Synthesis and Structure of Tetraphenylstibonium Organosulfonates Ph4SbOSO2R, R = C10H15O, C10H4(OH-1)(NO2)2-2,4, C10H7-1, C6H4(COOH-2)

The reaction of equimolar amounts of pentaphenylantimony with camphor-10-sulfonic, 2,4-dinitro-1-naphthol-7-sulfonic (flavianic), 1-naphthalenesulfonic, and 2-sulfobenzoic acids in benzene resulted in the synthesis of tetraphenylstibonium organosulfonates Ph4SbOSO2C10H15O∙H2O (I), Ph4SbOSO2C10H4(OH-1)(NO2)2-2,4∙PhH (II), Ph4SbOSO2(C10H7-1)∙H2O (III), and Ph4SbOSO2C6H4(COOH-2) (IV). According to X-ray diffraction data (CCDC no. 2119791 (I), 2121381 (II), 2116582 (III), and 2123516 (IV), the crystal of I contains trigonal-bipyramidal sulfonate molecules (the axial Sb−C and Sb−O bond lengths are 2.130(3) and 2.565(2) Å, respectively) and hydration water molecules, which form a centrosymmetric eight-membered ring (the S=O∙∙∙H−O−H∙∙∙O=S distances are 2.06 and 2.21 Å). In the molecules of II, the metal atom geometry is a distorted trigonal bipyramid (the axial Sb−C and Sb−O bonds are 2.133(2) and 2.643(3) Å, respectively). The Sb−O distance (2.842(3) Å) is longer in III than in I or II; the hydration water molecules form centrosymmetric twelve-membered rings with the anions (the S=O∙∙∙H−O−H∙∙∙O=S distances are 2.02 and 2.05 Å). Meanwhile, the crystal of compound IV consists of tetrahedral tetraphenylstibonium cations and (2-carboxy)benzenesulfonate anions with the intramolecular O−H∙∙∙O=S hydrogen bond (1.75 Å).