[en] We have developed a C₂ symmetric N₂O₂ ligand that forms only a single isomer of an octahedral Zn(II) complex. The rigidity of the complex allows detailed understanding of molecular recognition of dpen and dach. The tactical placement of N-(2-cyanoethyl) substitution in the host diamine was found to be critical in the chiral recognition for both electronic and steric reasons; the electronic effect of the cyanoethyl groups in 4 results in slowing down the rate of dissociation of dpen from the metal and the steric effect of the cyanoethyl groups results in increasing the stereoselectivity of the recognition. Rigid and C₂ symmetric chiral ligands are useful for crafting stereoselective catalysts. Binol, binap, dpen, dach, pybox, and salen ligands are just some of the 'privileged' C₂ symmetric ligands that have been used to construct a wide variety of interesting metal complexes as stereoselective catalysts. The C₂ symmetric N₂O₂ salen ligand forms trans octahedral complex. It is uncommon to find C₂ symmetric N₂O₂ ligands that form only one kind of cis octahedral complexes. For example, can in principle form three isomers of octahedral complexes (cis-α, cis-β or trans). In contrast, and should form only the C₂ symmetric cis octahedral complexes (cis-α) due to the connectivity of the ligand