Synthesis and structure of tetra(para-tolyl)antimony arenesulfonates p-Tol4SbOSO2C6H3(NO2)-2,4 and [p-Tol4Sb] [p-Tol4SbOC(O)C6H3(OH-4)SO3] ∙ H2O.
Authors:   South Ural State University, Chelyabinsk, Russia, Sharutin V. , Morozova K. 
Published: September 2024

Reaction of tetra(para-tolyl)stibonium bromide p-Tol4SbBr with 2,4-dinitrobenzenesulfonic acid in water synthesized tetra(para-tolyl)stibonium 2,4-dinitrobenzenesulfonate p-Tol4SbOSO2С6H3(NO2)2-2,4 (1), which was also synthesized from penta(para-tolyl)antimony and 2,4-dinitrobenzenesulfonic acid in benzene. The product of the reaction of penta(para-tolyl)antimony with sulfosalicylic acid (mole ratio 2:1, respectively) in benzene, followed by re-crystallization of the target product from water, was tetra(para-tolyl)stibonium sulfosalicylate hy-drate [p-Tol4Sb][p-Tol4SbOC(O)C6H3(OH-4)SO3]∙H2O (2). According to X-ray diffraction analy-sis, the antimony atoms in complex 1 have the coordination of a distorted tetragonal pyramid, and taking into account the coordination bond Sb∙∙∙OSO2С6H3(NO2)2-2,4 (2.877(3) Å), they form a dis-torted trigonal bipyramid, while the CSbО axial angle is 170.53(9). Complex 2 includes tetrahe-dral tetra(para-tolyl)stibonium cations, hydration water molecules and trigonal-bipyramidal sul-fosalicylate anions, in which tolyl substituents occupy equatorial positions and the oxygen atom is linked to the central atom by a polar covalent bond SbO (2.279(3) Å). In addition, the carbonyl oxygen atom is coordinated to the metal atom (the Sb∙∙∙O=C distance is 3.323(6) Å), which exceeds the sum of the covalent radii of the partner atoms (2.14 Å), but is shorter than the sum of Van der Waals radii of partner atoms (3.7 Å). In cation 2, the antimony atom is coordinated to one of the oxygen atoms of the sulfonate group of the sulfosalicylate substituent, and the Sb∙∙∙OSO2 distance (2.651(3) Å) is shorter than the similar distance in complex 1, and the CSbО angle is 176.51(13), therefore we can talk about trigonal bipyramidal coordination of both antimony atoms in complex 2. The crystallographic characteristics: 1 [C34H31N2O7SSb, M = 733.42; triclinic system, sp. gr. P-1; cell parameters: a = 9.819(3) Å, b = 11.531(4) Å, c = 15.778(6) Å;  = 93.631(18), β = 102.62(2),  = 110.333(13), V = 1615.7(10) Å3, Z = 2; calc = 1.508 g/cm3;  = 0.969 mm–1; F(000) = 744.0; region collection at 2q 5.86–58.38; –13 ≤ h ≤ 13, –15 ≤ k ≤ 15, –21 ≤ l ≤ 21; total reflections 67524; independent reflections 8685 (Rint = 0.0445); GOOF = 1.046; R-factor = 0.0308] and 2 [C63H62O7SSb2, M = 1206,69; monoclinic system, sp. gr. P21/c; cell pa-rameters: a = 21.132(15) Å, b = 13.644(9) Å, c = 21.796(19) Å; β = 111.52(3), V = 5846(8) Å3, Z = 4; calc = 1.371 g/cm3;  = 1.010 mm–1; F(000) = 2456.0; region collection by 2q 5.98–47.76; –24 ≤ h ≤ 24, –15 ≤ k ≤ 15, –24 ≤ l ≤ 24; total reflections 59879; independent reflections 8986 (Rint = 0.0621); GOOF = 1.028; R-factor = 0.0355]. Complete tables of atomic coordinates, bond lengths, and bond angles of compounds 1 and 2 have been deposited in the Cambridge Structural Data Center (CCDC 2216049 and 2233523; deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac. uk).