Cu3C36H16(NO2)4 crystallizes in the tetragonal I4/m space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(4) atom. The Cu(1)-O(1) bond length is 2.02 Å. The Cu(1)-O(2) bond length is 1.90 Å. The Cu(1)-O(3) bond length is 1.84 Å. The Cu(1)-O(4) bond length is 1.94 Å. In the second Cu site, Cu(2) is bonded in a square co-planar geometry to two equivalent N(1) and two equivalent N(2) atoms. Both Cu(2)-N(1) bond lengths are 2.07 Å. Both Cu(2)-N(2) bond lengths are 2.05 Å. There are nineteen inequivalent C sites. In the first C site, C(1) is bonded in a bent 120 degrees geometry to one C(3), one O(1), and one O(2) atom. The C(1)-C(3) bond length is 1.48 Å. The C(1)-O(1) bond length is 1.33 Å. The C(1)-O(2) bond length is 1.24 Å. In the second C site, C(2) is bonded in a distorted bent 120 degrees geometry to one C(5), one O(3), and one O(4) atom. The C(2)-C(5) bond length is 1.48 Å. The C(2)-O(3) bond length is 1.24 Å. The C(2)-O(4) bond length is 1.44 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one C(1), one C(4), and one C(8) atom. The C(3)-C(4) bond length is 1.37 Å. The C(3)-C(8) bond length is 1.44 Å. In the fourth C site, C(4) is bonded in a distorted trigonal planar geometry to one C(3), one C(5), and one H(1) atom. The C(4)-C(5) bond length is 1.40 Å. The C(4)-H(1) bond length is 0.95 Å. In the fifth C site, C(5) is bonded in a trigonal planar geometry to one C(2), one C(4), and one C(6) atom. The C(5)-C(6) bond length is 1.44 Å. In the sixth C site, C(6) is bonded in a distorted single-bond geometry to one C(5), one C(7), and one H(2) atom. The C(6)-C(7) bond length is 1.41 Å. The C(6)-H(2) bond length is 0.95 Å. In the seventh C site, C(7) is bonded in a trigonal planar geometry to one C(6), one C(8), and one C(9) atom. The C(7)-C(8) bond length is 1.37 Å. The C(7)-C(9) bond length is 1.50 Å. In the eighth C site, C(8) is bonded in a distorted single-bond geometry to one C(3), one C(7), and one H(3) atom. The C(8)-H(3) bond length is 0.95 Å. In the ninth C site, C(9) is bonded in a trigonal planar geometry to one C(10), one C(11), and one C(7) atom. The C(9)-C(10) bond length is 1.39 Å. The C(9)-C(11) bond length is 1.42 Å. In the tenth C site, C(10) is bonded in a distorted trigonal planar geometry to one C(13), one C(9), and one N(2) atom. The C(10)-C(13) bond length is 1.45 Å. The C(10)-N(2) bond length is 1.42 Å. In the eleventh C site, C(11) is bonded in a distorted trigonal planar geometry to one C(12), one C(9), and one N(1) atom. The C(11)-C(12) bond length is 1.40 Å. The C(11)-N(1) bond length is 1.41 Å. In the twelfth C site, C(12) is bonded in a distorted single-bond geometry to one C(11), one C(16), and one H(4) atom. The C(12)-C(16) bond length is 1.38 Å. The C(12)-H(4) bond length is 0.95 Å. In the thirteenth C site, C(13) is bonded in a distorted single-bond geometry to one C(10) and one H(5) atom. The C(13)-H(5) bond length is 0.95 Å. In the fourteenth C site, C(14) is bonded in a distorted trigonal planar geometry to one C(17), one C(19), and one N(2) atom. The C(14)-C(17) bond length is 1.44 Å. The C(14)-C(19) bond length is 1.44 Å. The C(14)-N(2) bond length is 1.41 Å. In the fifteenth C site, C(15) is bonded in a distorted single-bond geometry to one C(16), one C(18), and one N(1) atom. The C(15)-C(16) bond length is 1.44 Å. The C(15)-C(18) bond length is 1.40 Å. The C(15)-N(1) bond length is 1.30 Å. In the sixteenth C site, C(16) is bonded in a 3-coordinate geometry to one C(12), one C(15), and one H(6) atom. The C(16)-H(6) bond length is 0.95 Å. In the seventeenth C site, C(17) is bonded in a distorted single-bond geometry to one C(14) and one H(7) atom. The C(17)-H(7) bond length is 0.95 Å. In the eighteenth C site, C(18) is bonded in a distorted trigonal planar geometry to two equivalent C(15) and one H(8) atom. The C(18)-H(8) bond length is 0.95 Å. In the nineteenth C site, C(19) is bonded in a single-bond geometry to two equivalent C(14) and one H(9) atom. The C(19)-H(9) bond length is 0.95 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a trigonal planar geometry to one Cu(2), one C(11), and one C(15) atom. In the second N site, N(2) is bonded in a trigonal planar geometry to one Cu(2), one C(10), and one C(14) atom. There are nine inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(4) atom. In the second H site, H(2) is bonded in a single-bond geometry to one C(6) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(8) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(12) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one C(13) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one C(16) atom. In the seventh H site, H(7) is bonded in a single-bond geometry to one C(17) atom. In the eighth H site, H(8) is bonded in a single-bond geometry to one C(18) atom. In the ninth H site, H(9) is bonded in a single-bond geometry to one C(19) atom. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Cu(1) and one C(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Cu(1) and one C(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Cu(1) and one C(2) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Cu(1) and one C(2) atom. Linkers: 2 [O]C(=O)c1cc(cc(c1)C1=C2C=CC3=[N]2[Cu@@]24n5c1ccc5C=C1[N]2=C(C=C1)C(=c1n4c(=C3)cc1)c1cc(cc(c1)C(=O)[O])C(=O)[O])C(=O)[O] ,2 [O]C(=O)c1cc(cc(c1)C1=C2C=CC3=[N]2[Cu@]24n5c1ccc5C=C1[N]2=C(C=C1)C(=c1n4c(=C3)cc1)c1cc(cc(c1)C(=O)[O])C(=O)[O])C(=O)[O]. Metal clusters: 4 [C]1O[Cu]234O[C]O[Cu]2(O1)(O[C]O3)O[C]O4. RCSR code: ssb. The MOF has largest included sphere 12.83 A, density 0.87 g/cm3, surface area 3627.12 m2/g, accessible volume 0.70 cm3/g