ABSTRACT:The aromatic Schiff base N-salicylideneaniline (SA) represents the aristotype of a whole family of chromic derivatives. SA forms two photochromic polymorphs, R 1 and R 2 , both of which feature non-coplanar phenyl rings. Since many details of its reversible photoreactivity are still unexplained, we report the structure of a planar, thermochromic polymorph, named , and propose a new model for the structure of the R 1 -polymorph. Finally, we discuss structure-property relations between the polymorphs and the to R 1 phase transition.