Adducts of antimony and bismuth aryl compounds with carboxylic acids, phenols, and oximes

When the reaction products of triarylantimony or -bismuth with carboxylic acids, phenol, or oxime in the presence of tertiary butyl hydroperoxide (molar ratio 1:2:1, diethyl ether, 24 °C, 24 h) were recrystallized brom benzene or toluene, the adducts of antimony or bismuth aryl compounds with carboxylic acids, phenol, and oxime of the Ar3MX2 type were isolated as minor products. According to X-ray structural analysis performed at 293 K on a D8 Quest Bruker automatic four-circle diffractometer (two-coordinate CCD detector, Mo K α radiation, λ = 0.71073 Å, graphite monochromator), metal atoms in crystals m -Tol3Sb[OC(O)C6H3F2-2,5]2 ∙ HOC(O)C6H3F2-2,5 (1) [C42H31O6F6Sb, M 867.42; triclinic syngony, symmetry group P1 ; cell parameters: a = 8.78(5), b = 13.10(6), c = 16.64(8) Å; a = 102.86(19), β = 99.3(2), g = 98.0(3) degrees; V = 1813(16) Å3; Z 2; reflection index intervals -7 ≤ h ≤ 7, -11 ≤ k ≤ 11, -14 ≤ l ≤ 14; total reflections 14149; independent reflections 2603; R int 0.0284; GOOF 1.049; R 1 = 0.0348, wR 2 = 0.0938; residual electron density 0.55/-0.42 e/Å3]; p -Tol3Bi[OC(O)C6HF4]2∙HOC(O)C6HF4 (2) [C42H25O6F12Bi, M 1062.60; triclinic syngony, symmetry group P 1 ; cell parameters: a = 12.246(11), b = 12.976(18), c = 14.391(13) Å; a = 68.27(4), β = 69.89(3), g = 86.11(5) degrees; V = 1990(4) Å3; Z 2; reflection index intervals -15 ≤ h ≤ 15, -16 ≤ k ≤ 16, -18 ≤ l ≤ 18; total reflections 48542; independent reflections 9207; R int 0.0321; GOOF 1,136; R 1 = 0.0322, wR 2 = 0.0648; residual electron density 1.81/-1.08 e/Å3]; [(2-MeO-5-BrC6H3)3SbOC6H4Br-4]2O∙2HOC6H4Br-4 (3) [C66H54Br10O11Sb2, M 2065.69; monoclinic syngony, symmetry group C 21/c; cell parameters: a = 12.017(14), b = 25.54(3), c = 13.181(18) Å; β = 116.71(5) degrees; V = 3613(8) Å3; Z 2; reflection index intervals -13 ≤ h ≤ 13, -27 ≤ k ≤ 27, -12 ≤ l ≤ 12; total reflections 29461; independent reflections 4545; R int 0.0656; GOOF 1.062; R 1 = 0.0565 wR 2 = 0.1200; residual electron density 1.59/-1.31 e/Å3]; [(2-MeO)C6H4]3Sb[ON=CHC4H2O(NO2-2)]2 ∙ 2HON=CHC4H2O(NO2-2) ∙ ½PhH (4) [C44H38N8O19Sb, M 1104.57; triclinic syngony, symmetry group P1 ; cell parameters: a = 10.240(5), b = 14.480(8), c = 18.093(11) Å; a = 103.43(3), β = 104.50(2), g = 98.876(17) degrees; V = 2461(2) Å3; Z 2; reflection index intervals -13 ≤ h ≤ 13, -18 ≤ k ≤ 18, -23 ≤ l ≤ 23; total reflections 58643; independent reflections 10886; R int 0.0558; GOOF 1.061; R 1 = 0.0429, wR 2 = 0.1095; residual electron density 1.91/-0.51 e/Å3] have a distorted trigonal-bipyramidal coordination with the oxygen atoms in axial positions. Complete tables of atomic coordinates, bond lengths, and bond angles for the structures were deposited at the Cambridge Crystallographic Data Center (no. 2050322 for 1, no. 2045173 for 2, no. 2070387 for 3, no. 2119790 for 4; deposit@ccdc.cam.ac.uk; https www.ccdc.cam.ac.uk).