The DMASD + molecules in the larger [4 •5 8 •6 •10 2 ] cages are fully ordered, and their location was determined using a combination of force-field based modeling and Rietveld refinement (Figure ). As this published structure does not require any modifications prior to the DFT optimizations, it was taken as starting point. Furthermore, the NMR results of Paillaud et al. confirmed the absence of a dynamic disorder of the fluoride anions, agreeing with earlier results of Fyfe et al. 10 of the 12 vertices of the ] cage correspond to meeting points of three edges, and DFT optimizations were carried out with fluoride anions located at these 10 sites. Four of these Si atoms belong to the basal 4MR, four are located roughly in the equatorial plane, and another two form the apices of the cage. In the experimental structure, fluoride is bonded to one of these apical sites (F@Si3). All sites are visualized in Figure , colored according to their relative energy with respect to F@Si3. While the second apical site F@Si4 is very close in energy to the experimental one (ΔErel = 2.4 kJ mol -1 ), all equatorial positions are energetically unfavorable. On the other hand, one of the sites associated with the basal 4MR is energetically more favorable than the experimental position (F@Si10: ΔErel = -7.9 kJ mol -1 , the other 4MR sites are similar in energy to F@Si3). STF is the only of the studied zeolites where the lowest-energy fluoride location deviates from the experimentally observed position. In this context, it has to be noted that the structure of Mu-26 was refined from powder diffraction data. As the DMASD + cations could not be localized with Fourier difference methods, presumably due to disorder, their initial positions were obtained using force-field based modeling with the DREIDING force field. This is an important difference to the other four zeolites, where the crystal structures, including positions of the non-hydrogen OSDA atoms, were determined from single-crystal X-ray diffraction (XRD) data (in some cases using synchrotron radiation). For this reason, it seems plausible to attribute a larger degree of uncertainty to the position and orientation of the OSDA in this system, and the DFT