A variable-temperature study of a phase transition in barbituric acid dihydrate.

The crystal structure of barbituric acid dihydrate (C4H4N2O3*2H2O) has twice been reported as orthorhombic, space group Pnma, with all atoms (except for CH(2) H atoms) lying on the mirror plane [Al-Karaghouli et al. (1977). Acta Cryst. B33, 1655-1660; Jeffrey et al. (1961). Acta Cryst. 14, 881-887]. The present study has found that at low temperatures, below 200 K, the crystal structure is no longer orthorhombic but is non-merohedrally twinned monoclinic, space group P2(1)/n. This phase is stable down to 100 K. Above 220 K the crystal structure is orthorhombic, and between 200 and 220 K the structure undergoes a phase change, with the monoclinic-to-orthorhombic phase transition itself taking place at around 216-217 K. The size of the beta angle in the monoclinic structure is temperature dependent; at 100 K beta is around 94 degrees and it decreases in magnitude towards 90 degrees as the temperature increases. Although the hydrogen-bonding motifs are the same for both crystal systems, there are significant differences in the crystal packing, in particular the out-of-plane displacement of the two water molecules and the sp3-hybridized C atom of barbituric acid.