LiSO2Cl(CH2)4 crystallizes in the orthorhombic Pna2_1 space group. The structure consists of sixteen 02329_fluka molecules inside a LiSO2Cl framework. In the LiSO2Cl framework, Li(1) is bonded to one O(1), one O(2), and two equivalent Cl(1) atoms to form corner-sharing LiCl2O2 tetrahedra. The Li(1)-O(1) bond length is 2.00 Å. The Li(1)-O(2) bond length is 1.96 Å. There is one shorter (2.32 Å) and one longer (2.35 Å) Li(1)-Cl(1) bond length. S(1) is bonded in a distorted bent 120 degrees geometry to one O(1) and one O(2) atom. The S(1)-O(1) bond length is 1.47 Å. The S(1)-O(2) bond length is 1.47 Å. There are two inequivalent O sites. In the first O site, O(2) is bonded in a bent 150 degrees geometry to one Li(1) and one S(1) atom. In the second O site, O(1) is bonded in a bent 120 degrees geometry to one Li(1) and one S(1) atom. Cl(1) is bonded in a water-like geometry to two equivalent Li(1) atoms. Linkers: 4 O=S1(=O)CCCC1. Metal clusters: 4 [Li]. The MOF has largest included sphere 1.40 A, density 1.63 g/cm3, surface area 4741.17 m2/g, accessible volume 0.12 cm3/g