Synthesis and structure of tris(triphenylstibine)silver carboxylatе complexes

Abstract

Several tris(triphenylstibine)silver carboxylate complexes (Ph3Sb)3AgOC(O)C6H3F2-2,5 (1), (Ph3Sb)3AgOC(O)C6H3F2-3,4 (2) and (Ph3Sb)3AgOC(O)C6H4Cl-2 (3) were synthesized by the interaction of equimolar amounts of nitrato-tris(triphenylstibine)silver with 2,5-difluorobenzoic acid, 3,4-difluorobenzoic acid and 2-chlorobenzoic acid in the presence of triethylamine in a methanol-acetonitrile solvent mixture (1:1 vol/vol). Complexes 1–3 were identified by IR spectroscopy and X-ray diffraction. Crystallographic characteristics are: 1 [C61H48AgF2O2Sb3, M = 1324.11; triclinic syngony, space group P-1; cell parameters: a = 13.43(3) Å, b = 13.84(2) Å, c = 15.04(2) Å, α = 91.28(6)°, β = 91.88(10)°, γ = 103.91(7)°, V = 2711(9) Å3, Z = 2; calc = 1.622 g/cm3;  = 1.833 mm–1; F(000) = 1296.0; collection area by 2q: 5.66–54.28; –16 ≤ h ≤ 16, –17 ≤ k ≤ 17, –18 ≤ l ≤ 19; total reflections 37821; independent reflections 11289 (Rint = 0.0625); GOOF = 1.046; R-factor = 0.1729]; 2 [C61H48AgF2O2Sb3, M = 1324.11; triclinic syngony, space group P-1; Cell parameters: a = 13.302(8) Å, b = 14.019(13) Å, c = 15.001(10) Å, α = 91.54(3)°, β = 92.26(2)°, γ = 104.88(4)°, V = 2699(4) Å3, Z = 2; calc = 1.628 g/cm3;  = 1.891 mm–1; F(000) = 1295.0; collection area by 2q: 6.02–57; –17 ≤ h ≤ 17, –18 ≤ k ≤ 18, –19 ≤ l ≤ 20; Total reflections 148716; Independent reflections 13652 (Rint = 0.0500); GOOF = 1.051; R-factor = 0.0778]; 3 [C117H97Ag2ClNO2Sb6, M = 2530.64; triclinic syngony, space group P-1; cell parameters: a = 13.592(17) Å, b = 14.088(16) Å, c = 14.767(18) Å, α = 82.68(6)°, β = 87.65(7)°, γ = 76.11(4)°, V = 2722(6) Å3, Z = 1; calc = 1.544 g/cm3;  = 1.888 mm–1; F(000) = 1239.0; collection area by 2q: 5.992–53.718; –17 ≤ h ≤ 17, –17 ≤ k ≤ 17, –18 ≤ l ≤ 18; total reflections 57445; independent reflections 11587 (Rint = 0.0666); GOOF = 1.059; R-factor = 0.1345]. In complexes 1–3, the silver and antimony atoms have a distorted tetrahedral coordination. The SbAgSb angles in compounds 1–3 vary in the ranges: 107.80(11)–113.10(8)° (1), 109.33(5)–113.49(3)° (2), 110.52(8)–115.22(9)° (3). The OAgSb angles vary in the ranges: 78.9(9)–121.5(7)° (1), 90.5(3)–128.7(3)° (2), 89.6(8)–121.6(8)° (3). The OAgSb angles vary in a wide range and make the greatest contribution to distortion of the coordination polyhedron of the silver atom. The angles at the antimony atoms vary in the ranges of 96.5(12)–123.4(4)° (1), 96.0(5)–104.4(3)° (2), 97.1(8)–101.8(6)° (3). The CSbAg valence angles are larger than the CSbC angles in all structures. The Ag–O(1) distances in compounds 1–3 exceed the sum of the covalent radii of silver and oxygen (2.00 Å) and equal 2.30(3), 2.291(10), and 2.43(3) Å, respectively. The Ag∙∙∙O(2) distances to the carbonyl oxygen atom are 3.06(3) (1), 3.03(1) (2), and 3.04(3) (3) Å. In all compounds the Ag∙∙∙O(2) distance exceeds the Ag–O(1) bond length; therefore, the carboxylate ligand is monodentate. The Ag–Sb bond lengths in complexes 1–3 are equal to 2.693(4), 2.728(4), 2.796(4) Å; 2.7242(17), 2.686(2), 2.7770(17) Å; 2.753(3), 2.701(3), 2.721(3) Å, respectively. The C–Sb distances vary within the ranges: 2.111(12)–2.193(18) Å, 2.059(5)–2.216(7) Å, 2.10(3)–2.169(19) Å for compounds 1–3, respectively. Complete tables of atomic coordinates, bond lengths and valence angles of compounds 1–3 have been deposited with the Cambridge Crystallographic Data Centre (CCDC 2340012 (1), 2340008 (2) and 2340026 (3); deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk).