Reactions of acetonyltriphenylphosphonium and 2-butene-1,4-bis(triphenylphosphonium) chlorides with nitric acid

Reactions of acetonyltriphenylphosphonium and 2-butene-1,4-bis(triphenylphosphonium) chlorides with nitric acid synthesized alkyltriphenylphosphonium compounds [Ph3PCH2C(O)Me]NO3 (1) and [Ph3PCH2CH=CHCH2PPh3][NO3]2 ∙ 2H2O (2), respectively. The resulting compounds were characterized by IR spectroscopy and X-ray diffraction analysis (XRD). According to the X-ray diffraction data, acetonyltriphenylphosphonium nitrate (1) [C21H20NO4P, M = 381.35; monoclinic system, sp. gr. C2/c; cell parameters: a = 14.301(13) Å, b = 12.756(11) Å, c = 21.40(2) Å; a = 90.00°, β = 90.66(3)°, g = 90.00°, V = 3904(8) Å3, Z = 8; rcalc = 1.298 g/cm3; m = 0.167 mm-1; F(000) = 1600.0; collection region at 2q: 5.7-56.96°; -16 ≤ h ≤ 19, -17 ≤ k ≤ 17, -28 ≤ l ≤ 28; total reflections 46344; independent reflections 4894 (Rint = 0.0808); GOOF = 1.034; R-factor = 0.0631] and (2-butene-1,4-bis(triphenylphosphonium nitrate hydrate (2) [C40H40N2O8P2, M = 738.68; triclinic system, space group P-1; cell parameters: a = 9.259(7) Å, b = 9.514(6) Å, c = 12.247(9) Å; a = 68.43(4)°, β = 72.47(5)°, g = 84.06(3)°, V = 956.7(12) Å3, Z = 2; rcalc = 1.282 g/cm3; m = 0.168 mm-1; F(000) = 388.0; collection region for 2q: 5.9- 54.34°; -11 ≤ h ≤ 11, -12 ≤ k ≤ 12, -15 ≤ l ≤ 15; total reflections 21543; independent reflections 4219 (Rint = 0.0354); GOOF = 1.029; R-factor = 0.0493] have an ionic structure and consist of organyltriphenylphosphonium cations with a slightly distorted tetrahedral coordination of the phosphorus atom (the CPC angles vary between 105.5(3)-111.8(2)° for 1 and 107.61(11)-111.28(11)° for 2; the P-C distances are 1.751(6)-1.805(5) Å and 1.792(2)-1.815(2) Å, respectively) and planar trigonal nitrate anions (the sums of the ONO angles equal to 359.5° and 360°, respectively). Complete tables of atomic coordinates, bond lengths, and bond angles of nitrates 1 and 2 have been deposited in the Cambridge Structural Data Bank (CCDC 2338987 (1), 2335887 (2); deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk).