Oxidation of tris(2-methoxy-5-chlorophenyl)antimony with tert-butyl hydroperoxide in the presence of compounds containing a mobile hydrogen atom

Oxidation of tris(2-methoxy-5-chlorophenyl)antimony with tert-butyl hydroperoxide in di-ethyl ether in the presence of water and 2,5-dimethylbenzenesulfonic acid, after recrystallization from tol-uene, leads to formation of tris(2-methoxy-5-chlorophenyl)antimony oxide {[(2-MeO)(5-Cl)C6H3]3SbO}2 (1) and the solvate of tris(2-methoxy-5-chlorophenyl)antimony 2,5-dimethylbenzenesulfonate with tolu-ene [(2-MeO)(5-Cl)C6H3]3Sb[OSO2C6H3Me2-2,5]2 ∙ TolH (2), respectively; the compounds have been structurally characterized by X-ray diffraction analysis (XRD). According to the XRD data [(1) [C42H36O8Cl6Sb2, M 1124.91; triclinic syngony, symmetry group P-1; cell parameters: a = 12.00(5), b = 13.25(5), c = 15.22(8) Å; α = 103.71(17)°, β = 91.54(18)°, γ = 104.39(14)°; V = 2267(17) Å3, Z = 2, ρcalc = 1.648 g/cm3, μ = 1.595 mm−1, F(000) = 1112.0, 2θ data acquisition range, deg: 6.28−55.48, crystal size 0.31×0.3×0.1 mm; reflection index ranges –15 ≤ h ≤ 15, –16 ≤ k ≤ 17, –19 ≤ l ≤ 19; total reflections 28402; independent reflections 9758; Rint 0.0709; GOOF 1.163; R1 = 0.1049, wR2 = 0.2352; residual elec-tron density 2.93/–2.50 e/Å3], (2) [C81H80O18Cl6S4Sb2, M 1925.91; monoclinic syngony, symmetry group P21/n ; cell parameters: a = 15.11(2), b = 18.76(4), c = 16.05(4) Å; β = 115.72(9)°; V = 4214(15) Å3, Z = 2, ρcalc = 1.518 g/cm3, μ = 0.997 mm−1, F(000) = 1956.0, 2θ data acquisition range, deg: 5.814−57, crystal size 0.25×0.17×0.1 mm; reflection index ranges –19 ≤ h ≤ 20, –25 ≤ k ≤ 25, –22 ≤ l ≤ 22; total reflections 144626; independent reflections 10442; Rint 0.5431; GOOF 1.036; R1 = 0.1105, wR2 = 0.2247; residual electron density 2.34/–1.18 e/Å3], in two types of crystallographically independent symmetrical molecules of the centrosymmetric dimer 1, the antimony atoms have a distorted square-pyramidal coordination with two oxygen atoms joining two antimony atoms into a whole. In the trigonal-bipyramidal molecules 2 the oxygen atoms occupy axial positions. In molecules 2 there are weak intramolecular contacts between the central metal atom and the oxygen of the sulfonate groups Sb∙∙∙O=SO2 [3.360(18), 3.490(18) Å], which are located in the cis-position relative to each other. Complete tables of atomic coordinates, bond lengths and valence angles have been deposited at the Cambridge Crystallographic Data Centre (No. 2050329 (1), 2076853 (2); deposit@ccdc.cam.ac.uk; https://www.ccdc.cam.ac.uk).