NaC4NH4S2O5(CH)2 crystallizes in the orthorhombic Pna2_1 space group. The structure consists of eight 02329_fluka molecules inside a NaC4NH4S2O5 framework. In the NaC4NH4S2O5 framework, Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(4), one O(5), and two equivalent O(3) atoms. The Na(1)-O(1) bond length is 2.42 Å. The Na(1)-O(2) bond length is 2.39 Å. The Na(1)-O(4) bond length is 2.79 Å. The Na(1)-O(5) bond length is 2.33 Å. There is one shorter (2.33 Å) and one longer (2.47 Å) Na(1)-O(3) bond length. There are four inequivalent C sites. In the first C site, C(2) is bonded in a trigonal planar geometry to one C(1), one C(3), and one S(2) atom. The C(2)-C(1) bond length is 1.39 Å. The C(2)-C(3) bond length is 1.39 Å. The C(2)-S(2) bond length is 1.77 Å. In the second C site, C(3) is bonded in a distorted single-bond geometry to one C(2) and one H(1) atom. The C(3)-H(1) bond length is 1.09 Å. In the third C site, C(6) is bonded in a distorted single-bond geometry to one C(1) and one H(4) atom. The C(6)-C(1) bond length is 1.39 Å. The C(6)-H(4) bond length is 1.09 Å. In the fourth C site, C(1) is bonded in a trigonal planar geometry to one C(2), one C(6), and one S(1) atom. The C(1)-S(1) bond length is 1.78 Å. N(1) is bonded in a bent 120 degrees geometry to one S(1) and one S(2) atom. The N(1)-S(1) bond length is 1.59 Å. The N(1)-S(2) bond length is 1.59 Å. There are four inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(3) atom. In the second H site, H(4) is bonded in a single-bond geometry to one C(6) atom. In the third H site, H(5) is bonded in a single-bond geometry to one O(5) atom. The H(5)-O(5) bond length is 0.98 Å. In the fourth H site, H(6) is bonded in a single-bond geometry to one O(5) atom. The H(6)-O(5) bond length is 0.98 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to one C(1), one N(1), one O(1), and one O(2) atom to form distorted corner-sharing SCNO2 tetrahedra. The S(1)-O(1) bond length is 1.47 Å. The S(1)-O(2) bond length is 1.46 Å. In the second S site, S(2) is bonded to one C(2), one N(1), one O(3), and one O(4) atom to form distorted corner-sharing SCNO2 tetrahedra. The S(2)-O(3) bond length is 1.46 Å. The S(2)-O(4) bond length is 1.46 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Na(1) and one S(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Na(1) and one S(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one S(2) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Na(1) and one S(2) atom. In the fifth O site, O(5) is bonded in a distorted water-like geometry to one Na(1), one H(5), and one H(6) atom. Linkers: 4 O=S1(=O)[N]S(=O)(=O)c2ccccc21. Metal clusters: 4 [Na]. The MOF has largest included sphere 1.91 A, density 1.80 g/cm3, surface area 3486.40 m2/g, accessible volume 0.13 cm3/g