Cu3H21(C5N2)4 crystallizes in the triclinic P-1 space group. The structure consists of a Cu3H21(C5N2)4 framework. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a distorted trigonal planar geometry to one C(20), one N(5), and one N(6) atom. The Cu(1)-C(20) bond length is 1.82 Å. The Cu(1)-N(5) bond length is 2.00 Å. The Cu(1)-N(6) bond length is 1.90 Å. In the second Cu site, Cu(2) is bonded in a distorted trigonal planar geometry to one C(18), one N(1), and one N(7) atom. The Cu(2)-C(18) bond length is 1.82 Å. The Cu(2)-N(1) bond length is 1.99 Å. The Cu(2)-N(7) bond length is 1.93 Å. In the third Cu site, Cu(3) is bonded in a trigonal planar geometry to one C(19), one N(3), and one N(8) atom. The Cu(3)-C(19) bond length is 1.83 Å. The Cu(3)-N(3) bond length is 2.02 Å. The Cu(3)-N(8) bond length is 1.88 Å. There are twenty inequivalent C sites. In the first C site, C(1) is bonded in a distorted trigonal non-coplanar geometry to one C(2), one H(1), one H(2), and one H(3) atom. The C(1)-C(2) bond length is 1.49 Å. The C(1)-H(1) bond length is 1.10 Å. The C(1)-H(2) bond length is 1.10 Å. The C(1)-H(3) bond length is 1.10 Å. In the second C site, C(2) is bonded in a distorted trigonal planar geometry to one C(1), one C(3), and one N(2) atom. The C(2)-C(3) bond length is 1.40 Å. The C(2)-N(2) bond length is 1.35 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 1.42 Å. The C(3)-C(6) bond length is 1.49 Å. In the fourth C site, C(4) is bonded in a distorted trigonal planar geometry to one C(3), one C(5), and one N(1) atom. The C(4)-C(5) bond length is 1.49 Å. The C(4)-N(1) bond length is 1.35 Å. In the fifth C site, C(5) is bonded in a distorted trigonal non-coplanar geometry to one C(4), one H(6), one H(7), and one H(8) atom. The C(5)-H(6) bond length is 1.10 Å. The C(5)-H(7) bond length is 1.10 Å. The C(5)-H(8) bond length is 1.10 Å. In the sixth C site, C(6) is bonded in a distorted water-like geometry to one C(3), one C(7), one H(10), and one H(9) atom. The C(6)-C(7) bond length is 1.51 Å. The C(6)-H(10) bond length is 1.10 Å. The C(6)-H(9) bond length is 1.10 Å. In the seventh C site, C(7) is bonded in a distorted trigonal planar geometry to one C(6), one C(8), and one N(3) atom. The C(7)-C(8) bond length is 1.40 Å. The C(7)-N(3) bond length is 1.35 Å. In the eighth C site, C(8) is bonded in a distorted single-bond geometry to one C(7), one C(9), and one H(11) atom. The C(8)-C(9) bond length is 1.39 Å. The C(8)-H(11) bond length is 1.09 Å. In the ninth C site, C(9) is bonded in a distorted trigonal planar geometry to one C(10), one C(8), and one H(12) atom. The C(9)-C(10) bond length is 1.39 Å. The C(9)-H(12) bond length is 1.09 Å. In the tenth C site, C(10) is bonded in a distorted single-bond geometry to one C(11), one C(9), and one H(13) atom. The C(10)-C(11) bond length is 1.39 Å. The C(10)-H(13) bond length is 1.09 Å. In the eleventh C site, C(11) is bonded in a distorted trigonal planar geometry to one C(10), one C(12), and one N(3) atom. The C(11)-C(12) bond length is 1.51 Å. The C(11)-N(3) bond length is 1.35 Å. In the twelfth C site, C(12) is bonded in a water-like geometry to one C(11), one C(15), one H(14), and one H(15) atom. The C(12)-C(15) bond length is 1.49 Å. The C(12)-H(14) bond length is 1.10 Å. The C(12)-H(15) bond length is 1.10 Å. In the thirteenth C site, C(13) is bonded in a distorted trigonal non-coplanar geometry to one C(14), one H(16), one H(17), and one H(18) atom. The C(13)-C(14) bond length is 1.49 Å. The C(13)-H(16) bond length is 1.10 Å. The C(13)-H(17) bond length is 1.10 Å. The C(13)-H(18) bond length is 1.10 Å. In the fourteenth C site, C(14) is bonded in a distorted single-bond geometry to one C(13), one C(15), and one N(4) atom. The C(14)-C(15) bond length is 1.40 Å. The C(14)-N(4) bond length is 1.35 Å. In the fifteenth C site, C(15) is bonded in a trigonal planar geometry to one C(12), one C(14), and one C(16) atom. The C(15)-C(16) bond length is 1.42 Å. In the sixteenth C site, C(16) is bonded in a distorted single-bond geometry to one C(15), one C(17), and one N(5) atom. The C(16)-C(17) bond length is 1.49 Å. The C(16)-N(5) bond length is 1.35 Å. In the seventeenth C site, C(17) is bonded in a distorted trigonal non-coplanar geometry to one C(16), one H(19), one H(20), and one H(21) atom. The C(17)-H(19) bond length is 1.10 Å. The C(17)-H(20) bond length is 1.10 Å. The C(17)-H(21) bond length is 1.10 Å. In the eighteenth C site, C(18) is bonded in a linear geometry to one Cu(2) and one N(6) atom. The C(18)-N(6) bond length is 1.18 Å. In the nineteenth C site, C(19) is bonded in a linear geometry to one Cu(3) and one N(7) atom. The C(19)-N(7) bond length is 1.18 Å. In the twentieth C site, C(20) is bonded in a linear geometry to one Cu(1) and one N(8) atom. The C(20)-N(8) bond length is 1.18 Å. There are eight inequivalent N sites. In the first N site, N(1) is bonded in a 3-coordinate geometry to one Cu(2), one C(4), and one N(2) atom. The N(1)-N(2) bond length is 1.35 Å. In the second N site, N(2) is bonded in a 2-coordinate geometry to one C(2), one N(1), and one H(4) atom. The N(2)-H(4) bond length is 1.02 Å. In the third N site, N(3) is bonded in a trigonal planar geometry to one Cu(3), one C(11), and one C(7) atom. In the fourth N site, N(4) is bonded in a 3-coordinate geometry to one C(14), one N(5), and one H(5) atom. The N(4)-N(5) bond length is 1.36 Å. The N(4)-H(5) bond length is 1.02 Å. In the fifth N site, N(5) is bonded in a 3-coordinate geometry to one Cu(1), one C(16), and one N(4) atom. In the sixth N site, N(6) is bonded in a linear geometry to one Cu(1) and one C(18) atom. In the seventh N site, N(7) is bonded in a linear geometry to one Cu(2) and one C(19) atom. In the eighth N site, N(8) is bonded in a linear geometry to one Cu(3) and one C(20) atom. There are twenty-one 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(1) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(1) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one N(2) atom. In the fifth H site, H(5) is bonded in a single-bond geometry to one N(4) atom. In the sixth H site, H(6) is bonded in a single-bond geometry to one C(5) atom. In the seventh H site, H(7) is bonded in a single-bond geometry to one C(5) atom. In the eighth H site, H(8) is bonded in a single-bond geometry to one C(5) atom. In the ninth H site, H(9) is bonded in a single-bond geometry to one C(6) atom. In the tenth H site, H(10) is bonded in a single-bond geometry to one C(6) atom. In the eleventh H site, H(11) is bonded in a single-bond geometry to one C(8) atom. In the twelfth H site, H(12) is bonded in a single-bond geometry to one C(9) atom. In the thirteenth H site, H(13) is bonded in a single-bond geometry to one C(10) atom. In the fourteenth H site, H(14) is bonded in a single-bond geometry to one C(12) atom. In the fifteenth H site, H(15) is bonded in a single-bond geometry to one C(12) atom. In the sixteenth H site, H(16) is bonded in a single-bond geometry to one C(13) atom. In the seventeenth H site, H(17) is bonded in a single-bond geometry to one C(13) atom. In the eighteenth H site, H(18) is bonded in a single-bond geometry to one C(13) atom. In the nineteenth H site, H(19) is bonded in a single-bond geometry to one C(17) atom. In the twentieth H site, H(20) is bonded in a single-bond geometry to one C(17) atom. In the twenty-first H site, H(21) is bonded in a single-bond geometry to one C(17) atom. Linkers: 2 Cc1n[nH]c(C)c1Cc1cccc(Cc2c(C)n[nH]c2C)n1. Metal clusters: 6 [Cu]. The MOF has largest included sphere 5.21 A, density 1.31 g/cm3, surface area 4675.30 m2/g, accessible volume 0.36 cm3/g