CuC6H6(NO)2 crystallizes in the tetragonal P4_3 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 N(1), one N(3), one O(3), and one O(4) atom. The Cu(1)-N(1) bond length is 1.94 Å. The Cu(1)-N(3) bond length is 1.96 Å. The Cu(1)-O(3) bond length is 1.99 Å. The Cu(1)-O(4) bond length is 2.02 Å. In the second Cu site, Cu(2) is bonded in a distorted square co-planar geometry to one N(2), one N(4), one O(1), and one O(2) atom. The Cu(2)-N(2) bond length is 1.98 Å. The Cu(2)-N(4) bond length is 1.97 Å. The Cu(2)-O(1) bond length is 2.01 Å. The Cu(2)-O(2) bond length is 2.01 Å. There are twelve inequivalent C sites. In the first C site, C(1) is bonded in a trigonal non-coplanar geometry to one C(3); one H(3); and two equivalent H(1,2) atoms. The C(1)-C(3) bond length is 1.54 Å. The C(1)-H(3) bond length is 0.96 Å. Both C(1)-H(1,2) bond lengths are 0.96 Å. In the second C site, C(2) is bonded in a trigonal non-coplanar geometry to one C(4), one H(4), one H(5), and one H(6) atom. The C(2)-C(4) bond length is 1.41 Å. The C(2)-H(4) bond length is 0.96 Å. The C(2)-H(5) bond length is 0.96 Å. The C(2)-H(6) bond length is 0.96 Å. In the third C site, C(3) is bonded in a distorted trigonal planar geometry to one C(1), one C(5), and one N(1) atom. The C(3)-C(5) bond length is 1.35 Å. The C(3)-N(1) bond length is 1.29 Å. In the fourth C site, C(4) is bonded in a 3-coordinate geometry to one C(2), one C(5), and one N(2) atom. The C(4)-C(5) bond length is 1.45 Å. The C(4)-N(2) bond length is 1.38 Å. In the fifth C site, C(5) is bonded in a trigonal planar geometry to one C(3), one C(4), and one C(6) atom. The C(5)-C(6) bond length is 1.45 Å. In the sixth C site, C(6) is bonded in a distorted bent 120 degrees geometry to one C(5), one O(1), and one O(2) atom. The C(6)-O(1) bond length is 1.29 Å. The C(6)-O(2) bond length is 1.26 Å. In the seventh C site, C(7) is bonded in a trigonal non-coplanar geometry to one C(9); one H(7); and two equivalent H(8,9) atoms. The C(7)-C(9) bond length is 1.47 Å. The C(7)-H(7) bond length is 0.96 Å. Both C(7)-H(8,9) bond lengths are 0.96 Å. In the eighth C site, C(8) is bonded in a trigonal non-coplanar geometry to one C(10); one H(11); and two equivalent H(10,12) atoms. The C(8)-C(10) bond length is 1.54 Å. The C(8)-H(11) bond length is 0.96 Å. Both C(8)-H(10,12) bond lengths are 0.96 Å. In the ninth C site, C(9) is bonded in a 3-coordinate geometry to one C(11), one C(7), and one N(3) atom. The C(9)-C(11) bond length is 1.44 Å. The C(9)-N(3) bond length is 1.34 Å. In the tenth C site, C(10) is bonded in a distorted trigonal planar geometry to one C(11), one C(8), and one N(4) atom. The C(10)-C(11) bond length is 1.36 Å. The C(10)-N(4) bond length is 1.30 Å. In the eleventh C site, C(11) is bonded in a trigonal planar geometry to one C(10), one C(12), and one C(9) atom. The C(11)-C(12) bond length is 1.45 Å. In the twelfth C site, C(12) is bonded in a distorted bent 120 degrees geometry to one C(11), one O(3), and one O(4) atom. The C(12)-O(3) bond length is 1.23 Å. The C(12)-O(4) bond length is 1.28 Å. There are four inequivalent N sites. In the first N site, N(1) is bonded in a 3-coordinate geometry to one Cu(1), one C(3), and one N(2) atom. The N(1)-N(2) bond length is 1.37 Å. In the second N site, N(2) is bonded in a distorted trigonal planar geometry to one Cu(2), one C(4), and one N(1) atom. In the third N site, N(3) is bonded in a distorted trigonal planar geometry to one Cu(1), one C(9), and one N(4) atom. The N(3)-N(4) bond length is 1.39 Å. In the fourth N site, N(4) is bonded in a 3-coordinate geometry to one Cu(2), one C(10), and one N(3) atom. There are nine inequivalent H sites. In the first H site, H(1,2) is bonded in a single-bond geometry to one C(1) atom. In the second H site, H(3) is bonded in a single-bond geometry to one C(1) atom. In the third H site, H(4) is bonded in a single-bond geometry to one C(2) atom. In the fourth H site, H(5) is bonded in a single-bond geometry to one C(2) atom. In the fifth H site, H(6) is bonded in a single-bond geometry to one C(2) atom. In the sixth H site, H(7) is bonded in a single-bond geometry to one C(7) atom. In the seventh H site, H(8,9) is bonded in a single-bond geometry to one C(7) atom. In the eighth H site, H(10,12) is bonded in a single-bond geometry to one C(8) atom. In the ninth H site, H(11) is bonded in a single-bond geometry to one C(8) atom. There are four inequivalent O sites. In the first O site, O(1) is bonded in an L-shaped geometry to one Cu(2) and one C(6) atom. In the second O site, O(2) is bonded in an L-shaped geometry to one Cu(2) and one C(6) atom. In the third O site, O(3) is bonded in an L-shaped geometry to one Cu(1) and one C(12) atom. In the fourth O site, O(4) is bonded in an L-shaped geometry to one Cu(1) and one C(12) atom. Linkers: 6 CC1=N[N]C(C)=C1C([O])=O ,2 C[C]1N=NC(C)=C1C([O])=O. Metal clusters: 4 [C]1O[Cu]2(N=N[Cu]3(N=N2)O[C]O3)O1. The MOF has largest included sphere 5.29 A, density 1.23 g/cm3, surface area 4041.91 m2/g, accessible volume 0.40 cm3/g