Tris[(2-methoxy)(5-bromo)phenyl]antimony dicarboxylates [(2-MeO)(5-Br)C6H3]3Sb[OC(O)C6H3F2-2,3]2, [(2-MeO)(5-Br)C6H3]3Sb[OC(O)CH2OC6H2Cl3-2,4,5]2 • 1/2 TolH

Tris[(2-methoxy)(5-bromo)phenyl]antimony dicarboxylates [(2-MeO)(5-Br)C6H3]3Sb[OC(O)C6H3F2-2,3]2 (1), [(2-MeO)(5-Br)C6H3]3Sb[OC(O)CH2OC6H2Cl3-2,4,5]2 ∙ ½ TolH (2) were synthesized by interaction of tris[(2-methoxy)(5-bromo)phenyl]antimony and carboxylic acid in the presence of tert-butyl hydroperoxide (molar ratio 1:2:1) in ether at room temperature and structurally characterized after recrystallization from toluene. Crystallographic characteristics of 1 [C35H24Br3F4O7Sb, M = 994.00; triclinic syngony, space group P-1; cell parameters: a = 9.596(13) Å, b = 11.592(18) Å, c = 17.57(3) Å; a = 73.44(7)°, β = 86.25(7)°, g = 87.23(7)°, V = 1868(5) Å3, Z = 2; rcalc = 1.767 g/cm3; m = 4.011 mm-1; F(000) = 964.0; collection area by 2q: 5.54-48.88°; -11 ≤ h ≤ 11, -13 ≤ k ≤ 13, -20 ≤ l ≤ 20; total reflections 44182; independent reflections 6118 (Rint = 0.0341); GOOF = 1.039; R-factor = 0.0378]; 2 [C81H60Br6Cl12O18Sb2, M = 2469.61; triclinic system, space group Р-1; cell parameters: a = 12.214(7) Å, b = 14.000(9) Å, c = 15.358(6) Å; a = 95.32(2)°, β = 97.333(17)°, g = 111.15(3)°, V = 2402(2) Å3, Z = 1; rcalc = 1.707 g/cm3; m = 3.453 mm-1; F(000) = 1206.0; collection area by 2q: 5.84-56.998°; -16 ≤ h ≤ 16, -18 ≤ k ≤ 18, -20 ≤ l ≤ 20; total reflections 74550; independent reflections 12138 (Rint = 0.0588); GOOF = 1.019 ; R-factor = 0.0384]. From the X-ray diffraction data it follows that crystals 1-2 consist of trigonal-bipyramidal molecules with the oxygen atoms of carboxylate ligands in axial positions (solvate molecules of toluene are present in crystal 2). The OSbO angles in 1 and 2 are 172.78(12)°, 175.51(8)°, the Sb-С equatorial bond lengths are 2.111(5)-2.130(5), 2.108(3)-2.126(3) Å; and the Sb-O axial lengths equal 2.096(4), 2.133(4) Å; 2.099(3), 2.121(3) Å, respectively. Due to the bidentate nature of the carboxylate ligands in structures 1 and 2 there are intramolecular contacts between the Sb and O atoms of the carbonyl groups [3.056(5), 3.070(5) Å; 3.129(4), 3.129(4) Å]. The formation of intramolecular contacts Sb⋅⋅⋅O(=C) occurs within two different CSbC equatorial angles, as a result of which the CSbC equatorial angles differ slightly from each other [108.44(19)-129.16(19)° for 1; 112.46(12)-123.88(11)° for 2]. In addition, in molecules 1 and 2 there are intramolecular contacts Sb⋅⋅⋅OMe, which are 3.043(6)-3.172(6) Å, 3.097(4)-3.189(4) Å, respectively, therefore it can be considered that the coordination number of the central metal atom increases to CN = 10. Complete tables of atomic coordinates, bond lengths and valence angles of compounds 1 and 2 are deposited in the Cambridge Crystallographic Data Centre (CCDC No. 2060290, No. 2067753 deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk).