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

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 I 4 , a = 18.319(17), b = 18.319(17), c = 16.067(17) Å, a = β = g = 90.00 deg., V = 5392(8) Å3, Z = 8, rcalc = 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 ( R int = 0.1110), number of refined parameters 431, GOOF 0.863, R -factors for F 2>2σ( F 2): R 1 = 0.0492, wR 2 = 0.0988; C31H25O5SSb (2) - triclinic system, space group P 1 , a = 9.529(3), b = 10.584(3), c = 13.745(5) Å, a = 94.619(17), β = 97.731(18), g = 90.336(16) deg., V = 1369.0(7) Å3, Z = 2, rcalc = 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 ( R int = 0.0213), number of refined parameters 344, GOOF 1.122, R -factors for F 2>2σ( F 2): R 1 = 0.0201, wR 2 = 0.0509.