Reactions of pentaphenylantimony and penta-para-tolylanimony with calixarene [4-t-BuC6H2OH(S-2)]4

Pentaphenylantimony and penta-para-tolylantimony react with calixarene [4- t -BuC6H2OH(S-2)]4 (СArH) by way of arene elimination and formation of the [Ph4Sb]+[СAr]- × TolH (1), [ p -Tol4Sb]+[CAr]- × H2O (2) ionic products with a yield up to 96%. The compound has been identified by IR spectroscopy and X-ray diffraction analysis. According to the X-ray diffraction data, compounds 1 and 2 are ionic complexes with solvate molecules of toluene (1) and water (2). The cation has a tetrahedral coordination of the antimony atom with aryl ligands at the polyhedron vertices; the anion is represented by the deprotonated form of p - tert -butylthiacalix[4]arene. The three tert -butyl groups, the phenyl ring and solvated toluene in the structure of compound 1, and two tert -butyl fragments in the structure of compound 2 are disordered over two positions. The tetrahedral coordination of antimony atoms in the cations of compounds 1 and 2 is slightly distorted. The CSbC angles deviate from the theoretical value and vary within 106.0(4)-117.7(4)° (1), 105.75(15)-112.84(15)° (2). The average Sb-C bond lengths are 2.101(3) and 2.106(4) Å in structures 1 and 2, respectively. The [СAr]- anion is in the cone conformation, the upper rim of which is represented by the tert -butyl groups in the para -position, while the lower one is represented by hydroxy groups, one of which is deprotonated. The СAr-O- bond length (1.318(4) (1) and 1.326(4) (2) Å) is less than the average value of the СAr-OH bond lengths (1.338(4) (1) and 1.343(4) (2) Å), which indicates increasing multiplicity of the bond and localization of a negative charge on the oxygen atom. Intramolecular hydrogen bonds with the neiboring O atom are observed. The H∙∙∙O distances are 2.16, 1.69, 1.77 Å in 1 and 1.92, 1.79, 1.76 Å in 2. Dihedral angles between opposite phenoxide rings are 60.64° and 87.07° (1) and 83.85° and 80.42° (2), which indicates somewhat less symmetric anion in structure 1 than in structure 2. The formation of the crystal spatial structure is due to the formation of hydrogen bonds between ions with participation of oxygen and sulfur atoms, as well as СН∙∙∙π-interactions, while the ions form chains in the crystal of compound 1, and layers in the crystal of compound 2. Complete tables of atom coordinates, bond lengths and valence angles are deposited at the Cambridge Crystallographic Data Center (No. 1850118 (1); No. 2013220 (2); deposit@ccdc.cam.ac.uk or http://www.ccdc.cam.ac.uk/data_request/cif).