Synthesis and structure of ionic complex including antimony and bismuth [Ph4Sb]2 [p-Tol2Bi2Cl6] • 2PhH

The reaction of equimolar amounts of para-tolylbismuth dichloride with tetraphenylantimony chloride in benzene leads to formation of an ionic complex including antimony and bismuth [Ph4Sb]2 [p-Tol2Bi2Cl6] ∙ 2PhH (1). The structure of complex 1 has been established by X-ray diffraction analysis. The X-ray structural analysis was carried out on an automatic four-circle D8 Quest Bruker diffractometer (Мо Кα-radiation, λ = 0.71073 Å, graphite monochromator) at 293 K [C43H39Cl3SbBi, M 992.82; monoclinic syngony, space group С2/с; сell parameters: a = 22.93(2), b = 13.953(16), c = 26.35(3) Å; a = 90.00, β = 105.19(3), g = 90.00 deg., V = 8136(15) Å3, Z = 8; rcalc = 1.621 г/см3; 2q 5.84-57.2 deg., crystal size 0.5 × 0.16 × 0.03 mm3; index ranges -30 ≤ h ≤ 30, -18 ≤ k ≤ 18, -34 ≤ l ≤ 35, total reflections 116516, independent reflections 10179; Rint = 0.1439, GOOF 1.085, R-factors for F2 > 2σ(F2) R1 = 0.0552, wR2 = 0.1004; R-factors for all reflections R1 = 0.1097, wR2 = 0.1200; residual electron density (max/min) 0.97/-1.45 e/Å3]. In the molecule of crystal 1 the coordination of the antimony atom in cations is distorted tetrahedral (the СSbС angles are 104.8(3)°-113.2(3)°). The Sb-C bond lengths vary in a narrow range of values (2.081(7)-2.098(7) Å). The coordination of the bismuth atoms in centrosymmetric binuclear anions [p-Tol2Bi2Cl6] is slightly distorted octahedral: the ClBiCl cis-angles are in the range 81.95(10)-91.18(10)°, the ClBiCl trans-angles are 171.92(7), 172.84(7)°, the length of the Bi-C bond is 2.249(7) Å. The structural organization in crystal 1 is due to weak intermolecular contacts of the Cl···Н type, 2.73-2.94 Å. Complete tables of atomic coordinates, bond lengths and bond angles for structure 1 have been deposited at the Cambridge Crystallographic Data Centre (No. 2125624; deposit@ccdc.cam.ac.uk; https://www.ccdc.cam.ac.uk).