LiCO2CH2 crystallizes in the trigonal R-3 space group. The structure consists of eighteen 02329_fluka molecules inside a LiCO2 framework. In the LiCO2 framework, Li(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form a mixture of edge and corner-sharing LiO4 tetrahedra. There is one shorter (1.94 Å) and one longer (1.96 Å) Li(1)-O(1) bond length. There is one shorter (1.95 Å) and one longer (1.96 Å) Li(1)-O(2) bond length. 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 1.28 Å. The C(1)-O(2) bond length is 1.27 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to two equivalent Li(1) and one C(1) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to two equivalent Li(1) and one C(1) atom. Linkers: 3 [O]C(=O)CCC([O])=O. Metal clusters: 6 [Li]. The MOF has largest included sphere 2.68 A, density 1.46 g/cm3, surface area 3887.13 m2/g, accessible volume 0.14 cm3/g