Psilocin, the minor hallucinogenic component of the sacred Mexican mushroom Teonanácatl, crystallizes in the monoclinic space group P21/c with unit-cell dimensions a = 1060(3), b = 853(2), c = 1251(3) pm and β = 91.25(30)°. The structure, solved by direct methods and refined to R = 0.047, shows intermolecular hydrogen bonds between the ethylamino-nitrogen and the indole hydroxy-group. Disorder of the proton in this hydrogen bond indicates the crystal contains a statistical mixture of zwitterions and uncharged species. The molecular conformation of psilocin differs from that found in psilocybin.
The hallucinogenic compound psilocybin, found in the sacred Mexican mushroom Teonanácatl, forms crystals that include methanol molecules. The crystal structure shows two psilocybin molecules per asymmetric unit, both existing as zwitterions with different shapes, and a complex network of hydrogen bonds, including very short phosphate-to-phosphate bonds and connections to methanol. The substituents on the indole ring are notably bent out of the plane. Bond lengths were measured with high precision.