Expected reaction of diphenoxythiophoshorylchloride and diphenoxyphosphorylchloride in acetonitrile - First examples of an N-phosphorylated 3-aminocrotonitrile - Structural analyses

(PhO)(2)P(S)-NH-C (CH3)=CH-CN (PCNS) and (PhO)(2)P(O)-NH-C(CH3)=CH-CN (PCNO ) are formed by the reaction of acetonitrile with (PhO)(2)P(S)Cl and (PhO)( 2)P(O)Cl, respectively, in the presence of sodium hydride or sodium. Both c ompounds are Bronsted acids. PCNS forms monoclinic crystals, space group Pc with four crystallographically independent molecules in the asymmetric uni t. The skeleton atoms of the molecules form parallel layers via N . . . HN- and S . . . HC-hydrogen bonds. PCNO is orthorhombic, space group Pbca. Its crystal structure is built of ring-shaped dimers via pairs of O . . . HN h ydrogen bonds.