New Naphtho-und Benzonaphtho-kondensierte Pyridinokronen 5 -7 werden synthetisiert. Die neuen Kronenether bilden zahlreiche stiichiometrische kristalline EinschluDkomplexe mit typischen dipolar-aprotischen und apolaren Substanzen, darunter Dimethylformamid New naphtho-and benzonaphtho-fused pyridino crown compounds 5-7 are synthesized. The new crown ethers form numerous stoichiornetric crystalline inclusion complexes with typical dipolar-aprotic and apotar compounds including dimethylformamide and ureas, dirnethyi sulfoxide, nitro compounds, and nitriles or dioxane, benzene, and toluene. On the other hand, 5-7do not include alcohols and other protic compounds. As expected, the monobenzopyridino crown 4, synthesized as a reference compound, is unable to form inclusions. During the synthesis of 4 the 42-membered dimer macro ring 10 is also obtained. The structure of the crystalline dioxane inclusion compound of the trinaphthopyridino crown 7 is determined by X-ray structure analysis. It shows a specific crystal packing of the host molecules providing free lattice interspace which is occupied by the guest molecules. Based on the conformation of the host molecule and by comparison with the crystal structure of the benzo-analogous parent compound 2, conclusions for future design of host molecules for the crystal phase are drawn.