The F-Ge RDFs as well as trajectories of individual fluoride anions are visualised in Figure . Altogether, the findings mirror those discussed above for SiO2-AST systems: The RDFs show a single maximum, centred at a distance of about 2.75 Å. In GeO2-AST_TMA, the fluoride anions oscillate about the cage centre, whereas they are slightly displaced towards the oxygen atom participating in the hydrogen bond in GeO2-AST_QNU. Again, this displacement is best visible at 150 K. Neither system delivers any indications for the presence of Ge-F bonds that have been found to occur in mixed (Si,Ge) d4r cages. More interesting observations can be made when looking at the shape of the d4r cages. As discussed above, the DFT optimisations deliver a highly symmetric (cube-like) cage in GeO2-AST_TMA, but a distorted pyritohedron-like d4r cage in GeO2-AST_QNU. An inspection of the average structures of GeO2-AST_TMA (Figure ), for which a representative example is shown in Figure , reveals that all d4r cages exhibit this pyritohedron-like distortion, causing the loss of tetragonal symmetry described above. This indicates that GeO2-AST containing pyritohedron-like cages is intrinsically more stable than the higher-symmetry form with cube-like d4r cages, and that the distortion is not governed by the OSDA. A re-optimisation of a selected 150 K average structure and the 𝐼4 ̅ structure, using the same supercell, confirms this, as the structure with pyritohedron-like d4r cages is favoured by -2.5 kJ mol -1 per GeO2 formula unit (-26 kJ mol -1 per fluoride anion). Due to the reduced symmetry, two different orientations are possible for the pyritohedron-like d4r cages. In GeO2-AST_TMA, both orientations occur randomly, and such a statistical distribution has been dubbed "orientational glass" in previous studies of AST-and ASV-type systems. In contrast, a strict ordering is observed in GeO2-AST_QNU at 150 and 298 K, which can be attributed to the interaction with the ordered QNU cations. Only at the highest temperature, some d4r cages in GeO2-AST_QNU have a different orientation. Additionally, a few of the d4r cages in the 573 K average structures show no pyritohedral distortion at all, which probably indicates that a change in orientation occurs during the AIMD run of 7.5 ps. Although the published crystal structure of GeO2-AST contains cube-like d4r cages, it should be noted that the observed preference for distorted d4r cages agrees with the report of similarly distorted cages in the structurally related germanate ASU-7. This raises the question to what extent such deformations are a general feature of d4r-containing GeO2 zeotypes (or Ge-rich zeolites). The coexistence of different orientations, together with thermal motion, would render it difficult to pin this down with diffraction methods.