Hf(2)-O(3) bond lengths are 2.13 Å. Both Hf(2)-O(4) bond lengths are 2.13 Å. There are five inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one C(2), one C(4), and one S(1) atom. The C(1)-C(2) bond length is 1.34 Å. The C(1)-C(4) bond length is 1.48 Å. The C(1)-S(1) bond length is 1.74 Å. In the second C site, C(2) is bonded in a distorted single-bond geometry to one C(1), one C(3), and one H(1) atom. The C(2)-C(3) bond length is 1.42 Å. The C(2)-H(1) bond length is 0.93 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one C(2), one C(5), and one S(2) atom. The C(3)-C(5) bond length is 1.35 Å. The C(3)-S(2) bond length is 1.74 Å. In the fourth C site, C(4) is bonded in a distorted bent 120 degrees geometry to one C(1), one O(1), and one O(2) atom. The C(4)-O(1) bond length is 1.25 Å. The C(4)-O(2) bond length is 1.26 Å. In the fifth C site, C(5) is bonded in a distorted trigonal planar geometry to one C(3), one C(5), and one S(1) atom. The C(5)-C(5) bond length is 1.43 Å. The C(5)-S(1) bond length is 1.71 Å. H(1) is bonded in a single-bond geometry to one C(2) atom. There are two inequivalent S sites. In the first S site, S(2) is bonded in an L-shaped geometry to two equivalent C(3) atoms. In the second S site, S(1) is bonded in an L-shaped geometry to one C(1) and one C(5) atom. There are four inequivalent O sites. In the first O site, O(4) is bonded in a trigonal non-coplanar geometry to one Hf(1) and two equivalent Hf(2) atoms. In the second O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Hf(1) and one C(4) atom. In the third O site, O(2) is bonded in a 2-coordinate geometry to one Hf(2) and one C(4) atom. In the fourth O site, O(3) is bonded in a trigonal non-coplanar geometry to one Hf(1) and two equivalent Hf(2) atoms. Linkers: 24 [O]C(=O)c1cc2sc3cc(C([O])=O)sc3c2s1. Metal clusters: 1 O=[C]O[Hf]1234O[C]O[Hf]O[C]O[Hf]5(O[C]=O)(O1)(O2)O[Hf]12(O[C]=O)(O[C]O[Hf]O[C]O[Hf](O[C]=O)(O1)(O2)(O3)O4)O5 ,1 O=[C]O[Hf]1234O[C]O[Hf]5O[C]O[Hf]67(O[C]O[Hf]O[C]O[Hf]8(O[C]O5)(O6)(O7)O[Hf](O[C]=O)(O[C]=O)(O8)(O1)O2)(O3)O4 ,1 O=[C]O[Hf]123(O[C]=O)O[Hf]456(O[C]O[Hf]O[C]O[Hf]7(O[C]O[Hf]O[C]O4)(O5)(O6)O[Hf](O[C]=O)(O[C]=O)(O7)(O1)O2)O3 ,1 O=[C]O[Hf]1234O[C]O[Hf]O[C]O[Hf]56(O[C]O[Hf]O[C]O[Hf]7(O[C]=O)(O1)(O2)O[Hf](O[C]=O)(O[C]=O)(O5)(O6)O7)(O3)O4 ,1 O=[C]O[Hf]1234O[C]O[Hf]O[C]O[Hf]56(O[C]O[Hf]O[C]O[Hf]7(O[C]=O)(O5)(O6)O[Hf](O[C]=O)(O[C]=O)(O1)(O2)O7)(O3)O4 ,1 O=[C]O[Hf]123(O[C]=O)O[Hf]456(O[C]O[Hf]O[C]O[Hf]7(O[C]O[Hf]O[C]O4)(O1)(O2)O[Hf](O[C]=O)(O[C]=O)(O5)(O6)O7)O3. RCSR code: reo. The MOF has largest included sphere 26.23 A, density 0.75 g/cm3, surface area 2241.77 m2/g, accessible volume 1.09 cm3/g