Solid samples prepared from benzo-15-crown-5, its nitro, acetylamino and decanoylamino derivatives (Group I), and chloro-dibenzo-aza-crown ethers (Group II) with alkali metal salts were studied. The existence of solid adducts between LiBr, NaSCN, KSCN and crown ethers of group I was proved by DSC. The melting points of adducts of the same ligand were found to increase in KSCN