Cyanate is an ambidentate ligand which can donate the pair of electrons on the nitrogen atom or the oxygen atom, or both. Structurally the isomers can be distinguished by the geometry of the complex. In N-bonded cyanate complexes the M−NCO unit sometimes has a linear structure, but with O-bonded cyanate the M−O−C unit is bent. Thus, the silver cyanato complex, , has a linear structure as shown by X-ray crystallography. However, the crystal structure of silver cyanate shows zigzag chains of nitrogen atoms and silver atoms. There also exists a structure
    NCO
 Ni    Ni
    OCN
in which the Ni-N-C group is bent.
Infrared spectroscopy has been used extensively to distinguish between isomers. Many complexes of divalent metals are N-bonded. O-Bonding has been suggested for complexes of the type , M = Mo(III), Re(IV), and Re(V). The yellow complex  and orange complex  are linkage isomers and show differences in their infrared spectra which can be used for diagnosis.
The cyanate ion can bridge between two metal atoms by using both its donor atoms. For example, this structure is found in the compound . In this compound both the Ni−N−C unit and Ni−O−C unit are bent, even though in the first case donation is through the nitrogen atom.