Synthesis and Crystal Structure of [Ph4Bi(DMSO-O)][IrCl4(DMSO-S)2].
Abstract
Interaction of sodium hexachloroiridate (III) hydrate with tetraphenylbismuth nitrate in water followed by recrystallization from dimethyl sulfoxide has been used to synthesize the novel iridium ionic complexes [Ph4Bi(DMSO-O)][IrCl4(DMSO-S)2]. It has been structurally characterized. The X-ray diffraction pattern has been obtained at 293 K on an automatic diffractometer D8 Quest Bruker (MoKα-radiation, λ = 0.71073 Å, graphite monochromator) of crystal [C60H76Cl8Ir2Bi2S6O6, M 2171.53, the triclinic syngony, the symmetry group P-1; cell parameters: a 9.51(3), b 17.69(5), c 23.76(7) Å, α = 90.09(12) degrees, β = 90.54(16) degrees, γ = 105.50(14) degrees; V = 3852(20) Å3; the crystal size is 0.34×0.12×0.1 mm; intervals of reflection indexes are –9 ≤ h ≤ 9, –17 ≤ k ≤ 17,
–24 ≤ l ≤ 24; total reflections 32111; independent reflections 8144; Rint 0.0776; GOOF 1.118;
R1 = 0.0954, wR2 = 0.2137; residual electron density 3.63/–2.02 e/Å3], the bismuth atoms have distorted trigonal-bipyramidal coordination. The axial angles of СBiС 176.9(11)° (176.4(11)°); the sum of the angles of CBiC in the pseudo-equatorial plane is 349.3(15)° (349.3(15)°). The Bi–C bond lengths 2.01(5)-2.25(4) Å; Bi×××O bond lengths 2.73(2) Å (2.76(4) Å)). The iridium atoms in the centrosymmetric crystallographically independent anions [IrCl4(DMSO-S)2]- have a slightly distorted octahedral coordination (the trans-angles of ClIrCl and SIrS are equal to 180°; the cis angles of SIrCl and ClIrCl vary in the range 87.6(4)–92,4(4)°). The Ir–Cl bond lengths vary in the range 2.297(13)–2.375(11) Å; Ir–S bonds 2.267(10)–2.32(2) Å. The structural organization in crystal is caused by the weak van-der-Waals interactions: S=O∙∙∙H–С (2.38–2.70 Å) and Ir–Cl∙∙∙H–C (2.70–2.92 Å). Complete tables of coordinates of atoms, bond lengths and valence angles for structure are deposited at the Cambridge Structural Data Bank (no. 1989704; deposit@ccdc.cam.ac.uk; https://www.ccdc.cam.ac.uk).
