Metabolic pathways of dithiocarbamates from laboratory powder diffraction data

In order to correlate the reactivity and molecular structures of dithiocarb amates, the crystal structures of 6-dimethyl-amino-5-nitropyrimidin-4-yl N, N-diethyldithiocarbamate, C11H17N5O2S2, (Ia), and 6-methylamino-5-nitropyri midin-4-yl N,N-diethyldithiocarbamate, C10H15N5O2S2, (Ib), and of the produ ct of thermolysis of (Ib), namely 4-diethylamino-6-methylamino-5-nitropyrim idinium chloride monohydrate, C9H16N5O2+. Cl-.H2O, (II), have been determin ed from X-ray laboratory powder diffraction data. Conformational preference s in (Ia) and (Ib) were studied on the density functional theory (DFT) leve l. Deviation of the reaction centre of the molecule from planarity and brea kage of the secondary S . . .O contact cause switching between two alternat ive pathways of thermolysis.