(NaH2SO4)3CH crystallizes in the monoclinic P2_1/c space group. The structure consists of four 02329_fluka molecules inside a NaH2SO4 framework. In the NaH2SO4 framework, there are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(1), one O(3), one O(4), one O(6), one O(7), and two equivalent O(5) atoms. The Na(1)-O(1) bond length is 2.42 Å. The Na(1)-O(3) bond length is 2.36 Å. The Na(1)-O(4) bond length is 2.37 Å. The Na(1)-O(6) bond length is 2.55 Å. The Na(1)-O(7) bond length is 2.48 Å. There is one shorter (2.45 Å) and one longer (2.72 Å) Na(1)-O(5) bond length. In the second Na site, Na(2) is bonded in a distorted octahedral geometry to one O(10), one O(4), one O(5), one O(6), one O(7), and one O(8) atom. The Na(2)-O(10) bond length is 2.42 Å. The Na(2)-O(4) bond length is 2.39 Å. The Na(2)-O(5) bond length is 2.34 Å. The Na(2)-O(6) bond length is 2.34 Å. The Na(2)-O(7) bond length is 2.44 Å. The Na(2)-O(8) bond length is 2.40 Å. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to one O(1), one O(11), one O(12), one O(2), and one O(9) atom. The Na(3)-O(1) bond length is 2.38 Å. The Na(3)-O(11) bond length is 2.34 Å. The Na(3)-O(12) bond length is 2.35 Å. The Na(3)-O(2) bond length is 2.34 Å. The Na(3)-O(9) bond length is 2.35 Å. There are six inequivalent H sites. In the first H site, H(2) is bonded in a single-bond geometry to one O(10) atom. The H(2)-O(10) bond length is 0.98 Å. In the second H site, H(3) is bonded in a single-bond geometry to one O(10) and one O(3) atom. The H(3)-O(10) bond length is 0.99 Å. The H(3)-O(3) bond length is 1.77 Å. In the third H site, H(4) is bonded in a single-bond geometry to one O(11) atom. The H(4)-O(11) bond length is 0.98 Å. In the fourth H site, H(5) is bonded in a single-bond geometry to one O(11) atom. The H(5)-O(11) bond length is 0.99 Å. In the fifth H site, H(6) is bonded in a single-bond geometry to one O(12) atom. The H(6)-O(12) bond length is 0.98 Å. In the sixth H site, H(7) is bonded in a single-bond geometry to one O(12) atom. The H(7)-O(12) bond length is 0.98 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded in a distorted trigonal non-coplanar geometry to one O(1), one O(2), and one O(3) atom. The S(1)-O(1) bond length is 1.46 Å. The S(1)-O(2) bond length is 1.46 Å. The S(1)-O(3) bond length is 1.46 Å. In the second S site, S(2) is bonded in a distorted trigonal non-coplanar geometry to one O(4), one O(5), and one O(6) atom. The S(2)-O(4) bond length is 1.46 Å. The S(2)-O(5) bond length is 1.47 Å. The S(2)-O(6) bond length is 1.46 Å. In the third S site, S(3) is bonded in a distorted trigonal non-coplanar geometry to one O(7), one O(8), and one O(9) atom. The S(3)-O(7) bond length is 1.47 Å. The S(3)-O(8) bond length is 1.47 Å. The S(3)-O(9) bond length is 1.46 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(3), and one S(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Na(3) and one S(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one H(3), and one S(1) 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(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(1), and one S(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate 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 trigonal planar geometry to one Na(1), one Na(2), and one S(3) atom. In the eighth O site, O(8) is bonded in a distorted bent 120 degrees geometry to one Na(2) and one S(3) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Na(3) and one S(3) atom. In the tenth O site, O(10) is bonded in a water-like geometry to one Na(2), one H(2), and one H(3) atom. In the eleventh O site, O(11) is bonded in a distorted water-like geometry to one Na(3), one H(4), and one H(5) atom. In the twelfth O site, O(12) is bonded in a distorted water-like geometry to one Na(3), one H(6), and one H(7) atom. Linkers: 4 [O]S([O])([O])C(S([O])([O])[O])S([O])([O])[O]. Metal clusters: 12 [Na]. The MOF has largest included sphere 1.71 A, density 2.21 g/cm3, surface area 1763.49 m2/g, accessible volume 0.03 cm3/g