New tetraorganylphosphonium arenesulfonates

Abstract

The reaction of equimolar amounts of tetraorganylphosphonium bromides with arenesulfonic acids in water leads to ionic tetraorganylphosphonium arenesulfonates [Bu4P][OSO2C6H3(OH-4)(COOH-3)] (1), [Ph3PEt][OSO2С10H7-1] (2), [Ph3PCH2C≡CH][OSO2C6H3(NO2)2-2,4] (3), [Ph3PCH2СN][OSO2Naft-1)] ∙ H2O (4), [Ph3PCH2С6H4(OH-2)] [OSO2C6H3Сl2-2,5] ∙ H2O (5), [Ph3PCH2Ph][OSO2C6H3(OH-4)(COOH-3)] (6), [Ph3PC3H5-cyclo] [OSO2C6H3(OH-4)(COOH-3)] (7), [Ph3PCH=СHPPh3][OSO2C6H3Сl2-2,5]2 ∙ 2H2O (8), [Ph3PCH=СHPPh3][OSO2C6H4(COOH)-2]2 ∙ 6H2O (9), yielding up to 89%. The structural features of complexes 1–9 were established by X-ray diffraction. Crystals 1 [C23H341O6PS, M 476.59; monoclinic syngony, symmetry group P21/c; cell parameters: a = 10.15(2), b = 16.15(6), c = 16.65(4) Å; β = 92.62(4), V = 2703(13) Å3, Z = 4; calc = 1.171 g/cm3], 2 [C30H27O3PS, M 498.55; rhombic syngony, symmetry group Pbca; cell parameters: a = 18.344(10), b = 12.947(8), c = 21.051(12) Å;  = β =  = 90.00 deg., V = 5000(5) Å3, Z = 8; calc = 1.325 g/cm3], 3 [C27H21N2O7PS, M 548.49; rhombic syngony, symmetry group Pca21; cell parameters: a = 13.25(2), b = 12.098(17), c = 16.65(3) Å;  = β =  = 90.00 deg., V = 2669(7) Å3, Z = 4; calc = 1.365 g/cm3], 4 [C35H31O4PS, M 578/63; monoclinic syngony, symmetry group P21/c; cell parameters: a = 11.357(5), b = 21.717(10), c = 13.135(6) Å; β = 115.479(18) deg., V = 2925(2) Å3, Z = 4; calc = 1.314 g/cm3], 5 [C31H27Cl2O5PS, M 613.46; rhombic syngony, symmetry group Pbca; cell parameters: a = 14.945(15), b = 15.291(19), c = 25.06(3) Å; V = 5728(11) Å3, Z = 8; calc = 1.423 g/cm3] consist of tetrahedral tetraorganylphosphonium cations and arenesulfonate anions with a tetrahedral sulfur atom. The crystals of complexes 6 [C32H27O6PS, M 570.57; rhombic syngony, symmetry group P212121; cell parameters: a = 11.174(18), b = 20.98(3), c = 23.73(4) Å;  = β =  = 90.00 deg., V = 5565(16) Å3, Z = 8; calc = 1.362 g/cm3] and 7 [C56H52O13P2S2, M 1059.04; rhombic syngony, symmetry group Pbca; cell pa-rameters: a = 13.704(8), b = 17.611(8), c = 41.64(4) Å;  = β =  = 90.00 deg., V = 10050(16) Å3, Z = 8; calc = 1.400 g/cm3] contain similar pairs of tetraorganylphosphonium cations and arenesulfonate anions. Complex 8 [C50H42Cl4O8P2S2, M 1038.70; triclinic syngony, symmetry group -C 1; cell parameters: a = 22.911(7), b = 10.797(3), c = 20.488(6) Å;  = 90.00, β = 106.884(11),  = 90.00 deg., V = 4850(2) Å3, Z = 8; calc = 1,423 g/cm3] consists of doubly charged phosphonium cations and two types of crystallographically independent arenesulfonate anions, unlike 9 [C26H27O8PS, M 530.51; triclinic syngony, symmetry group P–1; cell parameters: a = 9.09(7), b = 10.797(3), c = 20.488(6) Å;  = 90.00, β = 106.884(11),  = 90.00 deg., V = 4850(2) Å3, Z = 8; calc = 1.423 g/cm3], which contains arenesulfonate anions of the same type. Compounds 4, 5, 7, and 9 are hydrates, in which the water molecules participate in crystal structuring (H∙∙∙O distances vary in the range of 2.08–2.72 Å). The P–C bond lengths vary in the range 1.453(4)–2.316(4) Å. The CPC bond angles take the values 91.0(3)°−128.38(19)°. The S–O distances vary within 1.314(2)–1.599(2) Å. Complete tables of atomic coordinates, bond lengths, and bond angles for the structures were deposited at the Cambridge Crystallographic Data Center (no. 2172943 (1), no. 2183774 (2), no. 2292652 (3), no. 2177234 (4), no. 2177802 (5), no. 2219877 (6), no. 2172945 (7), no. 2175821 (8), no. 2175822 (9), deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk).