NaC3H2S(O2Cl)2 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded to one O(2), one O(3), one O(4), and two equivalent O(1) atoms to form distorted corner-sharing NaO5 trigonal bipyramids. The Na(1)-O(2) bond length is 2.35 Å. The Na(1)-O(3) bond length is 2.35 Å. The Na(1)-O(4) bond length is 2.35 Å. There is one shorter (2.32 Å) and one longer (2.43 Å) Na(1)-O(1) bond length. There are three 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 S(1) atom. The C(1)-C(2) bond length is 1.41 Å. The C(1)-C(3) bond length is 1.41 Å. The C(1)-S(1) bond length is 1.83 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one C(1), one C(3), and one Cl(1) atom. The C(2)-C(3) bond length is 1.41 Å. The C(2)-Cl(1) bond length is 1.72 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one C(1), one C(2), and one Cl(2) atom. The C(3)-Cl(2) bond length is 1.71 Å. There are two inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(1) atom. The H(1)-O(1) bond length is 0.99 Å. In the second H site, H(2) is bonded in a single-bond geometry to one O(1) atom. The H(2)-O(1) bond length is 0.99 Å. S(1) is bonded in a distorted trigonal non-coplanar geometry to one C(1), one O(2), one O(3), and one O(4) atom. The S(1)-O(2) bond length is 1.47 Å. The S(1)-O(3) bond length is 1.46 Å. The S(1)-O(4) bond length is 1.46 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted water-like geometry to two equivalent Na(1), one H(1), and one H(2) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one S(1) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one S(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one S(1) atom. There are two inequivalent Cl sites. In the first Cl site, Cl(2) is bonded in a single-bond geometry to one C(3) atom. In the second Cl site, Cl(1) is bonded in a single-bond geometry to one C(2) atom. Linkers: 2 [O]S([O])([O])c1c(Cl)c(Cl)c(S([O])([O])[O])c(Cl)c1Cl. Metal clusters: 4 [Na]. The MOF has largest included sphere 1.72 A, density 2.18 g/cm3, surface area 2376.07 m2/g, accessible volume 0.03 cm3/g