Cu3C6N5H4I2 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a distorted water-like geometry to one N(3), one N(4), one I(1), and one I(2) atom. The Cu(1)-N(3) bond length is 1.99 Å. The Cu(1)-N(4) bond length is 2.03 Å. The Cu(1)-I(1) bond length is 2.68 Å. The Cu(1)-I(2) bond length is 2.65 Å. In the second Cu site, Cu(2) is bonded in a 1-coordinate geometry to one N(2), one I(2), and two equivalent I(1) atoms. The Cu(2)-N(2) bond length is 2.03 Å. The Cu(2)-I(2) bond length is 2.60 Å. There is one shorter (2.62 Å) and one longer (2.78 Å) Cu(2)-I(1) bond length. In the third Cu site, Cu(3) is bonded in a 4-coordinate geometry to one N(1), one N(5), one I(1), and one I(2) atom. The Cu(3)-N(1) bond length is 1.95 Å. The Cu(3)-N(5) bond length is 1.93 Å. The Cu(3)-I(1) bond length is 2.99 Å. The Cu(3)-I(2) bond length is 2.64 Å. There are six inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one C(2), one C(3), and one C(4) atom. The C(1)-C(2) bond length is 1.40 Å. The C(1)-C(3) bond length is 1.40 Å. The C(1)-C(4) bond length is 1.46 Å. In the second C site, C(2) is bonded in a distorted bent 120 degrees geometry to one C(1), one N(5), and one H(1) atom. The C(2)-N(5) bond length is 1.35 Å. The C(2)-H(1) bond length is 1.09 Å. In the third C site, C(3) is bonded in a distorted trigonal planar geometry to one C(1), one C(6), and one H(3) atom. The C(3)-C(6) bond length is 1.39 Å. The C(3)-H(3) bond length is 1.09 Å. In the fourth C site, C(4) is bonded in a distorted trigonal planar geometry to one C(1), one N(1), and one N(2) atom. The C(4)-N(1) bond length is 1.35 Å. The C(4)-N(2) bond length is 1.35 Å. In the fifth C site, C(5) is bonded in a distorted trigonal planar geometry to one C(6), one N(5), and one H(2) atom. The C(5)-C(6) bond length is 1.39 Å. The C(5)-N(5) bond length is 1.36 Å. The C(5)-H(2) bond length is 1.09 Å. In the sixth C site, C(6) is bonded in a distorted single-bond geometry to one C(3), one C(5), and one H(4) atom. The C(6)-H(4) bond length is 1.09 Å. There are five inequivalent N sites. In the first N site, N(1) is bonded in a distorted trigonal planar geometry to one Cu(3), one C(4), and one N(4) atom. The N(1)-N(4) bond length is 1.34 Å. In the second N site, N(2) is bonded in a 3-coordinate geometry to one Cu(2), one C(4), and one N(3) atom. The N(2)-N(3) bond length is 1.35 Å. In the third N site, N(3) is bonded in a distorted trigonal planar geometry to one Cu(1), one N(2), and one N(4) atom. The N(3)-N(4) bond length is 1.33 Å. In the fourth N site, N(4) is bonded in a distorted trigonal planar geometry to one Cu(1), one N(1), and one N(3) atom. In the fifth N site, N(5) is bonded in a trigonal planar geometry to one Cu(3), one C(2), and one C(5) atom. There are four inequivalent H sites. In the first H site, H(1) 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(5) atom. In the third H site, H(3) is bonded in a single-bond geometry to one C(3) atom. In the fourth H site, H(4) is bonded in a single-bond geometry to one C(6) atom. There are two inequivalent I sites. In the first I site, I(1) is bonded in a 4-coordinate geometry to one Cu(1), one Cu(3), and two equivalent Cu(2) atoms. In the second I site, I(2) is bonded in a distorted trigonal non-coplanar geometry to one Cu(1), one Cu(2), and one Cu(3) atom. Linkers: 4 c1cncc(C2=NN=N[N]2)c1. Metal clusters: 12 [Cu]. The MOF has largest included sphere 2.45 A, density 3.55 g/cm3, surface area 1935.11 m2/g, accessible volume 0.07 cm3/g