NaCuC6H6SO8CH crystallizes in the monoclinic C2/c space group. The structure consists of eight 02329_fluka molecules inside a NaCuC6H6SO8 framework. In the NaCuC6H6SO8 framework, there are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1), two equivalent O(6), and two equivalent O(7) atoms to form NaO6 octahedra that share  an edgeedge with one Na(2)O6 octahedra and edges with two equivalent Cu(1)O5 square pyramids. Both Na(1)-O(1) bond lengths are 2.36 Å. Both Na(1)-O(6) bond lengths are 2.38 Å. Both Na(1)-O(7) bond lengths are 2.43 Å. In the second Na site, Na(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(8) atoms to form distorted NaO6 octahedra that share  an edgeedge with one Na(1)O6 octahedra and edges with two equivalent Cu(1)O5 square pyramids. Both Na(2)-O(1) bond lengths are 2.31 Å. Both Na(2)-O(2) bond lengths are 2.40 Å. Both Na(2)-O(8) bond lengths are 2.49 Å. Cu(1) is bonded to one O(2), one O(5), one O(6), one O(7), and one O(8) atom to form distorted CuO5 square pyramids that share  an edgeedge with one Na(1)O6 octahedra and  an edgeedge with one Na(2)O6 octahedra. The Cu(1)-O(2) bond length is 2.50 Å. The Cu(1)-O(5) bond length is 1.92 Å. The Cu(1)-O(6) bond length is 1.90 Å. The Cu(1)-O(7) bond length is 2.00 Å. The Cu(1)-O(8) bond length is 2.02 Å. There are six inequivalent C sites. In the first 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)-C(2) bond length is 1.38 Å. The C(1)-C(6) bond length is 1.41 Å. The C(1)-S(1) bond length is 1.76 Å. In the second C site, C(2) is bonded in a distorted single-bond geometry to one C(1), one C(3), and one H(5) atom. The C(2)-C(3) bond length is 1.40 Å. The C(2)-H(5) bond length is 1.09 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one C(2), one C(4), and one C(7) atom. The C(3)-C(4) bond length is 1.43 Å. The C(3)-C(7) bond length is 1.48 Å. In the fourth C site, C(4) is bonded in a distorted single-bond geometry to one C(3) and one O(6) atom. The C(4)-O(6) bond length is 1.32 Å. In the fifth C site, C(6) is bonded in a distorted single-bond geometry to one C(1) and one H(7) atom. The C(6)-H(7) bond length is 1.09 Å. In the sixth C site, C(7) is bonded in a distorted bent 120 degrees geometry to one C(3), one O(4), and one O(5) atom. The C(7)-O(4) bond length is 1.26 Å. The C(7)-O(5) bond length is 1.31 Å. There are six inequivalent H sites. In the first H site, H(1) is bonded in a distorted linear geometry to one O(4) and one O(7) atom. The H(1)-O(4) bond length is 1.56 Å. The H(1)-O(7) bond length is 1.02 Å. In the second H site, H(2) is bonded in a distorted linear geometry to one O(3) and one O(7) atom. The H(2)-O(3) bond length is 1.59 Å. The H(2)-O(7) bond length is 1.01 Å. In the third H site, H(3) is bonded in a single-bond geometry to one O(8) atom. The H(3)-O(8) bond length is 0.97 Å. In the fourth H site, H(4) is bonded in a linear geometry to one O(5) and one O(8) atom. The H(4)-O(5) bond length is 1.53 Å. The H(4)-O(8) bond length is 1.03 Å. In the fifth H site, H(5) is bonded in a single-bond geometry to one C(2) atom. In the sixth H site, H(7) is bonded in a single-bond geometry to one C(6) atom. S(1) is bonded in a distorted trigonal non-coplanar geometry to one C(1), one O(1), one O(2), and one O(3) atom. The S(1)-O(1) bond length is 1.47 Å. The S(1)-O(2) bond length is 1.48 Å. The S(1)-O(3) bond length is 1.48 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), and one S(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(2), one Cu(1), and one S(1) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one H(2) and one S(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one C(7) and one H(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Cu(1), one C(7), and one H(4) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Na(1), one Cu(1), and one C(4) atom. In the seventh O site, O(7) is bonded in a distorted water-like geometry to one Na(1), one Cu(1), one H(1), and one H(2) atom. In the eighth O site, O(8) is bonded in a distorted water-like geometry to one Na(2), one Cu(1), one H(3), and one H(4) atom. Linkers: 4 [O]C(=O)c1cc(S([O])([O])[O])ccc1[O]. Metal clusters: 4 [Na] ,4 [Cu]. The MOF has largest included sphere 5.04 A, density 1.67 g/cm3, surface area 2653.67 m2/g, accessible volume 0.24 cm3/g