In the former system, the F-N RDF shows a distinct two-peak maximum at 150 K that develops into an unusually broad maximum at higher temperatures (Figure ). This observation is clearly related to off-centre displacements of the fluoride anions towards Al atoms, which lead to shorter and longer distances to the central nitrogen atoms of the surrounding TMA molecules. In the case of AlPO4-AST_QNU, the F-N RDF obtained for 150 K shows a first main maximum centred at ~4.9 Å and a secondary maximum centred at ~5. It has to be conceded that the assumption of a fully ordered arrangement of the QNU cations is a significant approximation. It cannot be expected that such a strict ordering would occur in real AST-type zeotypes, which are typically synthesised at temperatures of 450 to 480 K, where thermal motion of the OSDAs will be considerable. Nevertheless, the present work provides important new insights into the local structure of these systems, and it highlights the theoretical possibility to induce collective framework deformations through an ordering of the extra-framework species. It could be envisaged to judiciously choose other OSDAs that stabilise such distortions, which could be proposed on the basis of further computations. External fields might provide another possibility to induce an ordering of the OSDAs. While this work is not aimed at the prediction of any specific property of the investigated zeotypes, it can be anticipated that some material properties could be tuned through ordered distortions, which might be relevant for potential applications (e.g., in dielectrics).