The synthesis of 4-aryl-2H-pyran-2-ones 7 was accomplished by rearrangement of 6-aryl-2H-pyran-ones 5 with ethyl cyanoacetate 6 in the presence of a base in DMF at room temperature. The reaction products were achieved in good yields. The reaction products were characterized by their spectroscopic analysis. The structure of compound 7a was confirmed by its single crystal X-ray analysis. Moreover, single crystal X-ray study of compound 7a showed rare plausible peri oxygen-oxygen interactions between O2 and O3. Further compound 7a showed homodimer intermolecular H-bonding interactions between nitrogen and OH groups along with a-b plane. These non-covalent interactions stabilized compound 7a in the crystalline state. © 2021 Elsevier B.V.