A series of alkali metal azide-crown ether complexes, [Li(crown-4)(N3)], [Na(crown-5)(N3)], [Na(crown-5)(H2O)2]N3, [K(crown-6)(N3)(H2O)], [Rb(crown-6)(N3)(H2O)], [Cs(crown-6)(N3)]2, and [Cs(crown-6)(N3)(H2O)(MeOH)], has been synthesised. In most cases, single crystals were obtained, which allowed X-ray crystal structures to be derived. The structures obtained have been compared with molecular structures computed by density functional theory (DFT) calculations. This has allowed the effects of the crystal lattice on the structures to be investigated. Also, a study of the MNterminal metal–azide bond length and charge densities on the metal (M) and terminal nitrogen centre (Nterminal) in these complexes has allowed the nature of the metal–azide bond to be probed in each case. The bonding in these complexes is believed to be predominantly ionic or ion-dipole in character, with the differences in geometries reflecting the balance between maximising the coordination number of the metal centre and minimising ligand-ligand repulsions. The structures of the crown ether complexes determined in this work show the subtle interplay of such factors. The significant role of hydrogen bonding is also demonstrated, most clearly in the structures of the K and Rb dimers, but also in the chain structure of the hydrated Cs complex.