SYNTHESIS AND STRUCTURE OF TETRAPHENYLPHOSPHONIUM ARENESULFONATES

Abstract

Interaction between pentaphenylphosphorus and arenesulfonic acids (mole ratio 1:1) in the benzene solution of tetraphenylphosphonium arenesulfonates has led to [Ph4P]+[O3SAr]−, Ar = Ph (I), C6H4Me-4 (II), C6H3(Me2-2,5) (III) (hydrate with 1.5 molecules of water). According to X-ray analysis, which was performed in the automatic four-circle Bruker D8 Quest diffractometer (Mo Kα-radiation, λ = 0.71073 Å, graphite monochromator),  crystals I (C30H25O3PS, M 496.53 g/mol, crystal system moloclinic, space group P21/n, crystal size 0.25 × 0.2 × 0.15 mm), II(C31H27O3PS, M 510.56 g/mol, crystal system rhombic, space group Pna21, crystal size 0.48 × 0.18 × 0.12 mm) and III (C32H32O4.5PS, M 1097.16 g/mol, crystal system moloclinic, space group P2/c, crystal size 0.43 × 0.34 × 0.22 mm) include the tetrahedral cations (bond length equal 1.797(2)-1.799(2), 1.652(2)-1.999(3), 1.785(8)-1.815(7) Å; angles СРС equal 109.29(9)°-110.86(9)°, 104.04(13)°-115.14(12)°, 107.1(4)°-113.3(4)° in I, II and III respectively) and arenesulfonate anions (bond length equal S-O 1.4355(18)-1.4446(17), 1.313(3)-1.597(3), 1.431(6)-1.457(7) Å; angles ОSO 113.07(11)°-113.30(11)°, 107.5(2)°-117.2(2)°, 112.3(4)°-114.2(4)° in I, II and III respectively). In hydrate III the water molecules associate the cations and anions into the spatial grid through the intermolecular hydrogen bonds. The solvate [Ph4P]Br∙РhH (IV) has been obtained by the interaction of pentaphenylphosphorus with the hydrogen bromide. In IV the P-C bonds (1.7941(19)-1.803(2) Å) and angles СРС (107.93(9)°-112.96(9)°) are close to the similar values in the tetraphenylphosphonium arenesulfonates.