Na2CoH8(C5O2)4(CH)4 crystallizes in the tetragonal I4_1cd space group. The structure consists of thirty-two 02329_fluka molecules inside a Na2CoH8(C5O2)4 framework. In the Na2CoH8(C5O2)4 framework, Na(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(2), and two equivalent O(4) atoms. The Na(1)-O(1) bond length is 2.33 Å. The Na(1)-O(2) bond length is 2.34 Å. There is one shorter (2.35 Å) and one longer (2.38 Å) Na(1)-O(4) bond length. Co(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. Both Co(1)-O(1) bond lengths are 2.38 Å. Both Co(1)-O(2) bond lengths are 2.07 Å. Both Co(1)-O(3) bond lengths are 2.00 Å. There are ten inequivalent C sites. In the first C site, C(10) is bonded in a distorted single-bond geometry to one C(11) and one H(6) atom. The C(10)-C(11) bond length is 1.41 Å. The C(10)-H(6) bond length is 0.93 Å. In the second C site, C(11) is bonded in a trigonal planar geometry to one C(10), one C(2), and one C(6) atom. The C(11)-C(2) bond length is 1.44 Å. The C(11)-C(6) bond length is 1.42 Å. In the third C site, C(12) is bonded in a distorted bent 120 degrees geometry to one C(5), one O(3), and one O(4) atom. The C(12)-C(5) bond length is 1.53 Å. The C(12)-O(3) bond length is 1.27 Å. The C(12)-O(4) bond length is 1.23 Å. In the fourth C site, C(1) is bonded in a distorted bent 120 degrees geometry to one C(2), one O(1), and one O(2) atom. The C(1)-C(2) bond length is 1.52 Å. The C(1)-O(1) bond length is 1.24 Å. The C(1)-O(2) bond length is 1.27 Å. In the fifth C site, C(2) is bonded in a trigonal planar geometry to one C(1), one C(11), and one C(3) atom. The C(2)-C(3) bond length is 1.36 Å. In the sixth C site, C(3) is bonded in a distorted single-bond geometry to one C(2) and one H(1) atom. The C(3)-H(1) bond length is 0.93 Å. In the seventh C site, C(4) is bonded in a single-bond geometry to one C(5) and one H(2) atom. The C(4)-C(5) bond length is 1.36 Å. The C(4)-H(2) bond length is 0.93 Å. In the eighth C site, C(5) is bonded in a trigonal planar geometry to one C(12), one C(4), and one C(6) atom. The C(5)-C(6) bond length is 1.43 Å. In the ninth C site, C(6) is bonded in a trigonal planar geometry to one C(11), one C(5), and one C(7) atom. The C(6)-C(7) bond length is 1.43 Å. In the tenth C site, C(7) is bonded in a distorted single-bond geometry to one C(6) and one H(3) atom. The C(7)-H(3) bond length is 0.93 Å. There are four inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(3) atom. In the second H site, H(2) is bonded in a single-bond geometry to one C(4) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(7) atom. In the fourth H site, H(6) is bonded in a single-bond geometry to one C(10) atom. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Co(1), and one C(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Co(1), and one C(1) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Co(1) and one C(12) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one C(12) atom. Linkers: 8 [O]C(=O)c1ccc(C([O])=O)c2ccccc12. Metal clusters: 8 [Na] ,4 [Co]. The MOF has largest included sphere 5.69 A, density 1.20 g/cm3, surface area 3781.16 m2/g, accessible volume 0.34 cm3/g