Na2C6H8S2O11 crystallizes in the triclinic P-1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in an octahedral geometry to one O(10), one O(3), one O(4), one O(7), one O(8), and one O(9) atom. The Na(1)-O(10) bond length is 2.35 Å. The Na(1)-O(3) bond length is 2.41 Å. The Na(1)-O(4) bond length is 2.38 Å. The Na(1)-O(7) bond length is 2.36 Å. The Na(1)-O(8) bond length is 2.35 Å. The Na(1)-O(9) bond length is 2.29 Å. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(11), one O(2), one O(4), one O(5), one O(6), and one O(8) atom. The Na(2)-O(1) bond length is 2.41 Å. The Na(2)-O(11) bond length is 2.38 Å. The Na(2)-O(2) bond length is 2.40 Å. The Na(2)-O(4) bond length is 2.46 Å. The Na(2)-O(5) bond length is 2.87 Å. The Na(2)-O(6) bond length is 2.82 Å. The Na(2)-O(8) bond length is 2.42 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 1.77 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(1) atom. The C(2)-C(3) bond length is 1.39 Å. The C(2)-H(1) bond length is 1.08 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one C(2), one C(4), and one S(2) atom. The C(3)-C(4) bond length is 1.41 Å. The C(3)-S(2) bond length is 1.76 Å. In the fourth C site, C(4) is bonded in a distorted single-bond geometry to one C(3) and one O(1) atom. The C(4)-O(1) bond length is 1.36 Å. In the fifth C site, C(5) is bonded in a distorted single-bond geometry to one O(2) atom. The C(5)-O(2) bond length is 1.36 Å. In the sixth C site, C(6) is bonded in a distorted single-bond geometry to one C(1) and one O(3) atom. The C(6)-O(3) bond length is 1.36 Å. There are eight inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(2) atom. In the second H site, H(2) is bonded in a single-bond geometry to one O(1) atom. The H(2)-O(1) bond length is 0.99 Å. In the third H site, H(3) is bonded in a distorted single-bond geometry to one O(10) and one O(2) atom. The H(3)-O(10) bond length is 1.66 Å. The H(3)-O(2) bond length is 1.01 Å. In the fourth H site, H(4) is bonded in a single-bond geometry to one O(3) atom. The H(4)-O(3) bond length is 1.01 Å. In the fifth H site, H(5) is bonded in a single-bond geometry to one O(10) atom. The H(5)-O(10) bond length is 1.00 Å. In the sixth H site, H(6) is bonded in a single-bond geometry to one O(10) atom. The H(6)-O(10) bond length is 0.98 Å. In the seventh H site, H(7) is bonded in a single-bond geometry to one O(11) atom. The H(7)-O(11) bond length is 0.99 Å. In the eighth H site, H(8) is bonded in a single-bond geometry to one O(11) atom. The H(8)-O(11) bond length is 0.99 Å. 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(1), one O(4), one O(5), and one O(6) atom. The S(1)-O(4) bond length is 1.47 Å. The S(1)-O(5) bond length is 1.47 Å. The S(1)-O(6) bond length is 1.49 Å. In the second S site, S(2) is bonded in a distorted trigonal non-coplanar geometry to one C(3), one O(7), one O(8), and one O(9) atom. The S(2)-O(7) bond length is 1.48 Å. The S(2)-O(8) bond length is 1.48 Å. The S(2)-O(9) bond length is 1.46 Å. There are eleven inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Na(2), one C(4), and one H(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(2), one C(5), and one H(3) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one C(6), and one H(4) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one S(1) atom. In the fifth O site, O(5) is bonded in a single-bond geometry to one Na(2) and one S(1) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one Na(2) and one S(1) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one Na(1) and one S(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), and one S(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Na(1) and one S(2) atom. In the tenth O site, O(10) is bonded in a distorted water-like geometry to one Na(1), one H(3), one H(5), and one H(6) atom. In the eleventh O site, O(11) is bonded in a distorted water-like geometry to one Na(2), one H(7), and one H(8) atom. Linkers: 2 [O]S([O])([O])c1cc(S([O])([O])[O])c(O)c(O)c1O. Metal clusters: 4 [Na]. The MOF has largest included sphere 1.52 A, density 2.10 g/cm3, surface area 2242.90 m2/g, accessible volume 0.07 cm3/g