Tricarbonylbis(triphenylphosphane-κP)iridium(I) hexafluoridophosphate methanol monosolvate

In the title compound, [Ir(C18H15P)2(CO)3]PF6·CH3OH, the IrI atom is coordinated by two triphenylphosphine ligands in axial sites and three carbonyl ligands in the equatorial plane of a fairly regular trigonal bipyramid: the equatorial C—Ir—C angles range from 115.45 (9) to 126.42 (10)°. The small deviations from the ideal tetrahedral geometry around the P atoms are illustrated by C—P—C angles ranging from 104.08 (9) to 106.46 (9)°. In the crystal, the molecules are linked by weak C—H⋯F, C—H⋯O and C—H⋯π interactions.

In the title compound, [Ir(C 18 H 15 P) 2 (CO) 3 ]PF 6 ÁCH 3 OH, the Ir I atom is coordinated by two triphenylphosphine ligands in axial sites and three carbonyl ligands in the equatorial plane of a fairly regular trigonal bipyramid: the equatorial C-Ir-C angles range from 115.45 (9) to 126.42 (10) . The small deviations from the ideal tetrahedral geometry around the P atoms are illustrated by C-P-C angles ranging from 104.08 (9) to 106.46 (9) . In the crystal, the molecules are linked by weak C-HÁ Á ÁF, C-HÁ Á ÁO and C-HÁ Á Á interactions.
The main fragment of the crystal structure of the title compound, [Ir(CO) 3 (PPh 3 ) 2 ](PF 6 ).MeOH, was originally reported by Randall et al., 1991, in the trigonal form, crystallizing in the space group R3 with hydrogen sulfate as counter ion. In this case, the Ir(I) complex ( Figure 1) crystallizes with one hexafluoridophosphate anion and a methanol solvent molecule in the P2 1 /c spacegroup. The trigonal bipyramidal complex consists of three carbonyl groups in the equatorial plane and two triphenylphosphine ligands in the axial plane.

Experimental
CO was bubbled through a solution of [Ir(COD)(PPh 3 ) 2 ]PF 6 (cod = 1,5-cyclooctadiene) (50.0 mg, 0.0515 mmol) in benzene while the mixture was vigorously stirred under gentle reflux. Rapid displacement of COD occurs after which all solvents were evaporated. The product was filtered after the addition of methanol and diethyl ether. Slow evaporation of methanol solution gave yellow blocks. (Yield: 40.1 mg, 82%)

Refinement
The methine and aromatic H atoms were placed in geometrically idealized positions at C-H = 1.00 and 0.95 Å, respectively and constrained to ride on their parent atoms, with U iso (H) = 1.2U eq (C). The highest peak is located 0.79 Å from Ir1 and the deepest hole is situated 0.79 Å from F4.

Figure 1
Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen atoms have been omitted for clarity.

Special details
Experimental. The intensity data were collected on a Bruker X8 ApexII 4 K Kappa CCD diffractometer using an exposure time of ?? s/frame. A total of ??? frames were collected with a frame width of 0.5\ % covering up to θ = 28.0 ° with 99.9% completeness accomplished. Spectroscopy data: 1 H NMR (300 MHz, (CD 3 ) 2 CO): δ = 7.5-7.8 (m, 30H). 31 P NMR (121 MHz, (CD 3 ) 2 CO): δ = -1.6 (s), -143.0 (m, PF 6 ). ν(CO): 1989, 2008, 2025 cm -1 . Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes. Refinement. Refinement of F 2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F 2 , conventional R-factors R are based on F, with F set to zero for negative F 2 . The threshold expression of F 2 > 2σ(F 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.