4-Phenoxymethylcoumarin was synthesized 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 synthesized as possible anti-microbial agents. Introduction of biocompatible fragments like vanillin and paracetamol resulted in novel 4-aryloxymethylcoumarins V and VI which exhibited anti-inflammatory, analgesic and interesting photo physical 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 possessing chloro/bromo substituents have been subjected to X-ray diffraction studies.