Synthesis and structure of benzyl- and (4-carboxybutyl)triphenylphosphonium nitrates

Abstract

Interaction of benzyl- and (4-carboxybutyl)triphenylphosphonium bromides with nitric acid synthesized phosphorus complexes [Ph3PCH2Ph]NO3 (1) and [Ph3P(CH2)4COOH]NO3 (2), respectively. The obtained compounds were characterized by IR spectroscopy and X-ray diffraction analysis. According to the X-ray diffraction data, benzyltriphenylphosphonium nitrate (1) [C25H22NO3P, M = 415.41; triclinic crystal system, P–1 space group; cell parameters: a = 9.573(7) Å, b = 10.272(10) Å, c = 12.066(11) Å;  = 105.42(4), β = 107.06(4),  = 92.73(4), V = 1083.3(16) Å3, Z = 2; calc = 1.273 g/cm3;  = 0.153 mm–1; F(000) = 436.0; 2q 5.68–54.32; –12 ≤ h ≤ 12, –13 ≤ k ≤ 13, –15 ≤ l ≤ 15; collected reflections 26281; independent reflections 4802 (Rint = 0.0345); GOOF = 1.038; R-factor 0.0451] and 4-carboxybutyltriphenylphosphonium nitrate (2) [C23H24NO5P, M = 425.40; monoclinic crystal system, P21/n space group; cell parameters: a = 8.937(16) Å, b = 17.86(3) Å, c = 13.71(2) Å;  = 90.00, β = 95.04(11),  = 90.00, V = 2180(6) Å3, Z = 4; calc = 1.296 g/cm3;  = 0.160 mm–1; F(000) = 896.0; 2q 5.72–55.48; –11 ≤ h ≤ 11, –22 ≤ k ≤ 23, –17 ≤ l ≤ 17; collected reflections 18882; independent reflections 4732 (Rint = 0.0952); GOOF = 1.040; R-factor 0.0729] have an ionic structure and consist of organyltriphenylphosphonium cations with a slightly distorted tetrahedral-coordinated phosphorus atom (the CPC angles vary in the range 107.10(8)–111.56(10) for 1 and 107.62(10)–111.99(16) for 2; the P–C distances are 1.791(2)–1.803(2) Å and 1.786(4)–1.803(4) Å, respectively) and planar trigonal nitrate anions (the sums of the ONO angles are 359.6 and 360). The structural organization in crystal 1 is determined only by the interionic hydrogen bonds C–H∙∙∙O–NO2 (2.24–2.61 Å). Crystal 2, in addition to the C–H∙∙∙O–NO2 interactions (2.12–2.72 Å), also contains the O–H∙∙∙O–NO2 contacts (2.12 and 2.42 Å), C–H∙∙∙O=C (2,63 Å), as well as C–H∙∙∙NO3 (2.60 Å). Complete tables of atomic coordinates, bond lengths, and bond angles of nitrates 1 and 2 are deposited with the Cambridge Crystallographic Data Centre (CCDC 2331486 (1), 2331490 (2); deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk).