Eleven complexes of a hybrid ligand 4'-(4'''-benzo-15-crown-5)-methyloxy-2,2':6',2''-terpyridine (L) were synthesized and characterised by elemental analysis, IR-spectroscopy and X-ray analysis. The crystal structures of seven complexes were determined either from single-crystal data ([NaNCS.L] (6)and [CuL2.NaNCS.Na(NCS)2]+.NCS-.CH3CN) (11) or from powder diffraction data ([CoL2]2+.2NCS- (5) and [ML2]2+.2PF6-.nEtOH.mH2O, M = Ni(II) (1), Co(II) (2), Cu(II) (3), Zn(II) (4)) and revealed good coordinating properties of the ligand L and structural diversity of the obtained compounds. In compounds 1-5, the pi-pi interactions between pyridine rings or between pyridine and benzene rings play an important role in association of the cations.