CuCN5H2 crystallizes in the hexagonal P6_122 space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a trigonal pyramidal geometry to one N(1), one N(4), one N(7), and one N(9) atom. The Cu(1)-N(1) bond length is 2.03 Å. The Cu(1)-N(4) bond length is 1.93 Å. The Cu(1)-N(7) bond length is 2.30 Å. The Cu(1)-N(9) bond length is 1.94 Å. In the second Cu site, Cu(2) is bonded in a trigonal planar geometry to one N(2) and two equivalent N(7) atoms. The Cu(2)-N(2) bond length is 2.00 Å. Both Cu(2)-N(7) bond lengths are 1.93 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one N(5) and two equivalent N(1) atoms. The C(1)-N(5) bond length is 1.33 Å. Both C(1)-N(1) bond lengths are 1.36 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one N(1), one N(2), and one N(8) atom. The C(2)-N(1) bond length is 1.36 Å. The C(2)-N(2) bond length is 1.36 Å. The C(2)-N(8) bond length is 1.33 Å. There are nine inequivalent N sites. In the first N site, N(4) is bonded in a 2-coordinate geometry to one Cu(1) and one N(3) atom. The N(4)-N(3) bond length is 1.18 Å. In the second N site, N(7) is bonded in a 3-coordinate geometry to one Cu(1), one Cu(2), and one N(6) atom. The N(7)-N(6) bond length is 1.19 Å. In the third 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 fourth N site, N(8) is bonded in a trigonal planar geometry to one C(2), one H(2), and one H(3) atom. The N(8)-H(2) bond length is 1.02 Å. The N(8)-H(3) bond length is 1.02 Å. In the fifth N site, N(5) is bonded in a trigonal planar geometry to one C(1) and two equivalent H(1) atoms. Both N(5)-H(1) bond lengths are 1.02 Å. In the sixth N site, N(6) is bonded in a linear geometry to one N(7) and one N(9) atom. The N(6)-N(9) bond length is 1.18 Å. In the seventh N site, N(2) is bonded in a trigonal planar geometry to one Cu(2) and two equivalent C(2) atoms. In the eighth N site, N(9) is bonded in a distorted bent 150 degrees geometry to one Cu(1) and one N(6) atom. In the ninth N site, N(3) is bonded in a linear geometry to two equivalent N(4) atoms. There are three inequivalent H sites. In the first H site, H(3) is bonded in a single-bond geometry to one N(8) atom. In the second H site, H(1) is bonded in a single-bond geometry to one N(5) atom. In the third H site, H(2) is bonded in a single-bond geometry to one N(8) atom. Linkers: 6 NC1=NC(=[N]=C([N]1)N)N. Metal clusters: 18 [Cu]. The MOF has largest included sphere 4.11 A, density 2.15 g/cm3, surface area 3007.73 m2/g, accessible volume 0.15 cm3/g