NaC5NH4SO5(CH)2 crystallizes in the orthorhombic Pnma space group. The structure consists of eight 02329_fluka molecules inside a NaC5NH4SO5 framework. In the NaC5NH4SO5 framework, Na(1) is bonded to one N(1), one O(2), one O(3), one O(4), and two equivalent O(1) atoms to form distorted NaNO5 octahedra that share corners with three equivalent S(1)CNO2 tetrahedra. The Na(1)-N(1) bond length is 2.56 Å. The Na(1)-O(2) bond length is 2.35 Å. The Na(1)-O(3) bond length is 2.32 Å. The Na(1)-O(4) bond length is 2.47 Å. Both Na(1)-O(1) bond lengths are 2.28 Å. There are five 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 C(7) atom. The C(2)-C(1) bond length is 1.49 Å. The C(2)-C(3) bond length is 1.41 Å. The C(2)-C(7) bond length is 1.40 Å. In the second C site, C(3) is bonded in a distorted single-bond geometry to one C(2) and one O(3) atom. The C(3)-O(3) bond length is 1.34 Å. In the third C site, C(6) is bonded in a distorted single-bond geometry to one C(7) and one H(5) atom. The C(6)-C(7) bond length is 1.38 Å. The C(6)-H(5) bond length is 1.09 Å. In the fourth C site, C(7) is bonded in a trigonal planar geometry to one C(2), one C(6), and one S(1) atom. The C(7)-S(1) bond length is 1.77 Å. In the fifth C site, C(1) is bonded in a distorted bent 120 degrees geometry to one C(2), one N(1), and one O(2) atom. The C(1)-N(1) bond length is 1.36 Å. The C(1)-O(2) bond length is 1.27 Å. N(1) is bonded in a distorted trigonal planar geometry to one Na(1), one C(1), and one S(1) atom. The N(1)-S(1) bond length is 1.62 Å. There are three 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 0.98 Å. In the second H site, H(2) is bonded in a linear geometry to one O(2) and one O(3) atom. The H(2)-O(2) bond length is 1.56 Å. The H(2)-O(3) bond length is 1.03 Å. In the third H site, H(5) is bonded in a single-bond geometry to one C(6) atom. S(1) is bonded to one C(7), one N(1), and two equivalent O(1) atoms to form distorted SCNO2 tetrahedra that share corners with three equivalent Na(1)NO5 octahedra. The corner-sharing octahedral tilt angles range from 26-64°. Both S(1)-O(1) bond lengths are 1.46 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Na(1) and one S(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(1), one C(1), and one H(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Na(1), one C(3), and one H(2) atom. In the fourth O site, O(4) is bonded in a water-like geometry to one Na(1) and two equivalent H(1) atoms. Linkers: 4 O=C1[N]S(=O)(=O)c2cccc(O)c21. Metal clusters: 4 [Na]. The MOF has largest included sphere 1.76 A, density 1.76 g/cm3, surface area 3544.06 m2/g, accessible volume 0.10 cm3/g