Tb(CO2)3(CH)2 crystallizes in the orthorhombic Fddd space group. The structure consists of thirty-two 02329_fluka molecules inside a Tb(CO2)3 framework. In the Tb(CO2)3 framework, Tb(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. Both Tb(1)-O(1) bond lengths are 2.33 Å. Both Tb(1)-O(2) bond lengths are 2.46 Å. Both Tb(1)-O(3) bond lengths are 2.43 Å. There are two inequivalent C sites. In the first C site, C(3) is bonded in a distorted bent 120 degrees geometry to two equivalent O(3) atoms. Both C(3)-O(3) bond lengths are 1.25 Å. In the second C site, C(1) is bonded in a 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 1.26 Å. There are three inequivalent O sites. In the first O site, O(2) is bonded in a distorted water-like geometry to one Tb(1) and one C(1) atom. In the second O site, O(1) is bonded in a 2-coordinate geometry to one Tb(1) and one C(1) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Tb(1) and one C(3) atom. Linkers: 4 [O]C(=O)/C=C/C([O])=O ,2 [O]C(=O)C([O])=O. Metal clusters: 4 [Tb]. The MOF has largest included sphere 4.31 A, density 2.07 g/cm3, surface area 2404.10 m2/g, accessible volume 0.21 cm3/g