The first precise molecular structure of a monomeric transition metal cyanide, copper(I) cyanide

Copper(I) cyanide is an important reagent in organic, organometallic, and supramolecular chemistry because of both the copper center and the versatile cyanide ligand. Solid-phase CuCN and many of its derivatives show oligomeric or polymeric structures, a trait shared by other metal cyanides. Often, it is difficult to specify the orientation of the cyano ligand in an X-ray structure. Here the first preparation and precise structure of a monomeric transition metal cyanide is reported. Gas-phase reaction between copper vapor and cyanogen (NCCN) clearly gives CuCN (not CuNC). The precise structure of CuCN so produced is determined by millimeter/submillimeter-wave spectroscopy. Because of the highly efficient synthesis and the presence of significant amounts of two copper isotopes, such strong signals were seen that natural-abundance materials allowed observation of transitions for the four isotopomers ⁶³Cu¹²C¹⁴N, ⁶⁵Cu¹²C¹⁴N, ⁶³Cu¹³C¹⁴N, and ⁶³Cu¹²C¹⁵N and the determination of r_o, _r, and r_m⁽²⁾structures. All data unequivocally show a linear geometry and that the carbon of cyanide is bound to copper with a Cu-C distance of 1.82962(4) Å in the structure, which is likely to be closest to the equilibrium geometry.