Na4CoC52H20(NO4)4 crystallizes in the orthorhombic Imma space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. Both Na(1)-O(1) bond lengths are 2.38 Å. Both Na(1)-O(2) bond lengths are 2.34 Å. Both Na(1)-O(3) bond lengths are 2.46 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms. Both Na(2)-O(1) bond lengths are 2.29 Å. Both Na(2)-O(2) bond lengths are 2.41 Å. Both Na(2)-O(4) bond lengths are 2.44 Å. Co(1) is bonded in a rectangular see-saw-like geometry to two equivalent N(1) and two equivalent N(2) atoms. Both Co(1)-N(1) bond lengths are 1.97 Å. Both Co(1)-N(2) bond lengths are 1.98 Å. There are thirteen inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one C(12), one C(3), and one C(8) atom. The C(1)-C(12) bond length is 1.52 Å. The C(1)-C(3) bond length is 1.38 Å. The C(1)-C(8) bond length is 1.39 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one C(7), one C(8), and one C(9) atom. The C(2)-C(7) bond length is 1.50 Å. The C(2)-C(8) bond length is 1.38 Å. The C(2)-C(9) bond length is 1.39 Å. In the third C site, C(3) is bonded in a distorted single-bond geometry to one C(1), one C(4), and one H(1) atom. The C(3)-C(4) bond length is 1.37 Å. The C(3)-H(1) bond length is 0.95 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one C(13), one C(3), and one C(9) atom. The C(4)-C(13) bond length is 1.51 Å. The C(4)-C(9) bond length is 1.40 Å. In the fifth C site, C(5) is bonded in a trigonal planar geometry to one C(11), one C(7), and one N(1) atom. The C(5)-C(11) bond length is 1.42 Å. The C(5)-C(7) bond length is 1.39 Å. The C(5)-N(1) bond length is 1.37 Å. In the sixth C site, C(6) is bonded in a distorted trigonal planar geometry to one C(10), one C(7), and one N(2) atom. The C(6)-C(10) bond length is 1.44 Å. The C(6)-C(7) bond length is 1.38 Å. The C(6)-N(2) bond length is 1.37 Å. In the seventh C site, C(7) is bonded in a trigonal planar geometry to one C(2), one C(5), and one C(6) atom. In the eighth C site, C(8) is bonded in a distorted single-bond geometry to one C(1), one C(2), and one H(2) atom. The C(8)-H(2) bond length is 0.95 Å. In the ninth C site, C(9) is bonded in a distorted single-bond geometry to one C(2), one C(4), and one H(3) atom. The C(9)-H(3) bond length is 0.95 Å. In the tenth C site, C(10) is bonded in a distorted single-bond geometry to one C(6) and one H(4) atom. The C(10)-H(4) bond length is 0.95 Å. In the eleventh C site, C(11) is bonded in a distorted single-bond geometry to one C(5) and one H(5) atom. The C(11)-H(5) bond length is 0.95 Å. In the twelfth C site, C(12) is bonded in a distorted bent 120 degrees geometry to one C(1), one O(1), and one O(3) atom. The C(12)-O(1) bond length is 1.24 Å. The C(12)-O(3) bond length is 1.23 Å. In the thirteenth C site, C(13) is bonded in a distorted bent 120 degrees geometry to one C(4), one O(2), and one O(4) atom. The C(13)-O(2) bond length is 1.24 Å. The C(13)-O(4) bond length is 1.24 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a distorted trigonal planar geometry to one Co(1) and two equivalent C(5) atoms. In the second N site, N(2) is bonded in a distorted trigonal planar geometry to one Co(1) and two equivalent C(6) atoms. There are five 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(8) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(9) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(10) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one C(11) atom. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Na(1), one Na(2), and one C(12) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Na(1), one Na(2), and one C(13) atom. In the third O site, O(3) is bonded in an L-shaped geometry to one Na(1) and one C(12) atom. In the fourth O site, O(4) is bonded in an L-shaped geometry to one Na(2) and one C(13) atom. Linkers: 4 [O]C(=O)c1cc(cc(c1)C1=C2C=CC3=[N]2[Co@]24n5c1ccc5C(=C1[N]2=C(C=C1)C(=c1n4c(=C3c2cc(cc(c2)C(=O)[O])C(=O)[O])cc1)c1cc(cc(c1)C(=O)[O])C(=O)[O])c1cc(cc(c1)C(=O)[O])C(=O)[O])C(=O)[O]. Metal clusters: 16 [Na]. The MOF has largest included sphere 9.31 A, density 0.71 g/cm3, surface area 3994.81 m2/g, accessible volume 0.85 cm3/g