Cu4C12N9H18I crystallizes in the hexagonal P6_3 space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a distorted tetrahedral geometry to three equivalent N(1) and one I(1) atom. All Cu(1)-N(1) bond lengths are 1.98 Å. The Cu(1)-I(1) bond length is 2.72 Å. In the second Cu site, Cu(2) is bonded in a distorted bent 150 degrees geometry to one N(2), one N(3), and one I(1) atom. The Cu(2)-N(2) bond length is 1.87 Å. The Cu(2)-N(3) bond length is 1.88 Å. The Cu(2)-I(1) bond length is 2.94 Å. There are four inequivalent C sites. In the first C site, C(1) is bonded in a distorted trigonal planar geometry to one C(2), one N(2), and one N(3) atom. The C(1)-C(2) bond length is 1.48 Å. The C(1)-N(2) bond length is 1.34 Å. The C(1)-N(3) bond length is 1.36 Å. In the second C site, C(2) is bonded in a distorted trigonal non-coplanar geometry to one C(1), one H(1), one H(2), and one H(3) atom. The C(2)-H(1) bond length is 1.10 Å. The C(2)-H(2) bond length is 1.10 Å. The C(2)-H(3) bond length is 1.10 Å. In the third C site, C(3) is bonded in a distorted trigonal planar geometry to one C(4), one N(1), and one N(3) atom. The C(3)-C(4) bond length is 1.48 Å. The C(3)-N(1) bond length is 1.33 Å. The C(3)-N(3) bond length is 1.37 Å. In the fourth C site, C(4) is bonded in a distorted trigonal non-coplanar geometry to one C(3), one H(4), one H(5), and one H(6) atom. The C(4)-H(4) bond length is 1.10 Å. The C(4)-H(5) bond length is 1.10 Å. The C(4)-H(6) bond length is 1.10 Å. There are three inequivalent N sites. In the first N site, N(1) is bonded in a 3-coordinate geometry to one Cu(1), one C(3), and one N(2) atom. The N(1)-N(2) bond length is 1.38 Å. In the second N site, N(2) is bonded in a 3-coordinate geometry to one Cu(2), one C(1), and one N(1) atom. In the third N site, N(3) is bonded in a trigonal planar geometry to one Cu(2), one C(1), and one C(3) atom. There are six inequivalent H sites. In the first H site, H(5) is bonded in a single-bond geometry to one C(4) atom. In the second H site, H(6) is bonded in a single-bond geometry to one C(4) atom. In the third H site, H(1) is bonded in a single-bond geometry to one C(2) atom. In the fourth H site, H(2) is bonded in a single-bond geometry to one C(2) atom. In the fifth H site, H(3) is bonded in a single-bond geometry to one C(2) atom. In the sixth H site, H(4) is bonded in a single-bond geometry to one C(4) atom. I(1) is bonded in a distorted tetrahedral geometry to one Cu(1) and three equivalent Cu(2) atoms. Linkers: 2 CC1=[N]=C(N=N1)C ,1 CC1=NC(C)=N[N]1 ,2 CC1=NN=C(C)[N]1. Metal clusters: 1 C[C]1N([Cu]/N=N\[Cu](I)(/N=N\[Cu])/N=N\[Cu])[C](C)N([Cu](I)(/N=N\[Cu])/N=N\[Cu])N1[Cu]. The MOF has largest included sphere 2.54 A, density 2.21 g/cm3, surface area 3498.92 m2/g, accessible volume 0.15 cm3/g