CoC6NH3SO2 crystallizes in the orthorhombic C222_1 space group. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded in a 6-coordinate geometry to two equivalent N(1), two equivalent S(1), and two equivalent O(1) atoms. Both Co(1)-N(1) bond lengths are 2.09 Å. Both Co(1)-S(1) bond lengths are 2.55 Å. Both Co(1)-O(1) bond lengths are 2.03 Å. In the second Co site, Co(2) is bonded in a tetrahedral geometry to two equivalent S(1) and two equivalent O(2) atoms. Both Co(2)-S(1) bond lengths are 2.23 Å. Both Co(2)-O(2) bond lengths are 1.92 Å. There are six inequivalent C sites. In the first C site, C(1) is bonded in a distorted trigonal planar geometry to one C(2), one N(1), and one S(1) atom. The C(1)-C(2) bond length is 1.40 Å. The C(1)-N(1) bond length is 1.36 Å. The C(1)-S(1) bond length is 1.75 Å. In the second C site, C(2) is bonded in a distorted single-bond geometry to one C(1) and one H(1) atom. The C(2)-H(1) bond length is 1.09 Å. In the third C site, C(3) is bonded in a distorted single-bond geometry to one C(4) and one H(2) atom. The C(3)-C(4) bond length is 1.40 Å. The C(3)-H(2) bond length is 1.09 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one C(3), one C(5), and one C(6) atom. The C(4)-C(5) bond length is 1.40 Å. The C(4)-C(6) bond length is 1.49 Å. In the fifth C site, C(5) is bonded in a distorted trigonal planar geometry to one C(4), one N(1), and one H(3) atom. The C(5)-N(1) bond length is 1.34 Å. The C(5)-H(3) bond length is 1.09 Å. In the sixth C site, C(6) is bonded in a distorted bent 120 degrees geometry to one C(4), one O(1), and one O(2) atom. The C(6)-O(1) bond length is 1.27 Å. The C(6)-O(2) bond length is 1.28 Å. N(1) is bonded in a distorted trigonal planar geometry to one Co(1), one C(1), and one C(5) atom. There are three inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(2) atom. In the second H site, H(2) is bonded in a single-bond geometry to one C(3) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(5) atom. S(1) is bonded in a 3-coordinate geometry to one Co(1), one Co(2), and one C(1) atom. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Co(1) and one C(6) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Co(2) and one C(6) atom. Linkers: 4 [O]C(=O)[C]1C=CC(=S)N=C1. Metal clusters: 4 [Co]. The MOF has largest included sphere 4.71 A, density 1.58 g/cm3, surface area 3336.32 m2/g, accessible volume 0.23 cm3/g