Synthesis and Structure of Tetra(p-tolyl)antimony Arenesulfonates p-Tol4SbOSO2С6H3(NO2)2-2,4 and p-Tol4Sbp-Tol4SbOC(O)C6H3(OH-4)SO3 ∙ H2O

By reacting tetra(p-tolyl)stibonium bromide p-Tol4SbBr with 2,4-dinitrobenzenesulfonic acid in water, tetra(p-tolyl)stibonium 2,4-dinitrobenzenesulfonate p-Tol4SbOSO2С6H3(NO2)2-2,4 (1) was synthesized, which was also synthesized from penta(p-tolyl)antimony and 2,4-dinitrobenzenesulfonic acid in benzene. The product of the reaction of penta(p-tolyl)antimony with sulfosalicylic acid (molar ratio 2 : 1, respectively) in benzene, followed by recrystallization of the target product from water, is tetra(p-tolyl)stibonium sulfosalicylate hydrate p-Tol4Sbp-Tol4SbOC(O)C6H3(OH-4)SO3 ∙ H2O (2). According to X-ray diffraction analysis, 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)—a distorted trigonal bipyramid, while the axial angle CSbО was 170.53(9)°. Complex 2 includes tetrahedral tetra(p-tolyl)stibonium cations, hydration water molecules, and trigonal-bipyramidal sulfosalicylate 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)°, one can describe the coordination of both antimony atoms in complex 2 as trigonal bipyramidal. The crystallographic characteristics: 1 C34H31N2O7SSb, M = 733.42; triclinic system, space group P-1; cell parameters: a = 9.819(3) Å, b = 11.531(4) Å, c = 15.778(6) Å; α = 93.631(18)°, β = 102.62(2)°, γ = 110.333(13)°, V = 1615.7(10) Å3, Z = 2; ρcalc = 1.508 g/cm3; μ = 0.969 mm–1; F(000) = 744.0; region collection at 2θ 5.86°–58.38°; –13 ≤ h ≤ 13, –15 ≤ k ≤ 15, –21 ≤ l ≤ 21; total reflections 67 524; independent reflections 8685 (Rint = 0.0445); GOOF = 1.046; R-factor = 0.0308 and 2 C63H62O7SSb2, M = 1206.69; monoclinic system, space group P21/c; cell parameters: 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; ρcalc = 1.371 g/cm3; μ = 1.010 mm–1; F(000) = 2456.0; region collection by 2θ 5.98°–47.76°; –24 ≤ h ≤ 24, –15 ≤ k ≤ 15, –24 ≤ l ≤ 24; total reflections 59 879; 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.