Synthesis, spectroscopic investigations, and X-ray crystal structure of 2-substituted-1,2,3,4-tetrahydroquinazoline ring, obtained from 3-hydroxy benzaldehyde and 2-(aminomethyl)aniline are presented. The X-ray structure and spectroscopic evidence show that the product, which is a ring chain tautomerized Schiff base, appears in a 100% ring form, both in the liquid and in the solid state. The crystal structure of the compound presents a unique supramolecular architecture consisting of hexamers, offering channels of radius 5.79 angstrom down the c axis. Supplemental materials are available for this article. Go to the publisher's online edition of Mol. Cryst. Liq. Cryst. to view the free supplemental file.