NaC3H5S(NO2)2 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form edge-sharing NaO6 octahedra. The Na(1)-O(1) bond length is 2.39 Å. The Na(1)-O(3) bond length is 2.41 Å. There is one shorter (2.34 Å) and one longer (2.38 Å) Na(1)-O(2) bond length. There is one shorter (2.43 Å) and one longer (2.57 Å) Na(1)-O(4) bond length. There are three inequivalent C sites. In the first C site, C(3) is bonded in a distorted bent 120 degrees geometry to one C(2), one N(1), and one H(5) atom. The C(3)-C(2) bond length is 1.41 Å. The C(3)-N(1) bond length is 1.34 Å. The C(3)-H(5) bond length is 1.08 Å. In the second C site, C(1) is bonded in a distorted bent 120 degrees geometry to one C(2), one N(2), and one H(4) atom. The C(1)-C(2) bond length is 1.39 Å. The C(1)-N(2) bond length is 1.34 Å. The C(1)-H(4) bond length is 1.08 Å. In the third C site, C(2) is bonded in a trigonal planar geometry to one C(1), one C(3), and one S(1) atom. The C(2)-S(1) bond length is 1.75 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a distorted single-bond geometry to one C(3) atom. In the second N site, N(2) is bonded in a 2-coordinate geometry to one C(1) and one H(3) atom. The N(2)-H(3) bond length is 1.04 Å. There are five inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(4) atom. The H(1)-O(4) bond length is 0.99 Å. In the second H site, H(2) is bonded in a single-bond geometry to one O(4) atom. The H(2)-O(4) bond length is 0.98 Å. In the third H site, H(3) is bonded in a single-bond geometry to one N(2) and one O(1) atom. The H(3)-O(1) bond length is 1.73 Å. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(1) atom. In the fifth H site, H(5) 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 C(2), one O(1), one O(2), and one O(3) atom. The S(1)-O(1) bond length is 1.48 Å. The S(1)-O(2) bond length is 1.47 Å. The S(1)-O(3) bond length is 1.47 Å. There are four inequivalent O sites. In the first O site, O(4) 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(1) is bonded in a 3-coordinate geometry to one Na(1), one H(3), and one S(1) atom. In the third O site, O(2) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one S(1) atom. In the fourth O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Na(1) and one S(1) atom. Linkers: 4 [O]S([O])([O])c1cn[nH]c1 ,4 O. Metal clusters: 4 [Na]. The MOF has largest included sphere 1.51 A, density 1.89 g/cm3, surface area 3037.42 m2/g, accessible volume 0.07 cm3/g