Synthesis, spectroscopic study, X-ray crystallography and ab initio calculations of the two new phosphoramidates: C6H5OP(O)(NHC6H11)2 and [N(CH3)(C6H11)]P(O)(2-C5H4N-NH)2

GHOLIVAND, K.; CARLOS OMAR, DELLA VÉDOVA; ERBEN, M. F.; REZA MAHZOUNI, HAMID; ZAHRA SHARIATINIA,; SHADI AMIRI,

JOURNAL OF MOLECULAR STRUCTURE

Elsevier

Lugar: Amsterdam; Año: 2008 vol. 874 p. 178 - 186

0022-2860

Two new phosphoramidates with formula C6H5OP(O)(NHC6H11)2 (1) and [N(CH3)(C6H11)]P(O)(2-C5H4N-NH)2 (2) were synthesized and characterized by 1H, 13C, 31P NMR and IR spectroscopies and elemental analyses. The crystal structures of these compounds were determined using X-ray crystallography. Compound 1 [triclinic, P1, a = 8.8679(16), b = 10.230(2), c = 12.511(2), a= 95.918(4), b= 103.948(4), c= 110.818(4), Z = 2] forms a centrosymmetric dimmer via two equal intermolecular P=O···H-N hydrogen bonds. In this structure, intermolecular hydrogen bonds are also formed between the crystallization solvent and phosphoramidate molecules. Compound 2 [monoclinic, P21/c, a = 11.4760(7)A˚, b = 18.5607(12)A˚, c= 8.6227(6) A˚, b= 108.751(5), Z= 4] produces a one-dimensional polymeric chain through intermolecular P=O···H-N hydrogen bonds, and a weaker intramolecular N···H-N hydrogen bond has been also observed in the crystal. Ab initio quantum chemical calculations were performed for molecules 1 and 2 by the density functional three-parameter hybrid (DFT/B3LYP) and the Hartree-Fock (HF) methods, using the 6-31G* basis set. The compound 1:CH3OH pair was also calculated as observed in the crystal. The computed geometrical parameters are in good agreement with the experimental results.