CuH18(C3N2)5 crystallizes in the monoclinic P2_1/c space group. There are two 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(11), one N(14), and one N(4) atom. The Cu(1)-N(1) bond length is 2.00 Å. The Cu(1)-N(11) bond length is 2.31 Å. The Cu(1)-N(14) bond length is 2.01 Å. The Cu(1)-N(4) bond length is 2.08 Å. In the second Cu site, Cu(2) is bonded in a square pyramidal geometry to one N(12), one N(17), one N(2), one N(5), and one N(7) atom. The Cu(2)-N(12) bond length is 2.03 Å. The Cu(2)-N(17) bond length is 1.99 Å. The Cu(2)-N(2) bond length is 2.49 Å. The Cu(2)-N(5) bond length is 2.03 Å. The Cu(2)-N(7) bond length is 2.04 Å. There are thirty inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one N(1), one N(3), and one H(1) atom. The C(1)-N(1) bond length is 1.31 Å. The C(1)-N(3) bond length is 1.36 Å. The C(1)-H(1) bond length is 0.94 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one N(2), one N(3), and one H(2) atom. The C(2)-N(2) bond length is 1.32 Å. The C(2)-N(3) bond length is 1.37 Å. The C(2)-H(2) bond length is 0.94 Å. In the third C site, C(3) is bonded to one C(4), one C(8), one C(9), and one N(3) atom to form distorted corner-sharing CC3N tetrahedra. The C(3)-C(4) bond length is 1.55 Å. The C(3)-C(8) bond length is 1.54 Å. The C(3)-C(9) bond length is 1.55 Å. The C(3)-N(3) bond length is 1.49 Å. In the fourth C site, C(4) is bonded in a water-like geometry to one C(3), one C(5), one H(3), and one H(4) atom. The C(4)-C(5) bond length is 1.54 Å. The C(4)-H(3) bond length is 0.98 Å. The C(4)-H(4) bond length is 0.98 Å. In the fifth C site, C(5) is bonded to one C(10), one C(4), one C(6), and one N(6) atom to form distorted corner-sharing CC3N tetrahedra. The C(5)-C(10) bond length is 1.54 Å. The C(5)-C(6) bond length is 1.53 Å. The C(5)-N(6) bond length is 1.49 Å. In the sixth C site, C(6) is bonded in a water-like geometry to one C(5); one C(7); and two equivalent H(5,6) atoms. The C(6)-C(7) bond length is 1.55 Å. Both C(6)-H(5,6) bond lengths are 0.98 Å. In the seventh C site, C(7) is bonded to one C(11), one C(6), one C(8), and one N(9) atom to form distorted corner-sharing CC3N tetrahedra. The C(7)-C(11) bond length is 1.54 Å. The C(7)-C(8) bond length is 1.55 Å. The C(7)-N(9) bond length is 1.48 Å. In the eighth C site, C(8) is bonded in a water-like geometry to one C(3); one C(7); and two equivalent H(7,8) atoms. Both C(8)-H(7,8) bond lengths are 0.98 Å. In the ninth C site, C(9) is bonded in a 3-coordinate geometry to one C(3); one N(10); and two equivalent H(9,10) atoms. The C(9)-N(10) bond length is 1.48 Å. Both C(9)-H(9,10) bond lengths are 0.98 Å. In the tenth C site, C(10) is bonded in a 3-coordinate geometry to one C(5); one N(10); and two equivalent H(11,12) atoms. The C(10)-N(10) bond length is 1.48 Å. Both C(10)-H(11,12) bond lengths are 0.98 Å. In the eleventh C site, C(11) is bonded in a 3-coordinate geometry to one C(7); one N(10); and two equivalent H(13,14) atoms. The C(11)-N(10) bond length is 1.47 Å. Both C(11)-H(13,14) bond lengths are 0.98 Å. In the twelfth C site, C(12) is bonded in a trigonal planar geometry to one N(5), one N(6), and one H(15) atom. The C(12)-N(5) bond length is 1.31 Å. The C(12)-N(6) bond length is 1.36 Å. The C(12)-H(15) bond length is 0.94 Å. In the thirteenth C site, C(13) is bonded in a trigonal planar geometry to one N(4), one N(6), and one H(16) atom. The C(13)-N(4) bond length is 1.30 Å. The C(13)-N(6) bond length is 1.36 Å. The C(13)-H(16) bond length is 0.94 Å. In the fourteenth C site, C(14) is bonded in a trigonal planar geometry to one N(7), one N(9), and one H(17) atom. The C(14)-N(7) bond length is 1.31 Å. The C(14)-N(9) bond length is 1.35 Å. The C(14)-H(17) bond length is 0.94 Å. In the fifteenth C site, C(15) is bonded in a trigonal planar geometry to one N(8), one N(9), and one H(18) atom. The C(15)-N(8) bond length is 1.31 Å. The C(15)-N(9) bond length is 1.37 Å. The C(15)-H(18) bond length is 0.94 Å. In the sixteenth C site, C(16) is bonded in a trigonal planar geometry to one N(11), one N(13), and one H(19) atom. The C(16)-N(11) bond length is 1.31 Å. The C(16)-N(13) bond length is 1.37 Å. The C(16)-H(19) bond length is 0.94 Å. In the seventeenth C site, C(17) is bonded in a trigonal planar geometry to one N(12), one N(13), and one H(20) atom. The C(17)-N(12) bond length is 1.32 Å. The C(17)-N(13) bond length is 1.36 Å. The C(17)-H(20) bond length is 0.94 Å. In the eighteenth C site, C(18) is bonded to one C(19), one C(23), one C(24), and one N(13) atom to form distorted corner-sharing CC3N tetrahedra. The C(18)-C(19) bond length is 1.54 Å. The C(18)-C(23) bond length is 1.54 Å. The C(18)-C(24) bond length is 1.55 Å. The C(18)-N(13) bond length is 1.48 Å. In the nineteenth C site, C(19) is bonded in a water-like geometry to one C(18), one C(20), one H(21), and one H(22) atom. The C(19)-C(20) bond length is 1.53 Å. The C(19)-H(21) bond length is 0.98 Å. The C(19)-H(22) bond length is 0.98 Å. In the twentieth C site, C(20) is bonded to one C(19), one C(21), one C(25), and one N(16) atom to form distorted corner-sharing CC3N tetrahedra. The C(20)-C(21) bond length is 1.54 Å. The C(20)-C(25) bond length is 1.54 Å. The C(20)-N(16) bond length is 1.49 Å. In the twenty-first C site, C(21) is bonded in a water-like geometry to one C(20), one C(22), one H(23), and one H(24) atom. The C(21)-C(22) bond length is 1.54 Å. The C(21)-H(23) bond length is 0.98 Å. The C(21)-H(24) bond length is 0.98 Å. In the twenty-second C site, C(22) is bonded to one C(21), one C(23), one C(26), and one N(19) atom to form distorted corner-sharing CC3N tetrahedra. The C(22)-C(23) bond length is 1.54 Å. The C(22)-C(26) bond length is 1.55 Å. The C(22)-N(19) bond length is 1.49 Å. In the twenty-third C site, C(23) is bonded in a water-like geometry to one C(18), one C(22), one H(25), and one H(26) atom. The C(23)-H(25) bond length is 0.98 Å. The C(23)-H(26) bond length is 0.98 Å. In the twenty-fourth C site, C(24) is bonded in a 3-coordinate geometry to one C(18); one N(20); and two equivalent H(27,28) atoms. The C(24)-N(20) bond length is 1.47 Å. Both C(24)-H(27,28) bond lengths are 0.98 Å. In the twenty-fifth C site, C(25) is bonded in a 3-coordinate geometry to one C(20); one N(20); and two equivalent H(29,30) atoms. The C(25)-N(20) bond length is 1.48 Å. Both C(25)-H(29,30) bond lengths are 0.98 Å. In the twenty-sixth C site, C(26) is bonded in a 3-coordinate geometry to one C(22); one N(20); and two equivalent H(31,32) atoms. The C(26)-N(20) bond length is 1.48 Å. Both C(26)-H(31,32) bond lengths are 0.98 Å. In the twenty-seventh C site, C(27) is bonded in a trigonal planar geometry to one N(14), one N(16), and one H(33) atom. The C(27)-N(14) bond length is 1.30 Å. The C(27)-N(16) bond length is 1.35 Å. The C(27)-H(33) bond length is 0.94 Å. In the twenty-eighth C site, C(28) is bonded in a trigonal planar geometry to one N(15), one N(16), and one H(34) atom. The C(28)-N(15) bond length is 1.31 Å. The C(28)-N(16) bond length is 1.36 Å. The C(28)-H(34) bond length is 0.94 Å. In the twenty-ninth C site, C(29) is bonded in a trigonal planar geometry to one N(17), one N(19), and one H(35) atom. The C(29)-N(17) bond length is 1.30 Å. The C(29)-N(19) bond length is 1.35 Å. The C(29)-H(35) bond length is 0.94 Å. In the thirtieth C site, C(30) is bonded in a trigonal planar geometry to one N(18), one N(19), and one H(36) atom. The C(30)-N(18) bond length is 1.31 Å. The C(30)-N(19) bond length is 1.36 Å. The C(30)-H(36) bond length is 0.94 Å. There are twenty inequivalent N sites. In the first N site, N(1) is bonded in a distorted trigonal planar geometry to one Cu(1), one C(1), 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 single-bond geometry to one Cu(2), one C(2), and one N(1) atom. In the third N site, N(3) is bonded in a trigonal planar geometry to one C(1), one C(2), and one C(3) atom. In the fourth N site, N(4) is bonded in a distorted trigonal planar geometry to one Cu(1), one C(13), and one N(5) atom. The N(4)-N(5) bond length is 1.38 Å. In the fifth N site, N(5) is bonded in a distorted trigonal planar geometry to one Cu(2), one C(12), and one N(4) atom. In the sixth N site, N(6) is bonded in a trigonal planar geometry to one C(12), one C(13), and one C(5) atom. In the seventh N site, N(7) is bonded in a distorted trigonal planar geometry to one Cu(2), one C(14), and one N(8) atom. The N(7)-N(8) bond length is 1.39 Å. In the eighth N site, N(8) is bonded in a distorted water-like geometry to one C(15) and one N(7) atom. In the ninth N site, N(9) is bonded in a trigonal planar geometry to one C(14), one C(15), and one C(7) atom. In the tenth N site, N(10) is bonded in a trigonal non-coplanar geometry to one C(10), one C(11), and one C(9) atom. In the eleventh N site, N(11) is bonded in a distorted trigonal planar geometry to one Cu(1), one C(16), and one N(12) atom. The N(11)-N(12) bond length is 1.39 Å. In the twelfth N site, N(12) is bonded in a distorted trigonal planar geometry to one Cu(2), one C(17), and one N(11) atom. In the thirteenth N site, N(13) is bonded in a trigonal planar geometry to one C(16), one C(17), and one C(18) atom. In the fourteenth N site, N(14) is bonded in a distorted trigonal planar geometry to one Cu(1), one C(27), and one N(15) atom. The N(14)-N(15) bond length is 1.38 Å. In the fifteenth N site, N(15) is bonded in a water-like geometry to one C(28) and one N(14) atom. In the sixteenth N site, N(16) is bonded in a trigonal planar geometry to one C(20), one C(27), and one C(28) atom. In the seventeenth N site, N(17) is bonded in a 3-coordinate geometry to one Cu(2), one C(29), and one N(18) atom. The N(17)-N(18) bond length is 1.38 Å. In the eighteenth N site, N(18) is bonded in a distorted water-like geometry to one C(30) and one N(17) atom. In the nineteenth N site, N(19) is bonded in a trigonal planar geometry to one C(22), one C(29), and one C(30) atom. In the twentieth N site, N(20) is bonded in a trigonal non-coplanar geometry to one C(24), one C(25), and one C(26) atom. There are twenty-eight inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one C(1) atom. In the second H site, H(2) is bonded in a single-bond geometry to one C(2) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(4) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(4) atom. In the fifth H site, H(5,6) is bonded in a single-bond geometry to one C(6) atom. In the sixth H site, H(7,8) is bonded in a single-bond geometry to one C(8) atom. In the seventh H site, H(9,10) is bonded in a single-bond geometry to one C(9) atom. In the eighth H site, H(11,12) is bonded in a single-bond geometry to one C(10) atom. In the ninth H site, H(13,14) is bonded in a single-bond geometry to one C(11) atom. In the tenth H site, H(15) is bonded in a single-bond geometry to one C(12) atom. In the eleventh H site, H(16) is bonded in a single-bond geometry to one C(13) atom. In the twelfth H site, H(17) is bonded in a single-bond geometry to one C(14) atom. In the thirteenth H site, H(18) is bonded in a single-bond geometry to one C(15) atom. In the fourteenth H site, H(19) is bonded in a single-bond geometry to one C(16) atom. In the fifteenth H site, H(20) is bonded in a single-bond geometry to one C(17) atom. In the sixteenth H site, H(21) is bonded in a single-bond geometry to one C(19) atom. In the seventeenth H site, H(22) is bonded in a single-bond geometry to one C(19) atom. In the eighteenth H site, H(23) is bonded in a single-bond geometry to one C(21) atom. In the nineteenth H site, H(24) is bonded in a single-bond geometry to one C(21) atom. In the twentieth H site, H(25) is bonded in a single-bond geometry to one C(23) atom. In the twenty-first H site, H(26) is bonded in a single-bond geometry to one C(23) atom. In the twenty-second H site, H(27,28) is bonded in a single-bond geometry to one C(24) atom. In the twenty-third H site, H(29,30) is bonded in a single-bond geometry to one C(25) atom. In the twenty-fourth H site, H(31,32) is bonded in a single-bond geometry to one C(26) atom. In the twenty-fifth H site, H(33) is bonded in a single-bond geometry to one C(27) atom. In the twenty-sixth H site, H(34) is bonded in a single-bond geometry to one C(28) atom. In the twenty-seventh H site, H(35) is bonded in a single-bond geometry to one C(29) atom. In the twenty-eighth H site, H(36) is bonded in a single-bond geometry to one C(30) atom. Linkers: 8 c1nncn1[C@]12CN3C[C@](n4cnnc4)(C1)C[C@@](n1cnnc1)(C3)C2. Metal clusters: 4 [N][N][Cu]1[N][N][Cu]N=N1. The MOF has largest included sphere 4.97 A, density 1.11 g/cm3, surface area 4172.51 m2/g, accessible volume 0.48 cm3/g