Crystal and molecular structure of salicylaldehyde azine

Abstract

The crystal and molecular structure of salicylaldehyde azine has been determined by Patterson and Fourier methods from three-dimensional X-ray data, and refined by anisotropic least-squares methods to a final R value of 0·087. The crystals are monoclinic, space group P2₁/c, with two molecules in the unit cell of dimensions a= 8·467, b= 6·318, c= 12·432 Å, β= 112°22′.

The molecules are centrosymmetric and nearly planar; the small deviations from planarity are indicative of intramolecular overcrowding between the two ortho-substituents in the benzene ring. The distribution of bond distances within the benzene ring is consistent with a significant contribution to the structure from a resonance quinonoid form. A strong internal hydrogen bond of 2·645 Å binds the phenolic hydroxy-group to the nearest nitrogen atom in the azine chain.

The molecules are packed in plane-to-plane stacks within the crystal, with a perpendicular spacing between adjacent molecules of about 3·4 Å, which in part accounts for its thermochromic properties.