Cu9C80H40(N2O)20 crystallizes in the orthorhombic Pnn2 space group. There are five inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a square pyramidal geometry to one N(13), one N(17), one N(7), one O(7), and one O(8) atom. The Cu(1)-N(13) bond length is 1.98 Å. The Cu(1)-N(17) bond length is 1.96 Å. The Cu(1)-N(7) bond length is 2.19 Å. The Cu(1)-O(7) bond length is 1.96 Å. The Cu(1)-O(8) bond length is 2.03 Å. In the second Cu site, Cu(2) is bonded in a trigonal bipyramidal geometry to one N(11), one N(4), one N(5), one O(2), and one O(4) atom. The Cu(2)-N(11) bond length is 1.94 Å. The Cu(2)-N(4) bond length is 2.03 Å. The Cu(2)-N(5) bond length is 2.20 Å. The Cu(2)-O(2) bond length is 1.91 Å. The Cu(2)-O(4) bond length is 1.91 Å. In the third Cu site, Cu(3) is bonded in a trigonal bipyramidal geometry to one N(14), one N(18), one N(8), one O(1), and one O(3) atom. The Cu(3)-N(14) bond length is 2.07 Å. The Cu(3)-N(18) bond length is 2.07 Å. The Cu(3)-N(8) bond length is 2.17 Å. The Cu(3)-O(1) bond length is 1.89 Å. The Cu(3)-O(3) bond length is 1.98 Å. In the fourth Cu site, Cu(4) is bonded in a distorted rectangular see-saw-like geometry to one O(10), one O(5), one O(6), and one O(9) atom. The Cu(4)-O(10) bond length is 1.89 Å. The Cu(4)-O(5) bond length is 2.04 Å. The Cu(4)-O(6) bond length is 1.97 Å. The Cu(4)-O(9) bond length is 1.93 Å. In the fifth Cu site, Cu(5) is bonded in an octahedral geometry to two equivalent N(10), two equivalent N(3), and two equivalent N(6) atoms. Both Cu(5)-N(10) bond lengths are 1.84 Å. Both Cu(5)-N(3) bond lengths are 2.17 Å. Both Cu(5)-N(6) bond lengths are 2.38 Å. There are forty inequivalent C sites. In the first C site, C(1) is bonded in a distorted bent 120 degrees geometry to one C(4), one N(1), and one N(2) atom. The C(1)-C(4) bond length is 1.43 Å. The C(1)-N(1) bond length is 1.26 Å. The C(1)-N(2) bond length is 1.33 Å. In the second C site, C(2) is bonded in a distorted single-bond geometry to one C(7) and one H(1,4) atom. The C(2)-C(7) bond length is 1.39 Å. The C(2)-H(1,4) bond length is 0.93 Å. In the third C site, C(3) is bonded in a distorted single-bond geometry to one C(4) and one H(2) atom. The C(3)-C(4) bond length is 1.39 Å. The C(3)-H(2) bond length is 0.93 Å. In the fourth C site, C(4) is bonded in a trigonal planar geometry to one C(1), one C(3), and one C(5) atom. The C(4)-C(5) bond length is 1.39 Å. In the fifth C site, C(5) is bonded in a distorted single-bond geometry to one C(4) and one H(3) atom. The C(5)-H(3) bond length is 0.93 Å. In the sixth C site, C(6) is bonded in a distorted single-bond geometry to one C(7) and one H(1,4) atom. The C(6)-C(7) bond length is 1.39 Å. The C(6)-H(1,4) bond length is 0.93 Å. In the seventh C site, C(7) is bonded in a trigonal planar geometry to one C(2), one C(6), and one C(8) atom. The C(7)-C(8) bond length is 1.54 Å. In the eighth C site, C(8) is bonded in a distorted bent 120 degrees geometry to one C(7), one O(5), and one O(6) atom. The C(8)-O(5) bond length is 1.20 Å. The C(8)-O(6) bond length is 1.38 Å. In the ninth C site, C(9) is bonded in a bent 120 degrees geometry to one C(34), one O(10), and one O(9) atom. The C(9)-C(34) bond length is 1.50 Å. The C(9)-O(10) bond length is 1.36 Å. The C(9)-O(9) bond length is 1.20 Å. In the tenth C site, C(10) is bonded in a distorted bent 120 degrees geometry to one C(11), one O(1), and one O(2) atom. The C(10)-C(11) bond length is 1.53 Å. The C(10)-O(1) bond length is 1.25 Å. The C(10)-O(2) bond length is 1.46 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(16) atom. The C(11)-C(12) bond length is 1.39 Å. The C(11)-C(16) bond length is 1.39 Å. In the twelfth C site, C(12) is bonded in a distorted single-bond geometry to one C(11) and one H(5) atom. The C(12)-H(5) bond length is 0.93 Å. In the thirteenth C site, C(13) is bonded in a single-bond geometry to one C(14) and one H(6) atom. The C(13)-C(14) bond length is 1.39 Å. The C(13)-H(6) bond length is 0.93 Å. In the fourteenth C site, C(14) is bonded in a trigonal planar geometry to one C(13), one C(15), and one C(18) atom. The C(14)-C(15) bond length is 1.39 Å. The C(14)-C(18) bond length is 1.47 Å. In the fifteenth C site, C(15) is bonded in a single-bond geometry to one C(14) and one H(7) atom. The C(15)-H(7) bond length is 0.93 Å. In the sixteenth C site, C(16) is bonded in a single-bond geometry to one C(11) and one H(8) atom. The C(16)-H(8) bond length is 0.93 Å. In the seventeenth C site, C(17) is bonded in a distorted bent 120 degrees geometry to one C(27), one N(15), and one N(16) atom. The C(17)-C(27) bond length is 1.56 Å. The C(17)-N(15) bond length is 1.22 Å. The C(17)-N(16) bond length is 1.46 Å. In the eighteenth C site, C(18) is bonded in a distorted water-like geometry to one C(14), one N(19), and one N(20) atom. The C(18)-N(19) bond length is 1.39 Å. The C(18)-N(20) bond length is 1.24 Å. In the nineteenth C site, C(19) is bonded in a distorted trigonal planar geometry to one C(20), one N(6), and one N(7) atom. The C(19)-C(20) bond length is 1.47 Å. The C(19)-N(6) bond length is 1.30 Å. The C(19)-N(7) bond length is 1.37 Å. In the twentieth C site, C(20) is bonded in a trigonal planar geometry to one C(19), one C(21), and one C(25) atom. The C(20)-C(21) bond length is 1.39 Å. The C(20)-C(25) bond length is 1.39 Å. In the twenty-first C site, C(21) is bonded in a distorted single-bond geometry to one C(20) and one H(9,12) atom. The C(21)-H(9,12) bond length is 0.93 Å. In the twenty-second C site, C(22) is bonded in a distorted single-bond geometry to one C(23) and one H(10,11) atom. The C(22)-C(23) bond length is 1.39 Å. The C(22)-H(10,11) bond length is 0.93 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(26) atom. The C(23)-C(24) bond length is 1.39 Å. The C(23)-C(26) bond length is 1.48 Å. In the twenty-fourth C site, C(24) is bonded in a distorted single-bond geometry to one C(23) and one H(10,11) atom. The C(24)-H(10,11) bond length is 0.93 Å. In the twenty-fifth C site, C(25) is bonded in a distorted single-bond geometry to one C(20) and one H(9,12) atom. The C(25)-H(9,12) bond length is 0.93 Å. In the twenty-sixth C site, C(26) is bonded in a distorted bent 120 degrees geometry to one C(23), one O(7), and one O(8) atom. The C(26)-O(7) bond length is 1.13 Å. The C(26)-O(8) bond length is 1.39 Å. In the twenty-seventh C site, C(27) is bonded in a trigonal planar geometry to one C(17), one C(28), and one C(32) atom. The C(27)-C(28) bond length is 1.35 Å. The C(27)-C(32) bond length is 1.38 Å. In the twenty-eighth C site, C(28) is bonded in a single-bond geometry to one C(27) and one H(13) atom. The C(28)-H(13) bond length is 0.93 Å. In the twenty-ninth C site, C(29) is bonded in a distorted single-bond geometry to one C(30) and one H(14) atom. The C(29)-C(30) bond length is 1.38 Å. The C(29)-H(14) bond length is 0.93 Å. In the thirtieth C site, C(30) is bonded in a trigonal planar geometry to one C(29), one C(31), and one C(33) atom. The C(30)-C(31) bond length is 1.30 Å. The C(30)-C(33) bond length is 1.58 Å. In the thirty-first C site, C(31) is bonded in a distorted single-bond geometry to one C(30), one C(32), and one H(15) atom. The C(31)-C(32) bond length is 1.41 Å. The C(31)-H(15) bond length is 0.93 Å. In the thirty-second C site, C(32) is bonded in a distorted trigonal planar geometry to one C(27), one C(31), and one H(16) atom. The C(32)-H(16) bond length is 0.93 Å. In the thirty-third C site, C(33) is bonded in a distorted bent 120 degrees geometry to one C(30), one O(3), and one O(4) atom. The C(33)-O(3) bond length is 1.29 Å. The C(33)-O(4) bond length is 0.99 Å. In the thirty-fourth C site, C(34) is bonded in a trigonal planar geometry to one C(35), one C(39), and one C(9) atom. The C(34)-C(35) bond length is 1.39 Å. The C(34)-C(39) bond length is 1.39 Å. In the thirty-fifth C site, C(35) is bonded in a distorted single-bond geometry to one C(34) and one H(17) atom. The C(35)-H(17) bond length is 0.93 Å. In the thirty-sixth C site, C(36) is bonded in a distorted single-bond geometry to one C(37) and one H(18) atom. The C(36)-C(37) bond length is 1.39 Å. The C(36)-H(18) bond length is 0.93 Å. In the thirty-seventh C site, C(37) is bonded in a trigonal planar geometry to one C(36), one C(38), and one C(40) atom. The C(37)-C(38) bond length is 1.39 Å. The C(37)-C(40) bond length is 1.44 Å. In the thirty-eighth C site, C(38) is bonded in a distorted single-bond geometry to one C(37), one C(39), and one H(19) atom. The C(38)-C(39) bond length is 1.39 Å. The C(38)-H(19) bond length is 0.93 Å. In the thirty-ninth C site, C(39) is bonded in a distorted trigonal planar geometry to one C(34), one C(38), and one H(20) atom. The C(39)-H(20) bond length is 0.93 Å. In the fortieth C site, C(40) is bonded in a distorted trigonal planar geometry to one C(37), one N(12), and one N(9) atom. The C(40)-N(12) bond length is 1.42 Å. The C(40)-N(9) bond length is 1.42 Å. There are twenty inequivalent N sites. In the first N site, N(1) is bonded in a distorted water-like geometry to one C(1) and one N(4) atom. The N(1)-N(4) bond length is 1.35 Å. In the second N site, N(2) is bonded in a distorted water-like geometry to one C(1) and one N(3) atom. The N(2)-N(3) bond length is 1.29 Å. In the third N site, N(3) is bonded in a trigonal planar geometry to one Cu(5), one N(2), and one N(4) atom. The N(3)-N(4) bond length is 1.21 Å. In the fourth N site, N(4) is bonded in a distorted trigonal planar geometry to one Cu(2), one N(1), and one N(3) atom. In the fifth N site, N(5) is bonded in a distorted trigonal planar geometry to one Cu(2), one N(6), and one N(8) atom. The N(5)-N(6) bond length is 1.34 Å. The N(5)-N(8) bond length is 1.30 Å. In the sixth N site, N(6) is bonded in a 3-coordinate geometry to one Cu(5), one C(19), and one N(5) atom. In the seventh N site, N(7) is bonded in a 3-coordinate geometry to one Cu(1), one C(19), and one N(8) atom. The N(7)-N(8) bond length is 1.38 Å. In the eighth N site, N(8) is bonded in a distorted trigonal planar geometry to one Cu(3), one N(5), and one N(7) atom. In the ninth N site, N(9) is bonded in a distorted water-like geometry to one C(40) and one N(10) atom. The N(9)-N(10) bond length is 1.42 Å. In the tenth N site, N(10) is bonded in a distorted trigonal planar geometry to one Cu(5), one N(11), and one N(9) atom. The N(10)-N(11) bond length is 1.42 Å. In the eleventh N site, N(11) is bonded in a distorted trigonal planar geometry to one Cu(2), one N(10), and one N(12) atom. The N(11)-N(12) bond length is 1.42 Å. In the twelfth N site, N(12) is bonded in a distorted water-like geometry to one C(40) and one N(11) atom. In the thirteenth N site, N(13) is bonded in a 3-coordinate geometry to one Cu(1), one N(14), and one N(16) atom. The N(13)-N(14) bond length is 1.35 Å. The N(13)-N(16) bond length is 1.34 Å. In the fourteenth N site, N(14) is bonded in a distorted trigonal planar geometry to one Cu(3), one N(13), and one N(15) atom. The N(14)-N(15) bond length is 1.36 Å. In the fifteenth N site, N(15) is bonded in a distorted water-like geometry to one C(17) and one N(14) atom. In the sixteenth N site, N(16) is bonded in a distorted water-like geometry to one C(17) and one N(13) atom. In the seventeenth N site, N(17) is bonded in a 3-coordinate geometry to one Cu(1), one N(18), and one N(20) atom. The N(17)-N(18) bond length is 1.31 Å. The N(17)-N(20) bond length is 1.33 Å. In the eighteenth N site, N(18) is bonded in a distorted trigonal planar geometry to one Cu(3), one N(17), and one N(19) atom. The N(18)-N(19) bond length is 1.26 Å. In the nineteenth N site, N(19) is bonded in a water-like geometry to one C(18) and one N(18) atom. In the twentieth N site, N(20) is bonded in a distorted bent 120 degrees geometry to one C(18) and one N(17) atom. There are seventeen inequivalent H sites. In the first H site, H(1,4) is bonded in a single-bond geometry to one C(2) atom. In the second H site, H(2) is bonded in a single-bond geometry to one C(3) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(5) atom. In the fourth H site, H(5) is bonded in a single-bond geometry to one C(12) atom. In the fifth H site, H(6) is bonded in a single-bond geometry to one C(13) atom. In the sixth H site, H(7) is bonded in a single-bond geometry to one C(15) atom. In the seventh H site, H(8) is bonded in a single-bond geometry to one C(16) atom. In the eighth H site, H(9,12) is bonded in a single-bond geometry to one C(21) atom. In the ninth H site, H(10,11) is bonded in a single-bond geometry to one C(22) atom. In the tenth H site, H(13) is bonded in a single-bond geometry to one C(28) atom. In the eleventh H site, H(14) is bonded in a single-bond geometry to one C(29) atom. In the twelfth H site, H(15) is bonded in a single-bond geometry to one C(31) atom. In the thirteenth H site, H(16) is bonded in a single-bond geometry to one C(32) atom. In the fourteenth H site, H(17) is bonded in a single-bond geometry to one C(35) atom. In the fifteenth H site, H(18) is bonded in a single-bond geometry to one C(36) atom. In the sixteenth H site, H(19) is bonded in a single-bond geometry to one C(38) atom. In the seventeenth H site, H(20) is bonded in a single-bond geometry to one C(39) atom. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Cu(3) and one C(10) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Cu(2) and one C(10) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Cu(3) and one C(33) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Cu(2) and one C(33) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one Cu(4) and one C(8) atom. In the sixth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one Cu(4) and one C(8) atom. In the seventh O site, O(7) is bonded in an L-shaped geometry to one Cu(1) and one C(26) atom. In the eighth O site, O(8) is bonded in an L-shaped geometry to one Cu(1) and one C(26) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one Cu(4) and one C(9) atom. In the tenth O site, O(10) is bonded in a distorted bent 120 degrees geometry to one Cu(4) and one C(9) atom. Linkers: 9 [O]C(=O)c1ccc(C2=N[N]N=N2)cc1 ,4 [O]C(=O)c1ccc(C2=N[N][N][N]2)cc1 ,7 [O]C(=O)c1ccc(C2=NN=N[N]2)cc1. Metal clusters: 1 [C]1O[Cu]23([N][N][Cu]45(N=N2)O[C]O[Cu]26(N=N[Cu]78([N][N@]2[N@@]4[N]3)([N][N@@]2[N@@]3[N][Cu]49([N][N][Cu]3%10(N=N4)O[C]O[Cu]2(N=N7)(N=N8)O[C]O%10)O[C]O9)N=N6)O[C]O5)O1 ,2 [C]1O[Cu]234O[C]O[Cu]2(O1)(O[C]O3)O[C]O4 ,1 [C]1O[Cu]23([N][N][Cu]45(N=N2)O[C]O[Cu]26(N=N[Cu]78([N][N@]2[N@]4[N]3)([N][N@@]2[N@]3[N][Cu]49([N][N][Cu]3%10(N=N4)O[C]O[Cu]2(N=N7)(N=N8)O[C]O%10)O[C]O9)N=N6)O[C]O5)O1. The MOF has largest included sphere 8.42 A, density 1.02 g/cm3, surface area 3783.04 m2/g, accessible volume 0.52 cm3/g