A series of 4,6-diaryl-3-cyano-2(1H)-pyridones 3a–c were synthesized with 70–90% yields through a multicomponent reaction involving aromatic aldehydes, ethyl cyanoacetate, acetophenone, and ammonium acetate under microwave irradiation at 100 °C for 30 minutes. A thorough characterization was conducted, including spectroscopic, spectrometric, thermal, and X-ray crystallographic analyses. This protocol stands out for forming four chemical bonds in a single step, utilizing an eco-friendly solvent, reduced reaction times, and enabling straightforward purification via simple filtration. The SC-XRD analysis showed that compounds 3a–c crystallized with six independent molecules in the asymmetric units due to the free rotation between aromatic fragments. In all cases, molecular dimers are formed by N-H‧‧‧O and C-H‧‧‧O hydrogen bonds forming chains through C-H‧‧‧π, C-N‧‧‧π, and π‧‧‧π interactions. These chains exhibited structural similarity across 3a–c and acted as supramolecular bricks, interconnected by C-H‧‧‧π, C-H‧‧‧Cl, C-H‧‧‧Br, and van der Waals forces. Intrachain and interchain C-N‧‧‧π and C-H‧‧‧N-C contacts involving the cyano group appeared crucial in crystal formation, representing an observation not commonly documented in literature.