Solid tryptophan as a pseudoracemate: physicochemical and crystallographic characterization.

The crystalline nature of solid tryptophan has been characterized by X-ray single crystal and powder diffraction analyses, differential scanning calorimetry, as well as measurement of solid-liquid equilibrium in water/isopropanol solution. Both the thermodynamic and crystallographic investigations have demonstrated unambiguously that solid tryptophan crystallizes in the form of a pseudoracemate (i.e., solid solution) with maximum melting over the entire enantiomeric composition range. Comparative single-crystal X-ray studies show that the crystal structures of racemic and enantiomeric tryptophan give very similar solid-state packing geometries dictated by hydrogen bonding interactions. Our results indicate that the insignificant difference between homochiral and heterochiral interactions accounts for the formation of a pseudoracemate for this system.