Adducts of Aryl Compounds of Antimony and Bismuth with Carboxylic Acids, Phenols, and Oximes

Abstract

During recrystallization from benzene or toluene of the products of interaction of triarylantimony or triarylbismuth with carboxylic acids, phenol, or oxime in the presence of tert-butyl hydroperoxide (molar ratio 1 : 2 : 1, diethyl ether, 24°C, 24 h), minor products, adducts of aryl compounds of antimony or bismuth of the Ar₃MX₂ type with carboxylic acids, phenol, and oxime are isolated. According to X-ray structural analysis conducted at 293 K using an automatic D8 Quest Bruker four-circle diffractometer (two-coordinate CCD detector, Mo K_α radiation, λ = 0.71073 Å, graphite monochromator), the metal atoms in the crystals of m-Tol₃Sb[OC(O)C₆H₃F₂-2,5]₂ ⋅ HOC(O)C₆H₃F₂-2,5 (1) [C₄₂H₃₁O₆F₆Sb, M 867.42; triclinic system, symmetry group P\(\bar {1}\); cell parameters a = 8.78(5) Å, b = 13.10(6) Å, c = 16.64(8) Å; α = 102.86(19)°, β = 99.3(2)°, γ = 98.0(3)°; V = 1813(16) ų; Z 2; reflection index intervals –7 ≤ h ≤ 7, –11 ≤ k ≤ 11, –14 ≤ l ≤ 14; total reflections 14 149; independent reflections 2603; R_int 0.0284; GOOF 1.049; R₁ = 0.0348, wR₂ = 0.0938; residual electron density 0.55/–0.42 e/ų], p‑Tol₃Bi[OC(O)C₆HF₄-3,4,5,6]₂ ⋅ HOC(O)C₆HF₄-3,4,5,6 (2) [C₄₂H₂₅O₆F₁₂Bi, M 1062.60; triclinic system, symmetry group P\(\bar {1}\); cell parameters a = 12.246(11) Å, b = 12.976(18) Å, c = 14.391(13) Å; α = 68.27(4)°, β = 69.89(3)°, γ = 86.11(5)°; V = 1990(4) ų; Z 2; reflection index intervals –15 ≤ h ≤ 15, ‒16 ≤ k ≤ 16, –18 ≤ l ≤ 18; total reflections 48 542; independent reflections 9207; R_int 0.0321; GOOF 1.136; R₁ = 0.0322, wR₂ = 0.0648; residual electron density 1.81/–1.08 e/ų], [(2-MeO-5-BrC₆H₃)₃SbOC₆H₄Br-4]₂O ⋅ 2HOC₆H₄Br-4 (3) [C₆₆H₅₄Br₁₀O₁₁Sb₂, M 2065.69; monoclinic system, symmetry group C2₁/c; cell parameters a = 12.017(14) Å, b = 25.54(3) Å, c = 13.181(18) Å; β = 116.71(5)°; V = 3613(8) ų; Z 2; reflection index intervals –13 ≤ h ≤ 13, –27 ≤ k ≤ 27, –12 ≤ l ≤ 12; total reflections 29 461; independent reflections 4545; R_int 0.0656; GOOF 1.062; R₁ = 0.0565, wR₂ = 0.1200; residual electron density 1.59/–1.31 e/ų], and [(2-MeO)C₆H₄]₃Sb[ON=CHC₄H₂(NO₂-2)]₂ ∙ 2HON=CHC₄H₂(NO₂-2) ∙ 1/2PhH (4) [C₄₄H₃₈N₈O₁₉Sb, M 1104.57; triclinic system, symmetry group P\(\bar {1}\); cell parameters a = 10.240(5) Å, b = 14.480(8) Å, c = 18.093(11) Å; α = 103.43(3)°, β = 104.50(2)°, γ = 98.876(17)°; V = 2461(2) ų; Z 2; reflection index intervals –13 ≤ h ≤ 13, –18 ≤ k ≤ 18, –23 ≤ l ≤ 23; total reflections 58 643; independent reflections 10 886; R_int 0.0558; GOOF 1.061; R₁ = 0.0429, wR₂ = 0.1095; residual electron density 1.91/–0.51 e/ų] show distorted trigonal-bipyramidal coordination with oxygen atoms in axial positions. Full tables of atom coordinates, bond lengths, and valence angles for the structures are deposited in the Cambridge Structural Database (no. 2050322 for 1, no. 2045173 for 2, no. 2070387 for 3, and no. 2119790 for 4; deposit@ccdc.cam.ac.uk; https://www.ccdc.cam.ac.uk).