RbH(CO2)2(CH)2 crystallizes in the orthorhombic Pca2_1 space group. The structure consists of eight 02329_fluka molecules inside a RbH(CO2)2 framework. In the RbH(CO2)2 framework, Rb(1) is bonded to one O(2), one O(3), three equivalent O(1), and three equivalent O(4) atoms to form edge-sharing RbO8 hexagonal bipyramids. The Rb(1)-O(2) bond length is 3.23 Å. The Rb(1)-O(3) bond length is 3.21 Å. There is one shorter (2.95 Å) and two longer (2.97 Å) Rb(1)-O(1) bond lengths. There are a spread of Rb(1)-O(4) bond distances ranging from 2.94-2.99 Å. There are two inequivalent C sites. In the first 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 1.26 Å. The C(1)-O(2) bond length is 1.30 Å. In the second 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 1.30 Å. The C(4)-O(4) bond length is 1.26 Å. H(3) is bonded in a linear geometry to one O(2) and one O(3) atom. The H(3)-O(2) bond length is 1.21 Å. The H(3)-O(3) bond length is 1.20 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to three equivalent Rb(1) and one C(1) atom. In the second O site, O(2) is bonded in a water-like geometry to one Rb(1), one C(1), and one H(3) atom. In the third O site, O(3) is bonded in a water-like geometry to one Rb(1), one C(4), and one H(3) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to three equivalent Rb(1) and one C(4) atom. Linkers: 4 [O]C(=O)/C=C\C([O])=O. Metal clusters: 4 [Rb]. The MOF has largest included sphere 1.85 A, density 2.18 g/cm3, surface area 3256.78 m2/g, accessible volume 0.08 cm3/g