Tetraphenylphosphorus and tetraphenylantimony (2-carboxy)benzenesulfonates. Synthesis and structure

Abstract

Tetraphenylphosphonium [Ph4P]+[OSO2C6H4(COOH-2)] (2-carboxy)benzenesulfonates (1) and tetraphenylstibonium [Ph4Sb]+[OSO2C6H4(COOH-2)] (2-carboxy)benzenesulfonates (2) were obtained by the interaction of pentaphenylphosphorus and pentaphenylantimony with 2-sulphobenzoic acid in benzene, yielding up to 90 %. Compounds 1 and 2 were also synthesized from tetraphenylphosphonium, -stibonium chlorides and 2-sulphobenzoic acid in water with maximal 89 % yield. The complexes were characterized by X-ray diffraction analysis and IR spectroscopy. They are colorless crystals with mp. 202С (1) and 160С (2), soluble in arenes and polar solvents. The IR spectrum of complexes 1 and 2 contains bands characterizing the vibrations of the P–C (763 cm–1) and Sb–C (447 cm–1) bonds, respectively. The spectra also contain vibrations of the following structural fragments: С=О (1705 (1) and 1718 (2) cm–1), ОSO2 (1261, 1170, 1157 (1) and 1251, 1170, 1157 (2) cm–1), О–Н (3396 (1) and 3419 (2) cm–1) and aromatic groups (3080, 3062, 1587, 14363, 1436, 723, 690 (1) and 3072, 3049, 1589, 1479, 1433, 738, 729 (2) cm–1). The X-ray diffraction analysis of the complexes was carried out on a D8 Quest Bruker automatic four-circle diffractometer (Mo Kα radiation, λ = 0.71073 Å, graphite monochromator) at 293 K. Crystallographic characteristics: C31H25O5SP (1)  tetragonal system, space group I4 ̅, a = 18.319(17), b = 18.319(17), c = 16.067(17) Å,  = β =  = 90.00 deg., V = 5392(8) Å3, Z = 8, calc = 1.332 g/cm3, F(000) = 2256.0, crystal size 0.16  0.16  0.12 mm, index ranges 24 ≤ h ≤ 24, 21 ≤ k ≤ 24, 21 ≤ l ≤ 21, total reflections 49841, independent reflections 6496 (Rint = 0.1110), number of refined parameters 431, GOOF 0.863, R-factors for F2>2σ(F2): R1 = 0.0492, wR2 = 0.0988; C31H25O5SSb (2)  triclinic system, space group P1 ̅, a = 9.529(3), b = 10.584(3), c = 13.745(5) Å,  = 94.619(17), β = 97.731(18),  = 90.336(16) deg., V = 1369.0(7) Å3, Z = 2, calc = 1.531 g/cm3, F(000) = 636.0, crystal size 0.36  0.28  0.26 mm, index ranges 12 ≤ h ≤ 12, 13 ≤ k ≤ 13, 17 ≤ l ≤ 17, total reflections 34082, independent reflections 6043 (Rint = 0.0213), number of refined parameters 344, GOOF 1.122, R-factors for F2>2σ(F2): R1 = 0.0201, wR2 = 0.0509.