A new two-fold interpenetrated pillar-layered metal-organic framework (MOF) was designed and synthesized based on zirconium cations, an amine-functionalized ligand, and a linear exo-bidentate bis-pyridine ligand. The structure of the prepared framework was evaluated using various techniques such as FT-IR, EDX, elemental mapping analysis, SEM, XRD, TGA/DTA, and BET. Then, catalytic application of the prepared zirconium-based MOF was successfully explored in the synthesis of novel 6H-chromeno[4,3-b]quinolin-6-ones 4(a-l) through a one-pot three-component condensation reaction of 4-hydroxycumarine, 1-naphthylamine, and aromatic aldehydes under solvent-free conditions at 110 °C. The pure products were obtained with high atom efficiency (AE) and short reaction times and characterized by FT‐IR, NMR, and mass spectrometry techniques.
