Synthesis and structure of antimony complexes [n-C5H11PPh3]2[Sb2I8(acetone)2] and [Ph4P]3[Sb2I9]•EtO(CH2)2OH

The interaction of antimony iodide with n -pentyltriphenylphosphonium iodide (1:1 mol.) in acetone and tetraphenylphosphonium iodide (3:2 mol.) in ethylene glycol monoethyl ether (ethyl cellosolve) has been used to synthesize ionic complexes [ n -C5H11PPh3]2[Sb2I8(acetone)2] and [Ph4P]3[Sb2I9]∙EtO(CH2)2OH. According to the X-ray analysis data obtained on an automatic diffractometer D8 Quest Bruker (MoKa-radiation, λ = 0.71073 Å, graphite monochromator) at 293 K, of crystals 1 [C26H32OPI4Sb, M 1020.84, the triclinic syngony, the symmetry group Р- 1; cell parameters: a = 10.573(4) Å, b = 13.303(5) Å, c = 13.569(5) Å, α = 117.749(16) degrees, β = 95.534(17) degrees, γ = 100.715(14) degrees; V = 1622.4(10) Å3; the crystal size is 0.32 × 0.22 × 0.13 mm; intervals of reflection indexes are -16 ≤ h ≤ 16, -20 ≤ k ≤ 20, -21 ≤ l ≤ 21; total reflections 98254; independent reflections 13003; Rint 0.0285; GOOF 1.037; R 1 = 0.0438, wR 2 = 0.0745; residual electron density 1.25/-2.06 e/Å3] and 2 [C76H70I9O2P3Sb2, M 2493.83, the triclinic syngony, the symmetry group Р- 1; cell parameters: a = 10.881(7) Å, b = 16.549(7) Å, c = 25.287(12) Å, α = 109.03(2) degrees, β = 94.67(2) degrees, γ = 98.52(3) degrees; V = 4216(4) Å3; the crystal size is 0.37×0.11×0.07 mm; intervals of reflection indexes are -14 ≤ h ≤ 14, -22 ≤ k ≤ 22, -33 ≤ l ≤ 33; total reflections 146846; independent reflections 21003; Rint 0.0708; GOOF 1.014; R 1 = 0.0763, wR 2 = 0.0967; residual electron density 1.23/-1.06 e/Å3], the phosphorus atoms in cations have a slightly distorted tetrahedral coordination with the CPC bond angles 107.48(11)-111.52(11) and 106.5(3)-113.3(3) degrees and similar P-C bond lengths 1.795(3)-1.802(2) Å and 1.787(5)-1.809(6) Å in 1 and 2, respectively. In the centrosymmetric [Sb2I8(acetone)2]2- anion, the antimony atoms have a distorted octahedral coordination ( trans -angles 171.476(9)-176.33(3) degrees, the acetone molecule occupies an axial position being coordinated by the oxygen atom (Sb∙∙∙O 2.820(10) Å). The Sb-Ib. bonds (3.0997(12) Å) are longer than Sb-Iterm: 2.7780(8)-2.9553(10) Å. In the [Sb2I9]3- anion trans -ISbI angles vary in the range 169.612(17)-173.426(19) degrees, Sb-Iterm. bonds 2.8613(13)-2.9609(12) Å are shorter than Sb-Ib: 3.0986(12)-3.2760(13) Å. Solvate ethyl cellosolve molecules form dimers via hydrogen bonds O(1)∙∙∙H(2A) 2.11 Å. Complete tables of coordinates of atoms, bond lengths and valence angles for structures 1 and 2 are deposited at the Cambridge Structural Data Bank (no. 1984511 (1), 2157456 (2); deposit@ccdc.cam.ac.uk; http: //www.ccdc.cam.ac.uk).