Dearylation of tri(ortho-tolyl)bismuth with mesitylenesulfonic acid

Abstract

The interaction of tri(ortho-tolyl)bismuth with mesitylenesulfonic acid dihydrate in ether has led to di(ortho-tolyl)bismuth mesitylenesulfonate hydrate. Its structure has been determined by X-ray diffraction analysis. The X-ray diffraction pattern for crystal 1 has been obtained at 293 K on an automatic diffractometer D8 Quest Bruker (MoKα-radiation, λ = 0.71073 Å, graphite monochromator), the results are the following: [C23H27О4SBi, M 608.48; triclinic syngony, the P–1 symmetry group; cell parameters: a = 8.872(7),  = 109.48(5), β = 92.55(2),  = 110.89(2); V = 1155.9(16) Å3; Z 1; the crystal size 0.32×0.1×0.06 mm; intervals of reflection indexes are –11 ≤ h ≤ 11, –15 ≤ k ≤ 15, –17 ≤ l ≤ 17; total reflections 30469; independent reflections 5781; Rint 0.0327; GOOF 1.044; R1 = 0.0330, wR2 = 0.0811; residual electron density 2.85/–2.12 e/Å3]. Complete tables of coordinates of atoms, bond lengths and valence angles for the structure are de-posited at the Cambridge Structural Data Bank (No. 2165866; deposit@ccdc.cam.ac.uk; https://www.ccdc.cam.ac.uk). The molecules in the hydrate crystal contain coordination-bound wa-ter, moreover, the Bi•••OH2 distance equals 2.487(4) Å, which is comparable to the Bi–O bond length (2.388(4) Å), in the BiOSO2Mez group, and the sum of the covalent radii of bismuth and oxygen (2.31 Å). The Bi–C bond lengths (2.235(5) and 2.237(5) Å) are somewhat lower than the sum of the covalent radii of bismuth and carbon atoms (2.36 Å), and the CBiC angle equals 97.77(19)°. Therefore, the bismuth atom with the oxygen atoms in axial positions should be consid-ered a trigonal bipyramid, with two aryl ligands including lone electron pairs in equatorial positions. The features of synthesis and structure of diarylbismuth arenesulfonates and their solvates with amino- and oxygen-containing ligands have been analyzed. The former are coordination polymers, while the latter are molecules with coordination-bound n-donor ligands.