shows a layered structure, with an inorganic layer made of face-sharing square antiprisms and a layer of organic cations located on the inversion center. The central Pb atom is eight-fold coordinated with Pb-Cl distances ranging from 2.8029(18) to 3.3869 (15), creating a distorted square antiprism. The structure described in this work is in very good agreement with previous works, for which optical data were note reported. On the other hand, (1,3-PDA)PbCl4 and (1,4-XDA)PbCl4 crystallize as 2D Dion-Jacobson (DJ) phases with n=1 comprising layers of PbCl6 octahedra separated by layers of organic cations. It is well known that the interaction between the ammonium group and the octahedral framework deeply affects the structure and properties of layered perovskites. 9,10 A useful parameter to explore this effect is the penetration depth, which is the distance between the N atom of the amino group and the plane of the terminal halides. The NH3 + penetration influences both the interoctahedral, in terms of the X-Pb-X angle, and intra-octahedral distortion parameters, in terms of octahedral elongation length (⟨λoct⟩) and bond angle variance (σ 𝑜𝑐𝑡 2 ). In particular, considering for comparison the bromide and chloride containing phenylamines reported so far, some general trends can be envisaged (Figure ). With the same organic cation, the penetration depth increases from the chloride to the bromide perovskites, probably as a consequence of the different strength of the hydrogen bond. The position and length of the substituents seems to play a role: 1,3-PDA cations have shorter depth of penetration, most likely because of the steric hindrance of the relatively close substituents, while the 1,4-PDA and 1,4-XDA cations have larger penetration and more regular octahedral layers. Among Similar but opposite trends can also be seen in the intra-octahedral distortion parameters (Figure ). In fact, the 1,3-PDA cations have small NH3 penetration, but give rise to large distortions within the octahedra. Among the 1,4 cations, the rigidity of 1,4-PDA again seems to affect the PbX6 octahedra, inducing a distortion close to the one found for the 1,3-PDA cations. On the other hand, the more flexible 1,4-XDA cations allow for more regular octahedra. When the same organic cation is involved, the distortion within the octahedra increases with the hardness of the halide from Br to Cl, as predicted by first-principles calculations and shown by local structure studies . Finally, in order to have further insight into the role of the flexibility of the organic cation, we extend the analysis of the intraoctahedral distortion including all the compounds with available crystal structure even if not showing a layered perovskite structure (Figure ). It is worth noting that the smallest distortion is shown by (1,4-PDA)PbI4 where symmetry constrains together with the edge sharing motif present in the structure give rise to regular lead-iodide octahedra. Then, the XDA cations have an increasing distortion, with 1,3-XDA cations generating a larger but very c)