CuC16(NO2)2 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a rectangular see-saw-like geometry to one N(1), one N(2), one O(5), and one O(7) atom. The Cu(1)-N(1) bond length is 2.03 Å. The Cu(1)-N(2) bond length is 2.04 Å. The Cu(1)-O(5) bond length is 1.96 Å. The Cu(1)-O(7) bond length is 1.97 Å. In the second Cu site, Cu(2) is bonded in a square co-planar geometry to two equivalent N(3) and two equivalent O(3) atoms. Both Cu(2)-N(3) bond lengths are 2.02 Å. Both Cu(2)-O(3) bond lengths are 2.01 Å. In the third Cu site, Cu(3) is bonded in a square co-planar geometry to two equivalent N(4) and two equivalent O(1) atoms. Both Cu(3)-N(4) bond lengths are 2.05 Å. Both Cu(3)-O(1) bond lengths are 1.97 Å. There are thirty-two inequivalent C sites. In the first C site, C(1) is bonded in a single-bond geometry to one C(2) and one N(1) atom. The C(1)-C(2) bond length is 1.38 Å. The C(1)-N(1) bond length is 1.33 Å. In the second C site, C(2) is bonded in a bent 120 degrees geometry to one C(1) and one C(3) atom. The C(2)-C(3) bond length is 1.37 Å. In the third C site, C(3) is bonded in a trigonal planar geometry to one C(2), one C(4), and one C(6) atom. The C(3)-C(4) bond length is 1.39 Å. The C(3)-C(6) bond length is 1.52 Å. In the fourth C site, C(4) is bonded in a bent 120 degrees geometry to one C(3) and one C(5) atom. The C(4)-C(5) bond length is 1.36 Å. In the fifth C site, C(5) is bonded in a single-bond geometry to one C(4) and one N(1) atom. The C(5)-N(1) bond length is 1.33 Å. In the sixth C site, C(6) is bonded in a distorted bent 120 degrees geometry to one C(3), one O(1), and one O(2) atom. The C(6)-O(1) bond length is 1.27 Å. The C(6)-O(2) bond length is 1.25 Å. In the seventh C site, C(7) is bonded in a single-bond geometry to one N(2) atom. The C(7)-N(2) bond length is 1.33 Å. In the eighth C site, C(8) is bonded in a single-bond geometry to one C(9) atom. The C(8)-C(9) bond length is 1.37 Å. In the ninth C site, C(9) is bonded in a trigonal planar geometry to one C(10), one C(12), and one C(8) atom. The C(9)-C(10) bond length is 1.39 Å. The C(9)-C(12) bond length is 1.53 Å. In the tenth C site, C(10) is bonded in a bent 120 degrees geometry to one C(11) and one C(9) atom. The C(10)-C(11) bond length is 1.39 Å. In the eleventh C site, C(11) is bonded in a single-bond geometry to one C(10) and one N(2) atom. The C(11)-N(2) bond length is 1.34 Å. In the twelfth C site, C(12) is bonded in a distorted bent 120 degrees geometry to one C(9), one O(3), and one O(4) atom. The C(12)-O(3) bond length is 1.27 Å. The C(12)-O(4) bond length is 1.26 Å. In the thirteenth C site, C(13) is bonded in a distorted single-bond geometry to one N(3) atom. The C(13)-N(3) bond length is 1.34 Å. In the fourteenth C site, C(14) is bonded in a distorted single-bond geometry to one C(15) atom. The C(14)-C(15) bond length is 1.38 Å. In the fifteenth C site, C(15) is bonded in a 5-coordinate geometry to one C(14), one C(16), one C(19), one C(20), and one C(22) atom. The C(15)-C(16) bond length is 1.38 Å. The C(15)-C(19) bond length is 1.40 Å. The C(15)-C(20) bond length is 1.39 Å. The C(15)-C(22) bond length is 1.50 Å. In the sixteenth C site, C(16) is bonded in a distorted single-bond geometry to one C(15) atom. In the seventeenth C site, C(17) is bonded in a distorted single-bond geometry to one N(3) atom. The C(17)-N(3) bond length is 1.35 Å. In the eighteenth C site, C(18) is bonded in a distorted single-bond geometry to one N(3) atom. The C(18)-N(3) bond length is 1.32 Å. In the nineteenth C site, C(19) is bonded in a distorted single-bond geometry to one C(15) atom. In the twentieth C site, C(20) is bonded in a distorted single-bond geometry to one C(15) atom. In the twenty-first C site, C(21) is bonded in a distorted single-bond geometry to one N(3) atom. The C(21)-N(3) bond length is 1.33 Å. In the twenty-second C site, C(22) is bonded in a distorted bent 120 degrees geometry to one C(15), one O(5), and one O(6) atom. The C(22)-O(5) bond length is 1.28 Å. The C(22)-O(6) bond length is 1.24 Å. In the twenty-third C site, C(23) is bonded in a 2-coordinate geometry to one C(31) and one N(4) atom. The C(23)-C(31) bond length is 0.89 Å. The C(23)-N(4) bond length is 1.33 Å. In the twenty-fourth C site, C(24) is bonded in a 2-coordinate geometry to one C(25) and one C(30) atom. The C(24)-C(25) bond length is 1.39 Å. The C(24)-C(30) bond length is 0.92 Å. In the twenty-fifth C site, C(25) is bonded in a 5-coordinate geometry to one C(24), one C(26), one C(29), one C(30), and one C(32) atom. The C(25)-C(26) bond length is 1.39 Å. The C(25)-C(29) bond length is 1.39 Å. The C(25)-C(30) bond length is 1.38 Å. The C(25)-C(32) bond length is 1.52 Å. In the twenty-sixth C site, C(26) is bonded in a 2-coordinate geometry to one C(25) and one C(29) atom. The C(26)-C(29) bond length is 1.01 Å. In the twenty-seventh C site, C(27) is bonded in a 2-coordinate geometry to one C(28) and one N(4) atom. The C(27)-C(28) bond length is 0.93 Å. The C(27)-N(4) bond length is 1.34 Å. In the twenty-eighth C site, C(28) is bonded in a 2-coordinate geometry to one C(27), one C(29), and one N(4) atom. The C(28)-C(29) bond length is 1.39 Å. The C(28)-N(4) bond length is 1.34 Å. In the twenty-ninth C site, C(29) is bonded in a 3-coordinate geometry to one C(25), one C(26), and one C(28) atom. In the thirtieth C site, C(30) is bonded in a 3-coordinate geometry to one C(24), one C(25), and one C(31) atom. The C(30)-C(31) bond length is 1.39 Å. In the thirty-first C site, C(31) is bonded in a 2-coordinate geometry to one C(23), one C(30), and one N(4) atom. The C(31)-N(4) bond length is 1.34 Å. In the thirty-second C site, C(32) is bonded in a distorted bent 120 degrees geometry to one C(25), one O(7), and one O(8) atom. The C(32)-O(7) bond length is 1.24 Å. The C(32)-O(8) bond length is 1.24 Å. There are four inequivalent N sites. In the first N site, N(1) is bonded in a trigonal planar geometry to one Cu(1), one C(1), and one C(5) atom. In the second N site, N(2) is bonded in a trigonal planar geometry to one Cu(1), one C(11), and one C(7) atom. In the third N site, N(3) is bonded in a 5-coordinate geometry to one Cu(2), one C(13), one C(17), one C(18), and one C(21) atom. In the fourth N site, N(4) is bonded in a 5-coordinate geometry to one Cu(3), one C(23), one C(27), one C(28), and one C(31) atom. There are eight inequivalent O sites. In the first O site, O(2) is bonded in a single-bond geometry to one C(6) atom. In the second O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Cu(2) and one C(12) atom. In the third O site, O(8) is bonded in a single-bond geometry to one C(32) atom. In the fourth O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Cu(1) and one C(32) atom. In the fifth O site, O(4) is bonded in a single-bond geometry to one C(12) atom. In the sixth O site, O(5) is bonded in a bent 120 degrees geometry to one Cu(1) and one C(22) atom. In the seventh O site, O(6) is bonded in a single-bond geometry to one C(22) atom. In the eighth O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Cu(3) and one C(6) atom. Linkers: 2 [C]12[C]3[C@@]42[C]2[C@]54[C@]46[C@@]73[C]1[N@]47[C@@]256.[O][C]=O ,4 [C]1[C][C][C]1.[C][C]1[C][C]([N])[C]1.[O][C]=O ,8 [O]C(=O)c1[c][c]n[c][c]1 ,2 [C]12[C]3[C@]42[C]2[C@@]54[C@@]46[C@]73[C]1[N@@]47[C@]256.[O][C]=O. Metal clusters: 8 O=[C]O[Cu]O[C]=O. The MOF has largest included sphere 6.44 A, density 0.85 g/cm3, surface area 4059.36 m2/g, accessible volume 0.75 cm3/g