Synthesis and Crystal Structure of Alkyltriphenylphosphonium Arenesulfonates [Ph3PR][OSO2Ar]

Abstract

The reaction of equimolar amounts of alkyltriphenylphosphonium bromides with
mesitylenesulfonic, 1-hydroxy-2,4-dinitro-7-naphthalenesulfonic, 2-carboxybenzenesulfonic and sulfosalicylic acids in water leads to the formation of ionic alkyltriphenylphosphonium arenesulfonates [Ph3PR][OSO2Ar], R = CH2Ph, Ar = С6H2Me3-2,4,6 (1), R = CH2ОMe,
Ar = C10H4(OH-1)(NO2)2-2,4 (2), R = (CH2)4Br, Ar = C6H4(COOH-2) (3), R = CH2ОН,
Ar = C6H3(COOH-3)(OH-4) (4). Structures of complexes 1‒4 have been established by X-ray diffraction analysis. Crystals 1 [C34H35O4PS, M 570.65; monoclinic syngony, space group P21/c; сell parameters: a = 11.083(12), b = 21.520(16), c = 12.768(10) Å;  = 90.00, β = 92.62(4),
 = 90.00 deg.; V = 3042(5) Å3, Z = 4; calc = 1.246 g/cm3], 2 [C30H25N2O9PS, M 620.55; triclinic syngony, space group P–1; сell parameters: a = 8.998(5), b = 12.347(5), c = 13.204(6) Å;
 = 82.92(2), β = 81.90(3),  = 83.92(2) deg.; V = 1435.2(12) Å3, Z = 2; calc = 1.436 g/cm3], 3 [C29H28O5PSBr, M 599.45; monoclinic syngony, space group P21/n; сell parameters:
a = 12.685(11), b = 16.178(13), c = 13.743(13) Å;  = 90.00, β = 90.39(3),  = 90.00 deg.;
V = 2820(4) Å3, Z = 4; calc = 1.412 g/cm3], and 4 [C26H27O9PS, M 546.50; monoclinic syngony, space group P21/n; сell parameters: a = 9.201(4), b = 10.113(15), c = 28.77(4) Å;  = 90.00,
β = 90.51(6),  = 90.00 deg.; V = 2677(7) Å3, Z = 4; calc = 1.356 g/cm3] consist of tetrahedral alkyltriphenylphosphonium cations and arenesulfonate anions with a tetrahedral sulfur atom. The P–C bond lengths vary within the range 1.717(3)−1.931(3) Å. The СРС valence angles take values 101.87(14)−122.99(13) deg. The S−C distances are close to each other and vary in range of values 1.752(5)−1.798(6) Å; the S−O bond lengths are 1.303(2)‒1.53(2) Å. Compounds 1 and 4 crystallize as hydrates. Cations and anions in complexes 1–4 are linked by weak hydrogen bonds of the S=O∙∙∙Н(Рh) [2.25‒2.67 Å] and S=O∙∙∙Н(C) [2.23–2.63 Å] type. Crystal structures 1, 2, 4 contain the CH∙∙∙π interactions. The spatial structure of crystals 1, 2 is formed with the participation of the π–π interactions. Complete tables of atomic coordinates, bond lengths and bond angles for structures have been deposited at the Cambridge Crystallographic Data Centre (no. 2164931 (1), no. 2168826 (2), no. 2163921 (3), no. 2168621 (4), deposit@ccdc.cam.ac.uk; https://www.ccdc.cam.ac.uk).