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

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), a = 109.48(5)°, β = 92.55(2)°, g = 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 deposited 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 water, 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 considered 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.