Oxidation of triarylantimony by cumyl hydroperoxide in the presence of 3-fluorophenylacetic, 2,5-difluorobenzoic, and benzenesulfonic acids

Oxidation of triphenylantimony, tris(3-fluorophenyl)antimony and tris[(2-methoxy)(5-chloro)phenyl]antimony by cumyl hydroperoxide in the presence of 3-fluorophenylacetic, 2,5-difluorobenzoic, and benzenesulfonic acids, respectively, led to the formation (after recrystallization of the target products from benzene) of triphenylantimony bis(3-fluorophenylacetate) Ph3Sb[OC(O)CH2C6H4F-3]2 (1), tris(3-fluorophenyl)antimony bis(2,5-difluorobenzoate) (3-FC6H4)3Sb[OC(O)C6H3F2-2,5]2 (2) and a solvate of tris[(2-methoxy)(5-chloro)phenyl]antimony bis(benzenesulfonate) with benzene [(2-MeO)(Cl-5)C6H3]3Sb[OSO2Ph]2 ∙ PhH (3), the structures of which were established by X-ray diffraction analysis (XRD). According to the X-ray diffraction data, crystals 1 [C34H27F2O4Sb, M = 659.30; monoclinic syngony, symmetry group C2/c; cell parameters: a = 22.732(16), b = 10.204(5), c = 17.248(11) Å; β = 134.63(2); V = 2847(3) Å3; Z = 4; calc = 1.538 g/cm3;  = 1.020 mm1; 2 6.54856.998 deg.; total reflections 28613; independent reflections 3605; number of refined parameters 188; Rint = 0.0284; GOOF 1.072; R1 = 0.0263, wR2 = 0.0718; residual electron density (max/min): 1.08/0.77 e/Å3], 2 [C32H18F7O4Sb, M = 721.21; triclinic syngony, symmetry group P-1; cell parameters: a = 8.982(11), b = 12.272(14), c = 13.511(14) Å;  = 93.40(5), β = 97.94(6),  = 103.65(5); V = 1427(3) Å3, Z = 2; calc = 1.679 g/cm3;  = 1.050 mm1; 2 6.0260.1 deg.; total reflections 84918; independent reflections 84918; number of refined parameters 397; Rint = 0.0542; GOOF 1.074; R1 = 0.0409, wR2 = 0.1012; residual electron density (max/min): 1.24/0.56 e/Å3; 3 [C39H34Cl3O9S2Sb, M = 938.88; triclinic syngony, symmetry group P-1; cell parameters: a = 10.234(11), b = 15.272(11), c = 15.425(12) Å;  = 118.34(2), β = 102.55(4),  = 91.52(3); V = 2047(3) Å3; Z = 2; calc = 1.523 g/cm3;  = 1.024 mm1; 2 6.0655.168 deg.; total reflections 48370; independent reflections 9408; number of refined parameters 486; Rint = 0.0464; GOOF 1.038; R1 = 0.0328, wR2 = 0.0767; residual electron density (max/min): 0.71/0.72 e/Å3,] consist of trigonal bipyramidal molecules with electronegative ligands in axial positions. The Sb−C distances are 2.070(3)−2.215(3) Å for 1, the Sb−C bond lengths vary in the range 2.103(3)−2.110(3) Å for 3 and are lower than in 2: 2.113(4)−2.121(4) Å; The OSbO bond angles are 178.08(8)° (1), 174.87(8)° (2) and 176.96(7)° (3). The Sb−O distances in 3 (2.107(2) and 2.149(2) Å) are comparable with those observed in 2 (2.104(3) and 2.128(3) Å) and are significantly higher than in 1 (2.030(2) and 2.030(2) Å). The benzene solvate molecule in 3 is disordered over two positions. The intramolecular Sb∙∙∙O contacts in 3 between the central metal atom and the oxygen atom of the sulfo group [3.289(5) and 3.312(6) Å] are significantly larger than the similar distances in dicarboxylates 1 [2.847(5) and 2.847(5) Å] and 2 [2.867(5) and 2.995(6) Å] and do not exceed the sum of their van der Waals radii (3.7 Å). Complete tables of atomic coordinates, bond lengths and bond angles for the structures have been deposited with the Cambridge Crystallographic Data Centre (No. 2178727 (1), No. 2055821 (2), (No. 2050627 (3), depos-it@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk).