Impact of the anion and chalcogen on the crystal structure and properties of 4,6-dimethyl-2-pyrimido(thio)nium halides

Abstract

By the reaction of urea or thiourea, acetylacetone and hydrogen halide (HF, HBr or HI), we have obtained seven new 4,6-dimethyl-2-pyrimido(thio)nium salts, which were characterized by single-crystal X-ray diffraction, namely, 4,6-dimethyl-2-oxo-2,3-dihydropyrimidin-1-ium bifluoride, C6H9N2O+·HF2 − or (dmpH)F2H, 4,6-dimethyl-2-oxo-2,3-dihydropyrimidin-1-ium bromide, C6H9N2O+·Br− or (dmpH)Br, 4,6-dimethyl-2-oxo-2,3-dihydropyrimidin-1-ium iodide, C6H9N2O+·I− or (dmpH)I, 4,6-dimethyl-2-oxo-2,3-dihydropyrimidin-1-ium iodide–urea (1/1), C6H9N2O+·I−·CH4N2O or (dmpH)I·ur, 4,6-dimethyl-2-sulfanylidene-2,3-dihydropyrimidin-1-ium bifluoride–thiourea (1/1), C6H9N2S+·HF2 −·CH4N2S or (dmptH)F2H·tu, 4,6-dimethyl-2-sulfanylidene-2,3-dihydropyrimidin-1-ium bromide, C6H9N2S+·Br− or (dmptH)Br, and 4,6-dimethyl-2-sulfanylidene-2,3-dihydropyrimidin-1-ium iodide, C6H9N2S+·I− or (dmptH)I. Three HCl derivatives were described previously in the literature, namely, 4,6-dimethyl-2-oxo-2,3-dihydropyrimidin-1-ium chloride, (dmpH)Cl, 4,6-dimethyl-2-sulfanylidene-2,3-dihydropyrimidin-1-ium chloride monohydrate, (dmptH)Cl·H2O, and 4,6-dimethyl-2-sulfanylidene-2,3-dihydropyrimidin-1-ium chloride–thiourea (1/1), (dmptH)Cl·tu. Structural analysis shows that in 9 out of 10 of these compounds, the ions form one-dimensional chains or ribbons stabilized by hydrogen bonds. Only in one compound are parallel planes present. In all the structures, there are charge-assisted N+—H...X − hydrogen bonds, as well as weaker CAr +—H...X − and π+...X − interactions. The structures can be divided into five types according to their hydrogen-bond patterns. All the compounds undergo thermal decomposition at relatively high temperatures (150–300 °C) without melting. Four oxopyrimidinium salts containing a π+...X −...π+ sandwich-like structural motif exhibit luminescent properties.