Synthesis and structure of alkyltriphenylphosphonium arenesulfonates

The interaction of equimolar amounts of alkyltriphenylphosphonium halide with mesitylene sulfonic, 2,5-dichlorobenzene sulfonic, and sulfosalicylic acids in water leads to the formation of alkyltriphenylphosphonium arenesulfonates [Ph3PR][OSO2Ar], R = CH2OMe, Ar = C6H2Me3-2,4,6 (1); R = CH2C(O)Me, Ar = C6H2Me3-2,4,6 (2); R = (CH2)2Br, Ar = C6H3Cl2-2,5 (3); R = (CH2)4COOH, Ar = C6H3(COOH-3)(OH-4) (4). Structures of complexes 1-4 have been established by X-ray diffraction analysis. Crystals 1 [С29H31O4PS, M 506.57; monoclinic syngony, space group P21/c; cell parameters: a = 13.228(9), b = 14.530(12), c = 14.192(10) Å; a = 90.00, β = 101.46(3), g = 90.00 deg.; V = 2673(3) Å3, Z = 4; rcalc = 1.259 g/cm3], 2 [С30H31O4PS, M 518.58; monoclinic syngony, space group P21/c; сell parameters: a = 12.569(8), b = 15.888(12), c = 13.819(10) Å; a = 90.00, β = 100.16(2), g = 90.00 deg.; V = 2716(3) Å3, Z = 4; rcalc = 1.268 g/cm3], 3 [С26H22BrCl2O3PS, M 596.28; monoclinic syngony, space group Cc; cell parameters: a = 21.731(15), b = 8.974(6), c = 14.794(9) Å; a = 90.00, β = 117.928(19), g = 90.00 deg.; V = 2549(3) Å3, Z = 4; rcalc = 1.554 g/cm3], 4 [С60H59O16.5P2S2, M 1170.12; triclinic syngony, space group P-1; cell parameters: a = 10.678(7), b = 11.025(5), c = 13.250(7) Å; a = 104.117(19), β = 104.13(2), g = 91.23(3) deg.; V = 1461.5(14) Å3, Z = 2; rcalc = 1.330 g/cm3] consist of alkyltriphenylphosphonium cations and arenesulfonate anions. Phosphorus atoms in cations 1-4 have a tetrahedral coordination [the CРС angles vary in the range 104.50(8)-115.41(9) deg.]. The P-C bond lengths are 1.7890(16)-1.823(3) Å, which is slightly less than the sum of their covalent radii (1.88 Å). The S-O distances in arenesulfonate anions differ insignificantly and take values of 1.441(3)-1.454(2) Å; the S-C bond lengths are 1.7706(15)-1.807(3) Å. The structural organization of crystals 1-4 is due to weak hydrogen bonds between cations and anions. Arenesulfonate anions in complex 4 are structured into dimers via strong hydrogen bonds. Complete tables of atomic coordinates, bond lengths and bond angles for structures have been deposited at the Cambridge Crystallographic Data Centre (No. 2161982 (1), No. 2162500 (2), No. 2162502 (3), No. 2167983 (4), deposit@ccdc.cam.ac.uk; http://www.ccdc. cam.ac.uk).