MnC4HSO2 crystallizes in the trigonal R-3c space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a distorted octahedral geometry to two equivalent S(1), two equivalent O(1), and two equivalent O(2) atoms. Both Mn(1)-S(1) bond lengths are 2.49 Å. Both Mn(1)-O(1) bond lengths are 2.28 Å. Both Mn(1)-O(2) bond lengths are 2.15 Å. In the second Mn site, Mn(2) is bonded in a rectangular see-saw-like geometry to two equivalent S(1) and two equivalent O(1) atoms. Both Mn(2)-S(1) bond lengths are 2.63 Å. Both Mn(2)-O(1) bond lengths are 2.24 Å. There are four inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one C(2), one C(3), and one C(4) atom. The C(1)-C(2) bond length is 1.50 Å. The C(1)-C(3) bond length is 1.39 Å. The C(1)-C(4) bond length is 1.41 Å. In the second C site, C(2) is bonded in a distorted bent 120 degrees geometry to one C(1), one O(1), and one O(2) atom. The C(2)-O(1) bond length is 1.28 Å. The C(2)-O(2) bond length is 1.24 Å. In the third C site, C(3) is bonded in a distorted single-bond geometry to one C(1), one C(4), and one H(1) atom. The C(3)-C(4) bond length is 1.40 Å. The C(3)-H(1) bond length is 0.95 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one C(1), one C(3), and one S(1) atom. The C(4)-S(1) bond length is 1.77 Å. H(1) is bonded in a single-bond geometry to one C(3) atom. S(1) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1), one Mn(2), and one C(4) atom. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(2), and one C(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Mn(1) and one C(2) atom. Linkers: 6 [O]C(=O)c1cc([S])c(C([O])=O)cc1[S]. Metal clusters: 12 [Mn]. The MOF has largest included sphere 11.32 A, density 1.04 g/cm3, surface area 2900.39 m2/g, accessible volume 0.54 cm3/g