Synthesis, structure, and photochemical properties of derivatives: (2-MeO-5-BrC6H3)3SbR2, R= OC(O)C6F5, ONCHC6H4Br-2, OSO2C6H4CH3-4

Oxidation of tris(5-bromo-2-methoxyphenyl)antimony with tertiary butyl hydroperoxide in diethyl ether in the presence of pentafluorobenzoic acid, 2-bromobenzaldoxime, and 4-methylbenzenesulfonic acid (1:1:2 mole ratio) leads to formation of bis(pentafluorobenzoate) tris(5-bromo-2-methoxyphenyl)antimony (1), bis(2-bromobenzaldoxymate) tris(5-bromo-2-methoxyphenyl)antimony (2), bis(4-methylbenzenesulfonate) tris(5-bromo-2-methoxyphenyl)antimony (3), respectively. The compounds have been identified by X-ray diffraction analysis. According to the X-ray diffraction data, the antimony atoms in crystals 1 [C35H18Br3F10O7Sb, M 1101.97; triclinic system, space group P1 ; cell parameters: a = 10.541(7), b = 13.427(11), c = 16.165(8) Å; a = 65.46(3), β = 72.34(3), g = 68.58(3) deg.; V = 1906(2) Å3; crystal size 0.65 × 0.3 × 0.25 mm; index ranges -14 ≤ h ≤ 14, -18 ≤ k ≤ 18, -21 ≤ l ≤ 21; total reflections 81715; independent reflections 9657; Rint 0.0475; GOOF 1.027; R1 = 0.0360, wR2 = 0.0839; residual electron density 1.59/-1.67 e/Å3], 2 [C35H28Br5N2O5Sb, M 1077.89; monoclinic system, space group P21/c; cell parameters: a = 13.378(6), b = 20.636(8), c = 14.251(8) Å; a = 90, β = 100.955(19), g = 90 deg.; V = 3863(3) Å3; crystal size 0.35×0.14×0.1 mm; index ranges -16 ≤ h ≤ 17, -27 ≤ k ≤ 27, -19 ≤ l ≤ 19; total reflections 103306; independent reflections 9780; Rint 0.0798; GOOF 1.021; R1 = 0.0520 wR2 = 0.1218; residual electron density 1.69/-1.54 e/Å3], 3 (benzene solvate) [C41H38Br3O9S2Sb, M 1100.31; triclinic system, space group P1 ; cell parameters: a = 9.643(6), b = 10.102(5), c = 23.634(14) Å; a = 77.74(3), β = 88.69(3), g = 74.82(3) deg.; V = 2170(2) Å3; crystal size 0.36×0.22×0.16 mm; index ranges -13 ≤ h ≤ 12, -13 ≤ k ≤ 13, -31 ≤ l ≤ 31; total reflections 84202; independent reflections 11146; Rint 0.0454; GOOF 1.066; R1 = 0.0385, wR2 = 0.0818; residual electron density 0.93/-0.78 e/Å3] have a distorted trigonal-bipyramidal coordination with the oxygen atoms of the carboxylate, oximate and sulfonate ligands in axial positions (the axial angles are 176.4(1)º for 1, 169.1(1)º for 2, 169.72(9)º for 3). The Sb-O distances are 2.086(2) and 2.120(2) Å for 1, 2.069(3) and 2.072(3) Å for 2, 2.134(3) and 2.118(3) Å for 3. The Sb-C bond lengths vary in the intervals 2.097(3)-2.108(3) Å in 1, 2.119(6)-2.123(6) Å in 2, 2.104(3)-2.123(3) Å in 3. Complete tables of atomic coordinates, bond lengths, and bond angles for the structures are deposited at the Cambridge Crystallographic Data Center (No. 2045964 for 1, No. 2064391 for 2, No. 2055547 for 3; deposit@ccdc.cam.ac.uk; https://www.ccdc.cam.ac.uk). The photocatalytic activity of the synthesized compounds was studied by photodestruction of methylene blue as an example.