4-Phenoxymethylcoumarin was reported by Balasubramanian et al by the reaction of 4-bromomethylcoumarin with phenol. Compound was subjected to the Claisen rearrangement at high temperature, which gave negative results. Subsequently a number of 4-aryloxymethylcoumarins were synthesised as possible anti-microbial agents. Introduction of biocompatible fragments like vanillin and paracetamol resulted in novel 4-aryloxymethylcoumarins, which exhibited anti-inflammatory, analgesic and interesting photophysical properties also. The first report on the X-ray diffraction studies on 4-aryloxymethylcoumarins has revealed that the molecules exist as head-tail dimers in solid state as observed in the case of 7-methyl-4-tolyloxymethylcoumarin. In the light of above observations following 4-aryloxymethylcoumarins using chloro/bromo substituents have been subjected to X-ray diffraction studies.