Method for synthesis of organyltriphenylphosphonium nitrates from organyltriphenylphosphonium chlorides and nitric acid

By the interaction of cyanomethyl- and acetonyltriphenylphosphonium chlorides with nitric acid the [Ph3PCH2CN]NO3 (1) and [Ph3PCH2C(O)Me]NO3 (2) phosphorus complexes were obtained, respectively. The obtained compounds were characterized by the IR spectroscopy method. Crystal structure of compound 1 was determined by the X-ray diffraction (XRD) analysis. According to the XRD data, cyanomethyltriphenylphosphonium nitrate (1) [C20H17N2O3P, M = 364.33; monoclinic crystal system, P 21/ n space group; cell parameters: a = 8.261(9) Å, b = 23.05(2) Å, c = 10.628(10) Å; a = 90.00°, β = 111.32(7)°, g = 90.00°, V = 1886(3) Å3, Z = 4; r(calc.) = 1.283 g/cm3; m = 0.167 mm-1; F (000) = 760.0; 2qmax: 6.46-56.7°; -11 ≤ h ≤ 11, -30 ≤ k ≤ 30, -14 ≤ l ≤ 14; reflections collected 41975; independent reflections 4673 ( R int = 0.0607); GOOF = 1.021; R -factor 4.97 %] has an ionic structure and consists of cyanomethyltriphenylphosphonium cation (slightly distorted coordination of the phosphorus atom; the CPC angles vary in the range 107.17(10)-110.59(11)°; the P-C distances vary within 1.792(2)-1.820(2) Å) and nitrate anion (square trigonal geometry; the sum of the ONO angles equals 359.99°). The structural organization in crystal 1 is caused by the interionic C-H∙∙∙O-NO2 hydrogen bonds (2.25-2.57 Å) of various strength and by the weak C-H∙∙∙NO3 contacts (2.68 Å). Complete tables of atomic coordinates, bond lengths, and bond angles for compound 1 are deposited with the Cambridge Crystallographic Data Centre (CCDC 2155177) and are available, free of charge, at deposit@ccdc.cam.ac.uk and http://www.ccdc.cam.ac.uk.