Reactions of pentaphenyl- and penta(para-tolyl)antimony with fumaric acid
Authors:   South Ural State University, Chelyabinsk, Russian Federation, Sharutin V. , Semenova A. 
Published: November 2023

The interaction of pentaphenylantimony with fumaric acid in benzene (24 h, 24 С, molar ratio 4:3) gave a solvate with benzene Ph4SbOC(O)CH=CHC(O)OSbPh4 ∙ 2Ph4SbOC(O)CH=CHC(O)H ∙ 3PhH (1). At a molar ratio of the initial reagents of 2:1, the binuclear derivative of fumaric acid Ph4SbOC(O)CH=CHC(O)OSbPh4 (2) was formed. In similar reactions of penta(para-tolyl)antimony with fumaric acid, the adduct p-Tol4SbOC(O)CH=CHC(O)OSbTol4 ∙ HOC(O)CH=CHC(O)OH ∙ 4PhH (3) and the solvate of the binuclear derivative of fumaric acid with benzene p-Tol4SbOC(O)CH=СHC(O)OSbTol4 ∙ 3PhH (4) were formed, respectively. According to X-ray diffraction analysis performed at 293 K on a D8 Quest Bruker automatic four-circle diffractometer (two-coordinate CCD detector, Mo Kα radiation, λ = 0.71073 Å, graphite monochromator), the antimony atoms in crystals 1 [C63H53O6Sb2, M 1149.55; triclinic syngony, symmetry group P–1; cell parameters: a = 9.938(4), b = 14.999(8), c = 19.088(8) Å;  = 92.833(17), β = 102.148(16),  = 99.02(3) degrees; V = 2737(2) Å3; crystal size 0.3 × 0.17 × 0.05 mm; reflec-tion index intervals –13 ≤ h ≤ 13, –20 ≤ k ≤ 20, –25 ≤ l ≤ 25; total reflections 89119; independent reflections 14039; Rint = 0.0698; GOOF 1.070; R1 = 0.0442, wR2 = 0.0675; residual electron density 0.47/–0.80 e/Å3], 2 [C26H21O2Sb, M 487.18; monoclinic syngony, symmetry group С2/с; cell parameters: a = 28.35(3), b = 10.453(15), c = 17.49(2) Å; β = 93.01(5) degrees; V = 5176(12) Å3; crystal size 0.2×0.12×0.08 mm; reflection index intervals –26 ≤ h ≤ 30, –11 ≤ k ≤ 11, –19 ≤ l ≤ 13; total reflections 6329; independent reflections 3283; Rint = 0.1220; GOOF 1.318; R1 = 0.1253 wR2 = 0.3080; residual electron density 2.09–4.45 e/Å3], 3 [C88H86O8Sb2, M 1515.09; triclinic syngony, symmetry group P–1; cell parameters: a = 13.35(2), b = 13.50(2), c = 14.15(2) Å;  = 67.02(5), β = 62.29(6),  = 65.63(6) degrees; V = 1994(5) Å3; crystal size 0.55 × 0.33 × 0.28 mm; reflection index intervals –17 ≤ h ≤ 17, –17 ≤ k ≤ 17, –18 ≤ l ≤ 18; total reflections 54923; independent reflections 9183; Rint = 0.0604; GOOF 1.069; R1 = 0.0494, wR2 = 0.1159; residual electron density 1.83–1.68 e/Å3], 4 [C39H38O2Sb, M 660.44; triclinic syngony, symmetry group P-1; cell parameters: a = 11.328(6), b = 12.416(7), c = 12.997(6) Å;  = 82.24(2), β = 72.87(2),  = 75.50(3) degrees; V = 1687.5(15) Å3; crystal size 0.23×0.17×0.05 mm; reflection index in-tervals –14 ≤ h ≤ 14, –15 ≤ k ≤ 15, –16 ≤ l ≤ 16; total reflections 40178; independent reflections 7469; Rint 0.2589; GOOF 1.029; R1 = 0.0627, wR2 = 0.1275; residual electron density 0.95/–1.72 e/Å3], have a distorted trigonal-bipyramidal coordination with the carbon and oxygen atoms in axial positions (axial angles are 173.65(10), 175.74(11) for 1, 176.6(7)° for 2, 176.07(10)° for 3, 178.41(16)° for 4). The Sb–O distances are 2.253(2) and 2.240(2) Å for 1, 2.262(17) Å for 2, 2.302(3) Å for 3, and 2.234(4) Å for 4. The Sb–C bond lengths vary in a narrow range of values (2.110(3)–2.176(3) Å for 1, 2.114(2)–2.18(3) Å for 2, 2.109(5)–2.188(4) Å for 3, 2.113(5)–2.184(5) Å for 4). Structural organization in crystals is due to weak intermolecular contacts of the C=O•••H type (1.83–2.71 Å for 1, 1.81–2.71 Å for 3, 2.69 Å for 4). In crystals 1, 3, 4 the blocks of two dicarboxylic acids are linked to each other via the -C=O•••HOC(O)-chains (1.83, 1.83, 1.81 Å, respectively). Complete tables of atomic coordinates, bond lengths, and bond angles for the structures were deposited at the Cambridge Crystallographic Data Center (no. 2217281 for 1, (no. 2214920 for 2, no. 2220380 for 3, no. 2217063 for 4; deposit@ccdc.cam.ac.uk; https://www.ccdc.cam.ac.uk).