Li4C5H5(SO5)2CH crystallizes in the orthorhombic Pnma space group. The structure consists of four 02329_fluka molecules inside a Li4C5H5(SO5)2 framework. In the Li4C5H5(SO5)2 framework, there are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a trigonal non-coplanar geometry to one O(1), one O(2), and one O(5) atom. The Li(1)-O(1) bond length is 1.95 Å. The Li(1)-O(2) bond length is 1.93 Å. The Li(1)-O(5) bond length is 1.93 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one H(2), one O(1), one O(4), and two equivalent O(5) atoms. The Li(2)-H(2) bond length is 1.42 Å. The Li(2)-O(1) bond length is 2.53 Å. The Li(2)-O(4) bond length is 2.08 Å. There is one shorter (2.03 Å) and one longer (2.06 Å) Li(2)-O(5) bond length. There are three inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one C(2), one C(3), and one S(1) atom. The C(1)-C(2) bond length is 1.42 Å. The C(1)-C(3) bond length is 1.38 Å. The C(1)-S(1) bond length is 1.74 Å. In the second C site, C(2) is bonded in a single-bond geometry to one C(1) and one O(5) atom. The C(2)-O(5) bond length is 1.33 Å. In the third C site, C(3) is bonded in a distorted single-bond geometry to two equivalent C(1) and one H(3) atom. The C(3)-H(3) bond length is 0.93 Å. There are three inequivalent H sites. In the first H site, H(3) is bonded in a single-bond geometry to one C(3) atom. In the second H site, H(1) is bonded in a single-bond geometry to one O(3) atom. The H(1)-O(3) bond length is 0.82 Å. In the third H site, H(2) is bonded in a bent 120 degrees geometry to one Li(2) and one O(3) atom. The H(2)-O(3) bond length is 0.82 Å. S(1) is bonded in a distorted trigonal non-coplanar geometry to one C(1), one O(1), one O(2), and one O(4) 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(4) bond length is 1.47 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Li(1), one Li(2), and one S(1) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Li(1) and one S(1) atom. In the third O site, O(3) is bonded in a water-like geometry to one H(1) and one H(2) atom. In the fourth O site, O(4) is bonded in a water-like geometry to one Li(2) and one S(1) atom. In the fifth O site, O(5) is bonded to one Li(1), two equivalent Li(2), and one C(2) atom to form distorted edge-sharing OLi3C trigonal pyramids. Linkers: 4 [O]c1cc([O])c(S([O])([O])[O])cc1S([O])([O])[O]. Metal clusters: 16 [Li]. The MOF has largest included sphere 4.11 A, density 1.38 g/cm3, surface area 3688.21 m2/g, accessible volume 0.25 cm3/g