CuCNHI crystallizes in the orthorhombic Pnma space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one N(2), one I(2), and two equivalent I(1) atoms to form corner-sharing CuI3N tetrahedra. The Cu(1)-N(2) bond length is 2.01 Å. The Cu(1)-I(2) bond length is 2.57 Å. Both Cu(1)-I(1) bond lengths are 2.61 Å. In the second Cu site, Cu(2) is bonded to one N(1), one I(2), and two equivalent I(1) atoms to form corner-sharing CuI3N tetrahedra. The Cu(2)-N(1) bond length is 2.02 Å. The Cu(2)-I(2) bond length is 2.58 Å. There is one shorter (2.60 Å) and one longer (2.61 Å) Cu(2)-I(1) bond length. There are two inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to two equivalent N(1) and one H(1) atom. Both C(1)-N(1) bond lengths are 1.34 Å. The C(1)-H(1) bond length is 1.09 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 1.34 Å. The C(2)-N(2) bond length is 1.34 Å. The C(2)-H(2) bond length is 1.09 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a trigonal planar geometry to one Cu(2), one C(1), and one C(2) atom. In the second N site, N(2) is bonded in a trigonal planar geometry to one Cu(1) and two equivalent C(2) atoms. 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(1) is bonded in a trigonal non-coplanar geometry to one Cu(1) and two equivalent Cu(2) atoms. In the second I site, I(2) is bonded in a trigonal non-coplanar geometry to one Cu(1) and two equivalent Cu(2) atoms. Linkers: 4 C1=NC=[N]=C[N]1. Metal clusters: 12 [Cu]. The MOF has largest included sphere 2.19 A, density 4.14 g/cm3, surface area 1861.35 m2/g, accessible volume 0.07 cm3/g