In particular, in (1,4-PDA)PbI4 the asymmetric unit contains a Pb atom on a site of 2/m symmetry and two I atoms on mirror planes and thus, by symmetry, the equatorial plane is defined by four equivalent positions for atom I2, whereas the two equivalent positions for atom I1 are necessarily axial. The symmetry constrains together with the edge sharing motif that occurs through the equatorial I atoms give rise to regular octahedra. (1,3-XDA)2PbBr6 comprises isolated and slightly distorted octahedra, characterized by a relatively high angle variance, suggesting a deviation of the Br-Pb-Br angles from 90°. The crystal cohesion is given by a framework of contacts between the amino groups and the bromide atoms. The organic molecule present in the asymmetric unit is tilted of 20° with respect to (001) plane. Coming to the layered perovskites, the octahedra show large distortion when cations where the nitrogen atoms are bound to sit in the same plane as the aromatic cation, such as the 1,3-PDA and 1,4-PDA, are present. On the other hand, the more flexible 1,4-XDA cation induces only a slight distortion in the PbBr6 octahedra. Analogously with the AEA cation, where one nitrogen atom is bound to aromatic plane and the other one is not, the octahedra adopt a distortion between the ones reported for 1,4-XDA and 1,4-PDA. Again, based on the present results, the 2D DJ perovskites reported in this work show an octahedral distortion increasing passing from (1,4-XDA)PbBr4 to (1,4-PDA)PbBr4 and to (1,3-PDA)PbBr4, with the last two showing, in particular, a significant increase in the octahedral angle variance with respect to (1,4-XDA)PbBr4. To further investigate the relationship between the structure of the perovskites, in particular the degree of octahedra distortion, and their optical properties, we performed an indepth spectroscopic study on the samples which present the 2D DJ structure: (1,3-PDA)PbBr4, (1,4-PDA)PbBr4, and (1,4-XDA)PbBr4.