A range of secondary dialkylammonium (R₂NH₂⁺) ions has been shown to thread through the cavities of appropriately-sized crown ether compounds to afford interwoven complexes. X-Ray crystallographic investigations to probe the solid-state properties of these supermolecules have revealed that many subtle factors—e.g., solvent of crystallisation, crown ether conformation and anion interactions—can influence the nature of the overall three-dimensional superstructures. Nonetheless, a family of building blocks—namely R₂NH₂⁺ ions and crown ethers—can be generated, which constitute a molecular meccano kit. By mixing and matching these modules in different ways, intricate interwoven supramolecular architectures can be constructed. From relatively simple beginnings—where one R₂NH₂⁺ ion is threaded through one monotopic crown ether (dibenzo[24]crown-8)—the designed evolution of the building blocks in the molecular meccano kit has led to more elaborate multiply encircled and/or multiply threaded superstructures. The effects of crown ether constitution, macroring size, and both crown ether as well as R₂NH₂⁺ ion substitution, upon the solid-state behaviour of these interwoven complexes have also been examined. A statistical analysis of the hydrogen bonding interactions observed in these systems has been carried out. It reveals that a reasonable correlation exists between N⁺–HO bond angle and HO bond length. The correlation between C–HO bond angle and HO distance is poor, suggesting that C–HO hydrogen bonding interactions are of secondary importance in determining the co-conformations adopted by these supermolecules.