The perchlorate of 2-{2-[4-(13-aza-1,4,7,10-tetroxa-13-cyclopentadecyl)phenyl]ethenyl}-3-ethylbenzothiazolium (3) has been synthesised and its structure determined in the crystalline state by X-ray diffraction and in solution in acetonitrile by ¹H NMR methods. Complexation with barium and silver cations in solution has been studied in comparison with other model azacrown molecules by spectrophotometric and potentiometric methods. With the exception of the puckered azacrown moiety, the structure of 3 is remarkably planar, consistent with extensive π-conjugation throughout the remainder of the molecule in both solid and solution states. Compound 3 forms a stable 1∶1 complex with Ba²⁺ ions in acetonitrile, with a stability constant of K₁ = 80 ± 10 dm³ mol^–1; the complexation results in major changes in the electronic absorption spectrum of 3, consistent with binding to the azacrown moiety. A model compound, phenylaza-15-crown-5 (2a), was found to bind Ba²⁺ to form both a 1∶1 ligand–metal complex (LM), with a stability constant of K₁ = (2.0 ± 0.2) × 10⁴ dm³ mol^–1, and a 2∶1 (L₂M) complex, with a stability constant of K₂ = 220 ± 20 dm³ mol^–1 for binding of the second ligand. The electronic absorption and NMR spectra both indicate binding of the ‘hard’ Ba²⁺ cation to the azacrown oxygen atoms. However, by contrast, the evidence from NMR data shows that the ‘soft’ Ag⁺ cation complexes with 2a mainly through a strong interaction with the azacrown nitrogen atom, giving a 1∶1 complex with a stability constant of K₁ = 6 ± 1 dm³ mol^–1, determined by potentiometry. No complexation of 3 with Ag⁺ is observed. Studies of the simple aza-15-crown-5 ether reveal strong complexation with both Ba²⁺ (K₁ × K₂ > 10¹² dm⁶ mol^–2) and Ag⁺ [K₁ = (1.15 ± 0.10) × 10⁴ dm³ mol^–1 and K₂ = 450 ± 20 dm³ mol^–1].