Reactions of Acetonyltriphenylphosphonium and 2-Butene-1,4-bis(triphenylphosphonium) Chlorides with Nitric Acid

Alkyltriphenylphosphonium nitrates [Ph₃PCH₂С(O)Me]NO₃ (1) and [Ph₃PCH₂CH=CHCH₂PPh₃][NO₃]₂ · 2H₂O (2) have been synthesized by reacting, respectively, acetonyl-triphenylphosphonium and trans-2-butene-1,4-bis(triphenylphosphonium) chlorides with nitric acid. The compounds have been characterized by IR spectroscopy and single-crystal X-ray diffraction. According to XRD data, acetonyltriphenylphosphonium nitrate (1) (C₂₁H₂₀NO₄P, FW = 381.35; monoclinic, space group С2/с; a = 14.301(13) Å, b = 12.756(11) Å, c = 21.40(2) Å; α = 90.00°, β = 90.66(3)°, γ = 90.00°, V = 3904(8) ų, Z = 8; ρ_X = 1.298 g/cm³; GOOF = 1.034; R = 0.0631) and trans-2-butene-1,4-bis(triphenylphosphonium) dinitrate dihydrate (2) (C₄₀H₄₀N₂O₈P₂, FW = 738.68; triclinic, space group P–1; a = 9.259(7) Å, b = 9.514(6) Å, c = 12.247(9) Å; α = 68.43(4)°, β = 72.47(5)°, γ = 84.06(3)°, V = 956.7(12) ų, Z = 1; ρ_X = 1.282 g/cm³; GOOF = 1.029; R = 0.0493) have ionic structure and consists of organyltriphenylphosphonium cations with a somewhat distorted tetrahedral coordination of the phosphorus atom (the CPC angle vary within 104.99(11)°−112.25(12)° for 1 and 107.61(11)°−111.28(11)° for 2; the P–C distances are 1.792(3)–1.802(3) Å and 1.792(2)–1.815(2) Å, respectively) and planar trigonal nitrate anions (the sums of the ONO angles are 359.5° and 360°, respectively). Complete tables of atomic coordinates and bond lengths and angles of nitrates 1 and 2 have been deposited with the Cambridge Crystallographic Data Centre (CCDC 2155176 (1), 2335887 (2); deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk).