Synthesis and structure of tri(meta-tolyl)bismuth bis(2,5-dichlorobenzenesulfonate) and tri(para-tolyl)bismuth bis(1-naphthalenesulfonate).

Abstract

The interaction of tri(meta-tolyl)bismuth with 2,5-dichlorobenzenesulfonic acid in the pres-ence of tert-butyl hydroperoxide in ether has led to tri(meta-tolyl)bismuth bis(2,5-dichlorobenzenesulfonate) (1) yielding 83%. Similarly, tri(para-tolyl)bismuth bis(1-naphthalenesulfonate) (2) has been obtained yielding 78%. Compounds 1 and 2 have also been synthesized by the reaction of triarylbismuth with arenesulfonic acid in the presence of air oxy-gen yielding up to 20%. The X-ray structural analysis has been carried out on an automatic four-circle D8 Quest Bruker diffractometer (CCD detector, Мо Kα-radiation, λ = 0.71073 Å, graphite monochromator) at 293 K. Crystals 1 [C33H27O6S2Cl4Bi, M 934.45; monoclinic syngony, space group С2/с; cell parameters: a = 42.153(17), b = 11.644(5), c = 14.659(7) Å; α = 90.00 deg., β = 102.73(2) deg., γ = 90.00 deg.; V = 7018(5) Å3; crystal size 0.33×0.28×0.13 mm3; index ranges –65 ≤ h ≤ 65, –18 ≤ k ≤ 18, –22 ≤ l ≤ 22; total reflections 90667; independent reflections 14068; Rint = 0.0709; GOOF 0.997; R1 = 0.0435, wR2 = 0.0683; residual electron density (max/min) 1.41/–1.58 e/Å3], and 2 [C41H35O6S2Bi, M 896.79; monoclinic syngony, space group P21/n; cell parameters: a = 17.624(14), b = 11.898(6), c = 20.118(12) Å; α = 90.00 deg., β = 99.17(4) deg., γ = 90.00 deg.; V = 4165(5) Å3; crystal size 0.5×0.46×0.27 mm3; index ranges –31 ≤ h ≤ 22, –20 ≤ k ≤ 20, –35 ≤ l ≤ 36; total reflections 91024; independent reflections 24316; Rint = 0.2080; GOOF 1.059; R1 = 0.1083, wR2 = 0.2566; residual electron density (max/min) 7.23/–5.92 e/Å3]. The bismuth atoms have a distorted trigonal-bipyramidal coordination. The OBiO axial angles are 179.64(9) and 174.4(2) deg.. respectively; the sums of the CBiC an-gles in the equatorial plane are 360 deg. The Bi–O bond lengths are 2.291(3), 2.297(3) Å, and 2.269(8), 2.272(7) Å; the intervals of variation in the Bi–C equatorial bond lengths are 2.176(4)–2.187(3) Å and 2.159(10)–2.214(8) Å. Structures 1 and 2 contain intramolecular contacts be-tween the bismuth atoms and the oxygen atom of the sulfonate ligands. The Bi•••O=С distances equal 3.309(3), 3.518(3) Å, and 3.355(14), 3.458(15), which is less than the sum of the Van der Waals radii of bismuth and oxygen (3.59 Å). Crystals 1 and 2 contain intermolecular contacts H∙∙∙O (2.442.72 Å and 2.532.65 Å); intermolecular contacts Cl∙∙∙Н (2.81 Å) are present in crystals 1. Complete tables of atomic coordinates, bond lengths and bond angles for structures have been deposited at the Cambridge Crystallographic Data Centre (No. 2153155 (1), No. 2157446 (2); deposit@ccdc.cam.ac.uk; https://www.ccdc.cam.ac.uk).