Cu3C2N3H2I2 crystallizes in the monoclinic P2/c space group. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a linear geometry to two equivalent N(1) atoms. Both Cu(1)-N(1) bond lengths are 1.86 Å. In the second Cu site, Cu(2) is bonded in a distorted bent 150 degrees geometry to two equivalent N(2) and two equivalent I(1) atoms. Both Cu(2)-N(2) bond lengths are 1.89 Å. Both Cu(2)-I(1) bond lengths are 3.10 Å. In the third Cu site, Cu(3) is bonded in a distorted single-bond geometry to one N(3), one I(2), and two equivalent I(1) atoms. The Cu(3)-N(3) bond length is 1.99 Å. The Cu(3)-I(2) bond length is 2.60 Å. There is one shorter (2.64 Å) and one longer (2.69 Å) Cu(3)-I(1) bond length. In the fourth Cu site, Cu(4) is bonded in a 4-coordinate geometry to two equivalent I(1) and two equivalent I(2) atoms. There is one shorter (2.66 Å) and one longer (2.68 Å) Cu(4)-I(1) bond length. There is one shorter (2.61 Å) and one longer (2.64 Å) Cu(4)-I(2) bond length. There are two 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 1.36 Å. The C(1)-N(3) bond length is 1.33 Å. The C(1)-H(1) bond length is 1.08 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one N(1), one N(2), and one H(2) atom. The C(2)-N(1) bond length is 1.36 Å. The C(2)-N(2) bond length is 1.33 Å. The C(2)-H(2) bond length is 1.09 Å. There are three inequivalent N sites. In the first N site, N(1) is bonded in a trigonal planar geometry to one Cu(1), one C(1), and one C(2) atom. In the second N site, N(2) is bonded in a distorted trigonal planar geometry to one Cu(2), one C(2), and one N(3) atom. The N(2)-N(3) bond length is 1.38 Å. In the third N site, N(3) is bonded in a 3-coordinate geometry to one Cu(3), one C(1), and one N(2) atom. There are two 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. There are two inequivalent I sites. In the first I site, I(2) is bonded in a 3-coordinate geometry to one Cu(3) and two equivalent Cu(4) atoms. In the second I site, I(1) is bonded in a 5-coordinate geometry to one Cu(2), two equivalent Cu(3), and two equivalent Cu(4) atoms. Linkers: 3 [N]1=CN=NC=1 ,1 C1=NC=N[N]1. Metal clusters: 12 [Cu]. The MOF has largest included sphere 1.91 A, density 4.34 g/cm3, surface area 1676.22 m2/g, accessible volume 0.02 cm3/g