2-Aminobenzothiazole phosphorus amides: Molecular and supramolecular structures, hydrogen bonds and sulfur donor–acceptor interactions

Nine phosphorus amides derived from 2-aminobenzothiazole (1): 2-aminobenzothiazole-diphenylphosphane (2) and their corresponding oxide (4), sulfide (5), and selenide (6), and 2-aminobenzothiazole-diethylphosphite (3), and their corresponding sulfide (7), and selenide (8), lithium 2-aminobenzothiazolide-diphenylphosphane (9) and its oxide (10) are reported. Preferred tautomers and conformers of 2–10 in solution have been identified using NMR spectroscopy. Oxidation of 2 and 3 produces 4–8 associated with migration of the anilinic proton to the endocyclic nitrogen leading a delocalized dienyl system. Migration of phenyl groups from 2 and chlorides from NHEt3Cl to Pb(NO3)2 afforded bis-(2-aminobenzothiazolium) tetrachloro-diphenyl plumbate (11). The X-ray diffraction structures obtained for 2, 7, 10 and 11 showed S⋯H–Ar, S⋯S, S⋯P, and S⋯Cl donor acceptor interactions in the solid state, and that compounds 2 and 7 form dimers by 6 and 4 intermolecular cooperative hydrogen bonds. New compounds were characterized by NMR, IR, mass spectrometry and elemental analyses.

Graphical abstractNine phosphorus amides derived from 2-aminobenzothiazole (1): 2-aminobenzothiazole-diphenylphosphane (2), 2-aminobenzothiazole-diethylphosphite (3), and lithium 2-aminobenzothiazolide-diphenylphosphane (9) and their corresponding oxidated compounds 4–8 and 10 are reported. In solution, preferred tautomers and conformers of 2–10 have been identified using NMR spectroscopy. Oxidation of 2 and 3 produces 4–8 associated with migration of the anilinic proton to the endocyclic nitrogen leading a delocalized dienyl system. Migration of phenyl groups from 2 and chlorides from NHEt3Cl to Pb(NO3)2 afforded bis-(2-aminobenzothiazolium) tetrachloro-diphenyl plumbate (11). Analysis of the X-ray diffraction structures of 2, 7, 10 and 11 showed S⋯H–Ar, S⋯S, S⋯P, and S⋯Cl donor acceptor interactions in the solid state, and that compounds 2 and 7 form dimers by 6 and 4 intermolecular cooperative hydrogen bonds.Figure optionsDownload full-size imageDownload as PowerPoint slide