Synthesis and structure of tris(5-bromo-2-metoxyphenyl)bismuth bis(bromodifluoroacetate)

The interaction of tris(5-bromo-2-methoxyphenyl)bismuth with bromodifluoroacetic acid in the presence of hydrogen peroxide in diethyl ether at the molar ratio (1: 2: 1) leads to the formation of tris(5-bromo-2-methoxyphenyl)bismuth bis(bromodifluoroacetate) (1) with 80 % yield after recrystallization from the benzene-petroleum ether mixture. The use of tert-butyl hydroperoxide as the oxidizing agent does not lead to the formation of the desired product. Compound 1 is characterized by IR spectroscopy and X-ray diffraction analysis. According to X-ray diffraction data, there are two types of crystallographically independent molecules in the crystal, the geometric characteristics of which differ slightly. The bismuth atom in the molecule has distorted trigonal-bipyramidal coordination with oxygen atoms of carboxylate substituents in axial positions and carbon atoms of the aryl groups at equatorial positions. The angles between the axial and equatorial substituents OBi(1,2)O and CBi(1,2)C are 169.3(5)°, 170.6(7)° and 113.1(8)° -123.5(8)°, 118.1(7)°- 123.1(8)°. The bond lengths of Bi(1,2)-O and Bi(1,2)-C are 2.256(16), 2.276(19) Å; 2.261(14), 2.316(16) Å and 2.15(2)-2.23(2) Å; 2.18(2)- 2.19(2) Å. The intramolecular distances between the valence-free non-bound atoms are Bi(1,2)⋅⋅⋅O(=C) (3.16(2), 3.57(4) Å, 3.11(2), 3.18(2) Å) and Bi(1,2)⋅⋅⋅OMe (3.00(2) - 3.17(2) Å, 3.04(2) - 3.14(2) Å) are less than the sum of the Van-der-Waals radii of Bi and O atoms. Crystallographic characteristics of 1: the space group P 1 ; cell parameters: a = 12.775(14) Å, b = 15.999(12) Å, c = 17.196(16) Å; α = 88.09(3) degrees, β = 68.67(5) degrees, γ = 87.92 (4) degrees; V = 3271 (5) Å3. Full tables of coordinates of atoms, bond lengths and valence angles are deposited at the Cambridge Structural Data Bank (no. 1833279; deposit@ccdc.cam.ac.uk; http: //www.ccdc. Cam.ac.uk).