Intramolecular ether oxygen coordination in the zinc complexes with dipicolylamine (DPA)-derived ligands

► The intramolecular ether oxygen coordination in the zinc complex was studied. ► The first crystal structure of ZnN3X2Oether (X = halogen) system is presented. ► The five-membered ring chelate in L could hold the ether oxygen coordination. ► The six-membered chelate in L′ is disfavored, dissociating the oxygen from metal. ► Extra metal binding site in LPy promotes the formation of six-membered chelate.