NaH(CO2)2CH2CH crystallizes in the orthorhombic Pbcn space group. The structure consists of eight 02329_fluka molecules and eight 02329_fluka molecules inside a NaH(CO2)2 framework. In the NaH(CO2)2 framework, Na(1) is bonded in a 6-coordinate geometry to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms. The Na(1)-O(2) bond length is 2.45 Å. The Na(1)-O(4) bond length is 2.37 Å. There is one shorter (2.37 Å) and one longer (2.62 Å) Na(1)-O(1) bond length. There is one shorter (2.40 Å) and one longer (2.44 Å) Na(1)-O(3) bond length. There are two inequivalent C sites. In the first C site, C(4) is bonded in a distorted bent 120 degrees geometry to one O(3) and one O(4) atom. The C(4)-O(3) bond length is 1.26 Å. The C(4)-O(4) bond length is 1.29 Å. In the second C site, C(1) is bonded in a distorted bent 120 degrees geometry to one O(1) and one O(2) atom. The C(1)-O(1) bond length is 1.24 Å. The C(1)-O(2) bond length is 1.32 Å. H(4) is bonded in a linear geometry to one O(2) and one O(4) atom. The H(4)-O(2) bond length is 1.10 Å. The H(4)-O(4) bond length is 1.39 Å. There are four inequivalent O sites. In the first O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one C(4), and one H(4) atom. In the second O site, O(1) is bonded in a distorted single-bond geometry to two equivalent Na(1) and one C(1) atom. In the third O site, O(2) is bonded in a distorted water-like geometry to one Na(1), one C(1), and one H(4) atom. In the fourth O site, O(3) is bonded in a distorted single-bond geometry to two equivalent Na(1) and one C(4) atom. Linkers: 4 [O]C(=O)[C@@H](CC(=O)O)[C@@H](CC(=O)O)C([O])=O. Metal clusters: 8 [Na]. The MOF has largest included sphere 1.62 A, density 1.91 g/cm3, surface area 2210.48 m2/g, accessible volume 0.05 cm3/g