Na2C6H6S2O9 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(5), one O(6), one O(7), and one O(9) atom. The Na(1)-O(1) bond length is 2.87 Å. The Na(1)-O(3) bond length is 2.38 Å. The Na(1)-O(5) bond length is 2.38 Å. The Na(1)-O(6) bond length is 2.31 Å. The Na(1)-O(7) bond length is 2.41 Å. The Na(1)-O(9) bond length is 2.30 Å. In the second Na site, Na(2) is bonded in an octahedral geometry to one O(1), one O(4), one O(5), one O(6), one O(8), and one O(9) atom. The Na(2)-O(1) bond length is 2.55 Å. The Na(2)-O(4) bond length is 2.33 Å. The Na(2)-O(5) bond length is 2.33 Å. The Na(2)-O(6) bond length is 2.32 Å. The Na(2)-O(8) bond length is 2.29 Å. The Na(2)-O(9) bond length is 2.44 Å. There are six inequivalent C sites. In the first C site, C(1) is bonded in a distorted single-bond geometry to one C(6) and one O(1) atom. The C(1)-C(6) bond length is 1.41 Å. The C(1)-O(1) bond length is 1.37 Å. In the second C site, C(2) is bonded in a distorted single-bond geometry to one O(2) atom. The C(2)-O(2) bond length is 1.37 Å. In the third C site, C(3) is bonded in a distorted single-bond geometry to one C(4) and one H(5) atom. The C(3)-C(4) bond length is 1.39 Å. The C(3)-H(5) bond length is 1.09 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one C(3), one C(5), and one S(1) atom. The C(4)-C(5) bond length is 1.40 Å. The C(4)-S(1) bond length is 1.77 Å. In the fifth C site, C(5) is bonded in a distorted single-bond geometry to one C(4), one C(6), and one H(6) atom. The C(5)-C(6) bond length is 1.39 Å. The C(5)-H(6) bond length is 1.09 Å. In the sixth C site, C(6) is bonded in a trigonal planar geometry to one C(1), one C(5), and one S(2) atom. The C(6)-S(2) bond length is 1.78 Å. There are six 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 1.00 Å. In the second H site, H(2) is bonded in a single-bond geometry to one O(2) and one O(4) atom. The H(2)-O(2) bond length is 1.00 Å. The H(2)-O(4) bond length is 1.76 Å. In the third H site, H(3) is bonded in a single-bond geometry to one O(9) atom. The H(3)-O(9) bond length is 0.98 Å. In the fourth H site, H(4) is bonded in a single-bond geometry to one O(9) atom. The H(4)-O(9) bond length is 0.99 Å. In the fifth H site, H(5) is bonded in a single-bond geometry to one C(3) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one C(5) atom. There are two inequivalent S sites. In the first S site, S(1) is bonded in a distorted trigonal non-coplanar geometry to one C(4), one O(3), one O(4), and one O(5) atom. The S(1)-O(3) bond length is 1.48 Å. The S(1)-O(4) bond length is 1.48 Å. The S(1)-O(5) bond length is 1.47 Å. In the second S site, S(2) is bonded in a distorted trigonal non-coplanar geometry to one C(6), one O(6), one O(7), and one O(8) atom. The S(2)-O(6) bond length is 1.47 Å. The S(2)-O(7) bond length is 1.48 Å. The S(2)-O(8) bond length is 1.46 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one Na(1), one Na(2), one C(1), and one H(1) atom. In the second O site, O(2) is bonded in a water-like geometry to one C(2) and one H(2) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to one Na(1) and one S(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(2), one H(2), and one S(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one S(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), and one S(2) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Na(1) and one S(2) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one Na(2) and one S(2) atom. In the ninth O site, O(9) is bonded in a distorted water-like geometry to one Na(1), one Na(2), one H(3), and one H(4) atom. Linkers: 4 [O]S([O])([O])c1cc(O)c(O)c(S([O])([O])[O])c1. Metal clusters: 8 [Na]. The MOF has largest included sphere 1.34 A, density 2.10 g/cm3, surface area 2434.96 m2/g, accessible volume 0.03 cm3/g