Metabolic pathways of dithiocarbamates from laboratory powder diffraction data.

In order to correlate the reactivity and molecular structures of dithiocarbamates, the crystal structures of 6-dimethylamino-5-nitropyrimidin-4-yl N,N-diethyldithiocarbamate, C11H17N5O2S2, (Ia), and 6-methylamino-5-nitropyrimidin-4-yl N,N-diethyldithiocarbamate, C10H15N5O2S2, (Ib), and of the product of thermolysis of (Ib), namely 4-diethylamino-6-methylamino-5-nitropyrimidinium chloride monohydrate, C9H16N5(O2)(+).Cl(-).H2O, (II), have been determined from X-ray laboratory powder diffraction data. Conformational preferences in (Ia) and (Ib) were studied on the density functional theory (DFT) level. Deviation of the reaction centre of the molecule from planarity and breakage of the secondary S...O contact cause switching between two alternative pathways of thermolysis.