Cu9C78H38(N6O31)2(C3NHO2)2 crystallizes in the orthorhombic Pnna space group. The structure consists of four (1e,3e)-2,3-dimethyl-1,4-dinitrobuta-1,3-diene molecules inside a Cu9C78H38(N6O31)2 framework. In the Cu9C78H38(N6O31)2 framework, there are five inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 5-coordinate geometry to one O(18), one O(23), one O(26), one O(27), and one O(9) atom. The Cu(1)-O(18) bond length is 1.95 Å. The Cu(1)-O(23) bond length is 2.53 Å. The Cu(1)-O(26) bond length is 1.97 Å. The Cu(1)-O(27) bond length is 1.95 Å. The Cu(1)-O(9) bond length is 1.90 Å. In the second Cu site, Cu(2) is bonded in a trigonal bipyramidal geometry to one O(14), one O(2), one O(23), one O(25), and one O(26) atom. The Cu(2)-O(14) bond length is 2.16 Å. The Cu(2)-O(2) bond length is 2.01 Å. The Cu(2)-O(23) bond length is 1.98 Å. The Cu(2)-O(25) bond length is 1.92 Å. The Cu(2)-O(26) bond length is 1.94 Å. In the third Cu site, Cu(3) is bonded in a 4-coordinate geometry to one O(13), one O(17), one O(26), one O(27), and one O(7) atom. The Cu(3)-O(13) bond length is 1.92 Å. The Cu(3)-O(17) bond length is 2.48 Å. The Cu(3)-O(26) bond length is 1.97 Å. The Cu(3)-O(27) bond length is 1.96 Å. The Cu(3)-O(7) bond length is 1.93 Å. In the fourth Cu site, Cu(4) is bonded in a 5-coordinate geometry to one O(1), one O(14), one O(24), and two equivalent O(25) atoms. The Cu(4)-O(1) bond length is 1.96 Å. The Cu(4)-O(14) bond length is 2.43 Å. The Cu(4)-O(24) bond length is 1.95 Å. There is one shorter (1.95 Å) and one longer (1.98 Å) Cu(4)-O(25) bond length. In the fifth Cu site, Cu(5) is bonded in a rectangular see-saw-like geometry to two equivalent O(17) and two equivalent O(27) atoms. Both Cu(5)-O(17) bond lengths are 2.01 Å. Both Cu(5)-O(27) bond lengths are 1.91 Å. There are thirty-nine inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one C(2), one C(3), and one C(9) atom. The C(1)-C(2) bond length is 1.43 Å. The C(1)-C(3) bond length is 1.36 Å. The C(1)-C(9) bond length is 1.51 Å. In the second C site, C(2) is bonded in a distorted trigonal planar geometry to one C(1), one C(4), and one N(1) atom. The C(2)-C(4) bond length is 1.37 Å. The C(2)-N(1) bond length is 1.49 Å. In the third C site, C(3) is bonded in a distorted trigonal planar geometry to one C(1), one C(7), and one N(2) atom. The C(3)-C(7) bond length is 1.41 Å. The C(3)-N(2) bond length is 1.63 Å. In the fourth C site, C(4) is bonded in a single-bond geometry to one C(2), one C(5), and one H(1) atom. The C(4)-C(5) bond length is 1.39 Å. The C(4)-H(1) bond length is 0.93 Å. In the fifth C site, C(5) is bonded in a trigonal planar geometry to one C(4), one C(6), and one C(7) atom. The C(5)-C(6) bond length is 1.49 Å. The C(5)-C(7) bond length is 1.38 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 1.25 Å. The C(6)-O(2) bond length is 1.26 Å. In the seventh C site, C(7) is bonded in a distorted single-bond geometry to one C(3), one C(5), and one H(2) atom. The C(7)-H(2) bond length is 0.93 Å. In the eighth C site, C(8) is bonded in a distorted trigonal planar geometry to one C(13), one C(9), and one N(3) atom. The C(8)-C(13) bond length is 1.40 Å. The C(8)-C(9) bond length is 1.35 Å. The C(8)-N(3) bond length is 1.51 Å. In the ninth C site, C(9) is bonded in a trigonal planar geometry to one C(1), one C(10), and one C(8) atom. The C(9)-C(10) bond length is 1.38 Å. In the tenth C site, C(10) is bonded in a distorted single-bond geometry to one C(9) and one H(3) atom. The C(10)-H(3) bond length is 0.93 Å. In the eleventh C site, C(11) is bonded in a distorted single-bond geometry to one C(12) and one H(4) atom. The C(11)-C(12) bond length is 1.39 Å. The C(11)-H(4) bond length is 0.93 Å. In the twelfth C site, C(12) is bonded in a trigonal planar geometry to one C(11), one C(13), and one C(14) atom. The C(12)-C(13) bond length is 1.37 Å. The C(12)-C(14) bond length is 1.50 Å. In the thirteenth C site, C(13) is bonded in a distorted single-bond geometry to one C(12), one C(8), and one H(5) atom. The C(13)-H(5) bond length is 0.93 Å. In the fourteenth C site, C(14) is bonded in a bent 120 degrees geometry to one C(12), one O(7), and one O(8) atom. The C(14)-O(7) bond length is 1.25 Å. The C(14)-O(8) bond length is 1.24 Å. In the fifteenth C site, C(15) is bonded in a distorted bent 120 degrees geometry to one C(16), one O(10), and one O(9) atom. The C(15)-C(16) bond length is 1.54 Å. The C(15)-O(10) bond length is 1.22 Å. The C(15)-O(9) bond length is 1.26 Å. In the sixteenth C site, C(16) is bonded in a trigonal planar geometry to one C(15), one C(17), and one C(21) atom. The C(16)-C(17) bond length is 1.38 Å. The C(16)-C(21) bond length is 1.35 Å. In the seventeenth C site, C(17) is bonded in a distorted single-bond geometry to one C(16) and one H(6) atom. The C(17)-H(6) bond length is 0.93 Å. In the eighteenth C site, C(18) is bonded in a distorted single-bond geometry to one C(19) and one H(7) atom. The C(18)-C(19) bond length is 1.33 Å. The C(18)-H(7) bond length is 0.93 Å. In the nineteenth C site, C(19) is bonded in a trigonal planar geometry to one C(18), one C(19), and one C(20) atom. The C(19)-C(19) bond length is 1.55 Å. The C(19)-C(20) bond length is 1.34 Å. In the twentieth C site, C(20) is bonded in a distorted trigonal planar geometry to one C(19), one C(21), and one N(4) atom. The C(20)-C(21) bond length is 1.40 Å. The C(20)-N(4) bond length is 1.47 Å. In the twenty-first C site, C(21) is bonded in a distorted single-bond geometry to one C(16), one C(20), and one H(8) atom. The C(21)-H(8) bond length is 0.93 Å. In the twenty-second C site, C(22) is bonded in a distorted bent 120 degrees geometry to one C(23), one O(13), and one O(14) atom. The C(22)-C(23) bond length is 1.51 Å. The C(22)-O(13) bond length is 1.25 Å. The C(22)-O(14) bond length is 1.24 Å. In the twenty-third C site, C(23) is bonded in a trigonal planar geometry to one C(22), one C(24), and one C(28) atom. The C(23)-C(24) bond length is 1.40 Å. The C(23)-C(28) bond length is 1.36 Å. In the twenty-fourth C site, C(24) is bonded in a distorted single-bond geometry to one C(23) and one H(9) atom. The C(24)-H(9) bond length is 0.93 Å. In the twenty-fifth C site, C(28) is bonded in a distorted single-bond geometry to one C(23) and one H(11) atom. The C(28)-H(11) bond length is 0.93 Å. In the twenty-sixth C site, C(29) is bonded in a distorted bent 120 degrees geometry to one C(30), one O(17), and one O(18) atom. The C(29)-C(30) bond length is 1.50 Å. The C(29)-O(17) bond length is 1.25 Å. The C(29)-O(18) bond length is 1.26 Å. In the twenty-seventh C site, C(30) is bonded in a trigonal planar geometry to one C(29), one C(31), and one C(35) atom. The C(30)-C(31) bond length is 1.37 Å. The C(30)-C(35) bond length is 1.37 Å. In the twenty-eighth C site, C(31) is bonded in a distorted single-bond geometry to one C(30) and one H(12) atom. The C(31)-H(12) bond length is 0.93 Å. In the twenty-ninth C site, C(32) is bonded in a distorted single-bond geometry to one C(33) and one H(13) atom. The C(32)-C(33) bond length is 1.38 Å. The C(32)-H(13) bond length is 0.93 Å. In the thirtieth C site, C(33) is bonded in a trigonal planar geometry to one C(32), one C(34), and one C(36) atom. The C(33)-C(34) bond length is 1.40 Å. The C(33)-C(36) bond length is 1.49 Å. In the thirty-first C site, C(34) is bonded in a distorted trigonal planar geometry to one C(33), one C(35), and one N(6) atom. The C(34)-C(35) bond length is 1.37 Å. The C(34)-N(6) bond length is 1.50 Å. In the thirty-second C site, C(35) is bonded in a distorted single-bond geometry to one C(30), one C(34), and one H(14) atom. The C(35)-H(14) bond length is 0.93 Å. In the thirty-third C site, C(36) is bonded in a trigonal planar geometry to one C(33), one C(37), and one C(42) atom. The C(36)-C(37) bond length is 1.43 Å. The C(36)-C(42) bond length is 1.39 Å. In the thirty-fourth C site, C(37) is bonded in a distorted single-bond geometry to one C(36) and one H(15) atom. The C(37)-H(15) bond length is 0.93 Å. In the thirty-fifth C site, C(38) is bonded in a distorted single-bond geometry to one C(39) and one H(16) atom. The C(38)-C(39) bond length is 1.35 Å. The C(38)-H(16) bond length is 0.93 Å. In the thirty-sixth C site, C(39) is bonded in a trigonal planar geometry to one C(38), one C(40), and one C(41) atom. The C(39)-C(40) bond length is 1.50 Å. The C(39)-C(41) bond length is 1.40 Å. In the thirty-seventh C site, C(40) is bonded in a distorted bent 120 degrees geometry to one C(39), one O(23), and one O(24) atom. The C(40)-O(23) bond length is 1.25 Å. The C(40)-O(24) bond length is 1.26 Å. In the thirty-eighth C site, C(41) is bonded in a distorted single-bond geometry to one C(39), one C(42), and one H(17) atom. The C(41)-C(42) bond length is 1.35 Å. The C(41)-H(17) bond length is 0.93 Å. In the thirty-ninth C site, C(42) is bonded in a distorted single-bond geometry to one C(36), one C(41), and one N(7) atom. The C(42)-N(7) bond length is 1.48 Å. There are six inequivalent N sites. In the first N site, N(1) is bonded in a trigonal planar geometry to one C(2), one O(3), and one O(4) atom. The N(1)-O(3) bond length is 1.21 Å. The N(1)-O(4) bond length is 1.22 Å. In the second N site, N(2) is bonded in a 5-coordinate geometry to one C(3), one O(28), one O(29), one O(32), and one O(33) atom. The N(2)-O(28) bond length is 1.31 Å. The N(2)-O(29) bond length is 1.31 Å. The N(2)-O(32) bond length is 1.43 Å. The N(2)-O(33) bond length is 1.29 Å. In the third N site, N(3) is bonded in a 5-coordinate geometry to one C(8), one O(30), one O(31), one O(5), and one O(6) atom. The N(3)-O(30) bond length is 1.22 Å. The N(3)-O(31) bond length is 1.35 Å. The N(3)-O(5) bond length is 1.29 Å. The N(3)-O(6) bond length is 1.28 Å. In the fourth N site, N(4) is bonded in a trigonal planar geometry to one C(20), one O(11), and one O(12) atom. The N(4)-O(11) bond length is 1.19 Å. The N(4)-O(12) bond length is 1.34 Å. In the fifth N site, N(6) is bonded in a trigonal planar geometry to one C(34), one O(19), and one O(20) atom. The N(6)-O(19) bond length is 1.20 Å. The N(6)-O(20) bond length is 1.23 Å. In the sixth N site, N(7) is bonded in a trigonal planar geometry to one C(42), one O(21), and one O(22) atom. The N(7)-O(21) bond length is 1.24 Å. The N(7)-O(22) bond length is 1.18 Å. There are nineteen 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(7) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(10) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(11) 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(17) atom. In the seventh H site, H(7) is bonded in a single-bond geometry to one C(18) atom. In the eighth H site, H(8) is bonded in a single-bond geometry to one C(21) atom. In the ninth H site, H(9) is bonded in a single-bond geometry to one C(24) atom. In the tenth H site, H(11) is bonded in a single-bond geometry to one C(28) atom. In the eleventh H site, H(12) is bonded in a single-bond geometry to one C(31) atom. In the twelfth H site, H(13) is bonded in a single-bond geometry to one C(32) atom. In the thirteenth H site, H(14) is bonded in a single-bond geometry to one C(35) atom. In the fourteenth H site, H(15) is bonded in a single-bond geometry to one C(37) atom. In the fifteenth H site, H(16) is bonded in a single-bond geometry to one C(38) atom. In the sixteenth H site, H(17) is bonded in a single-bond geometry to one C(41) atom. In the seventeenth H site, H(18) is bonded in a single-bond geometry to one O(25) atom. The H(18)-O(25) bond length is 0.98 Å. In the eighteenth H site, H(19) is bonded in a single-bond geometry to one O(26) atom. The H(19)-O(26) bond length is 0.98 Å. In the nineteenth H site, H(20) is bonded in a single-bond geometry to one O(27) atom. The H(20)-O(27) bond length is 0.98 Å. There are thirty-one inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Cu(4) and one C(6) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Cu(2) and one C(6) atom. In the third O site, O(3) is bonded in a single-bond geometry to one N(1) atom. In the fourth O site, O(4) is bonded in a single-bond geometry to one N(1) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one N(3) atom. In the sixth O site, O(6) is bonded in a single-bond geometry to one N(3) atom. In the seventh O site, O(7) is bonded in a water-like geometry to one Cu(3) and one C(14) atom. In the eighth O site, O(8) is bonded in a single-bond geometry to one C(14) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one Cu(1) and one C(15) atom. In the tenth O site, O(10) is bonded in a single-bond geometry to one C(15) atom. In the eleventh O site, O(11) is bonded in a single-bond geometry to one N(4) atom. In the twelfth O site, O(12) is bonded in a single-bond geometry to one N(4) atom. In the thirteenth O site, O(13) is bonded in a bent 120 degrees geometry to one Cu(3) and one C(22) atom. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one Cu(2), one Cu(4), and one C(22) atom. In the fifteenth O site, O(17) is bonded in a 3-coordinate geometry to one Cu(3), one Cu(5), and one C(29) atom. In the sixteenth O site, O(18) is bonded in a bent 120 degrees geometry to one Cu(1) and one C(29) atom. In the seventeenth O site, O(19) is bonded in a single-bond geometry to one N(6) atom. In the eighteenth O site, O(20) is bonded in a single-bond geometry to one N(6) atom. In the nineteenth O site, O(21) is bonded in a single-bond geometry to one N(7) atom. In the twentieth O site, O(22) is bonded in a single-bond geometry to one N(7) atom. In the twenty-first O site, O(23) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(2), and one C(40) atom. In the twenty-second O site, O(24) is bonded in a bent 120 degrees geometry to one Cu(4) and one C(40) atom. In the twenty-third O site, O(25) is bonded to one Cu(2), two equivalent Cu(4), and one H(18) atom to form a mixture of distorted edge and corner-sharing OCu3H tetrahedra. In the twenty-fourth O site, O(26) is bonded to one Cu(1), one Cu(2), one Cu(3), and one H(19) atom to form a mixture of distorted edge and corner-sharing OCu3H tetrahedra. In the twenty-fifth O site, O(27) is bonded to one Cu(1), one Cu(3), one Cu(5), and one H(20) atom to form a mixture of distorted edge and corner-sharing OCu3H tetrahedra. In the twenty-sixth O site, O(28) is bonded in a single-bond geometry to one N(2) atom. In the twenty-seventh O site, O(29) is bonded in a 2-coordinate geometry to one N(2) and one O(33) atom. The O(29)-O(33) bond length is 0.70 Å. In the twenty-eighth O site, O(30) is bonded in a single-bond geometry to one N(3) atom. In the twenty-ninth O site, O(31) is bonded in a single-bond geometry to one N(3) atom. In the thirtieth O site, O(32) is bonded in a distorted single-bond geometry to one N(2) atom. In the thirty-first O site, O(33) is bonded in a 2-coordinate geometry to one N(2) and one O(29) atom. Linkers: 16 [O]C(=O)c1ccc(-c2ccc(C([O])=O)cc2[N+](=O)[O-])c([N+](=O)[O-])c1 ,8 [N]O[O].[O]C(=O)c1c[c]c(-c2[c]cc(C([O])=O)cc2[N+](=O)[O-])cc1.[O]O[N]O[O].[O][O]. Metal clusters: 36 [Cu]. The MOF has largest included sphere 7.05 A, density 1.31 g/cm3, surface area 3588.69 m2/g, accessible volume 0.34 cm3/g