Минорный продукт [Ph3Sb(Cl)O]3C • PhH в реакции перераспределения лигандов арильных производных пятивалентной сурьмы

A. N. Efremov

doi:10.14529/chem190206

Authors

A. N. Efremov South Ural State University, Chelyabinsk

DOI:

https://doi.org/10.14529/chem190206

Keywords:

дихлорид трифенилсурьмы, бис(2, 4-дибромфеноксид) трифенилсурьмы, реакция перераспределения лигандов, трехкоординированный углерод, нейтральный комплекс, рентгеноструктурный анализ

Abstract

One of the reaction products of triphenylantimony dichloride and triphenylantimony bis(2,4-dibromophenoxide) (1:1 mol.) in benzene in air is the compound of three-coordinated carbon [Ph₃Sb(Cl)O]₃C × PhH (1). The compound has been identified by IR spectroscopy and X-ray diffraction analysis. According to the X-ray diffraction analysis the target product is a benzene solvate [С₆₁H₅₁Cl₃O₃Sb₃, М = 1303.65; the monoclinic system, space group P2₁/c; a 17.17(2), b 18.75(2); c 17.322(18) Å; α 90.00, β 90.58(5), γ 90.00 град.; V 5576(11) Å³; Z 4; µ 1.630 mm^–1; F(000) 2580.0; crystal size 0.28 × 0.22 × 0.11 mm; 2θ for data collection 6.4 - 36.8 degrees; index ranges −15 ≤ h ≤ 15, −16 ≤ k ≤ 16, −15 ≤ l ≤ 15; total reflections 24392; independent reflections 3981; R_int 0.0516; variables 632, GOOF 1.141; R₁ = 0.0392; wR₂ = 0.0912; residual electron density 0.43/–0.35 e/Å³]. The COSb angles in the compound 1 vary in the interval 123.3(8)-127.1(8)°. The C–O shortened distances (1.365(15)–1.385(15) Å) compared to the sum of the covalent radii of carbon and oxygen atoms (1.51 Å) indicate an increase in the multiplicity of these bonds. The abnormal reduction of Sb–O distances (1.986(7), 2.001(7), 2.011(7) Å) in the neutral molecule 1 compared to the sum of the covalent radii of antimony and oxygen atoms (2.14 Å) implies delocalization of the electron density in the CO₃Sb₃ core. The Sb – Cl distances are slightly longer than the sum of the covalent radii of antimony and chlorine atoms and are longer than ones in triphenylantimony dichloride. The antimony atoms have a distorted trigonal-bipyramidal coordination with heteroatoms in axial positions. The formation of the crystal structure is due to the formation of weak hydrogen bonds such as С···Н (2.72-2.90 Å) and Сl···Н (2.94 Å). Complete tables of coordinates of atoms, bond lengths and valence angles are deposited at the Cambridge Structural Data Bank (No. 1851485; deposit@ccdc.cam.ac.uk; http:// www.ccdc.cam.ac.uk/data_request/cif).

Author Biography

A. N. Efremov, South Ural State University, Chelyabinsk

аспирант кафедры теоретической и прикладной химии

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