Bis(acetyl­acetonato-κ2 O,O′)­aqua­(diacetyl­methanido-κC)iridium(III)

Qiao-Wen Chang; Ming-Jin Xie; Wei-Ping Liu; Xi-Zhu Chen; Qing-Song Ye

doi:10.1107/S160053680903760X

. 2009 Sep 30;65(Pt 10):m1264. doi: 10.1107/S160053680903760X

Bis(acetylacetonato-κ² O,O′)aqua(diacetylmethanido-κC)iridium(III)

Qiao-Wen Chang ^a, Ming-Jin Xie ^b, Wei-Ping Liu ^a,^*, Xi-Zhu Chen ^a, Qing-Song Ye ^a

PMCID: PMC2970352 PMID: 21577775

Abstract

In the crystal structure of the title compound, [Ir(C₅H₇O₂)₃(H₂O)], the Ir^III atom is six-coordinated and situated in a slightly distorted octahedral environment. The complex contains both Ir—O and Ir—C bonds and was isolated from a reaction mixture of IrCl₃(H₂O)_x, pentane-2,5-dione and NaHCO₃. O—H⋯O hydrogen bonding between the water molecules and the carbonyl O atoms of adjacent molecules leads to a layered motif extending parallel to (010).

Related literature

For background to the title compound, see: Bennett & Mitchell (1976 ▶); Bhalla et al. (2005 ▶); Gibson (1969 ▶); Matsumoto et al. (2000 ▶); Periana et al. (2002 ▶); Wong-Foy et al. (2003 ▶). For a related structure, see: Isakova et al. (1999 ▶); For background on hydrogen bonding, see: Desiraju (1996 ▶).

Experimental

Crystal data

[Ir(C₅H₇O₂)₃(H₂O)]
M _r = 507.54
Triclinic,
a = 7.7853 (13) Å
b = 7.9461 (13) Å
c = 16.362 (3) Å
α = 77.295 (2)°
β = 77.927 (2)°
γ = 60.918 (1)°
V = 856.7 (3) Å³
Z = 2
Mo Kα radiation
μ = 7.82 mm⁻¹
T = 293 K
0.15 × 0.13 × 0.09 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.387, T _max = 0.539
7435 measured reflections
3900 independent reflections
2885 reflections with I > 2σ(I)
R _int = 0.061

Refinement

R[F ² > 2σ(F ²)] = 0.058
wR(F ²) = 0.127
S = 1.03
3900 reflections
215 parameters
H-atom parameters constrained
Δρ_max = 2.37 e Å⁻³
Δρ_min = −1.88 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680903760X/er2069sup1.cif

e-65-m1264-sup1.cif^{(20.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680903760X/er2069Isup2.hkl

e-65-m1264-Isup2.hkl^{(191.2KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

Ir1—O1	2.015 (8)
Ir1—O4	2.017 (7)
Ir1—O3	2.026 (7)
Ir1—O2	2.029 (7)
Ir1—C11	2.131 (11)
Ir1—O5	2.155 (7)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5D⋯O7ⁱ	0.82	2.24	2.706 (11)	116
O5—H5E⋯O6ⁱⁱ	0.89	2.11	2.715 (11)	125

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

This work was financially supported by Yunnan Provincial Science and Technology Department of the People’s Republic of China (grant Nos. 2008IA008 and 2008CF002)

supplementary crystallographic information

Comment

[Ir(acac-O, O)₂(acac-C³)(H₂O)], as a novel, themally stable, homogeneous bis-acac-O, O—Ir(III) complex catalyst for the anti-Markovnikov, hydroarylation of olefins, has attracted considerable attention (Periana et al., 2002, Wong-Foy et al. 2003, Bhalla et al., 2005). Bennett et al. obtained [Ir(µ-acac-O,O,C³)(acac-O, O)(acac-C³)] and an unknown yellow solid as byproducts in the course of an attempt to improve the synthesis of Ir(acac)₃ (Bennett & Mitchell, 1976). However, they were unable to purify the yellow solid or characterize its structure. Recently Periana et al. successfully isolated this yellow product in pure form and proved it to be [Ir(acac-O, O)₂(acac-C³)(H₂O)] by spectroscopic data(Periana et al., 2002). Despite the thermal and oxidative stability of octahedral iridium (III)-carbon σ -bonded complexes, there are little well characterized γ-C-bonded β-diketone complexes of iridium (III) except [Ir(µ-acac-O,O,C³)(acac-O, O)(acac-C³)] (Gibson, 1969, Matsumoto et al., 2000).

Recently the single-crystal of the compound was obtained in our laboratory and we report its crystallographic structure. In the complex, the central Ir atom is coordinated by a octahedron of four oxygen atoms of two acetylacetone ligands, one carbon atom of one acetylacetone ligand and one oxygen atom of water molcule. The average Ir—O bond length of two acetylacetone ligands is 2.02 Å, which agree with the literature data of Ir(acac)₃ (Isakova et al., 1999), however, Ir—O bond length of coordinated water is 2.15 Å, which is longer than the former, whereas Ir—C bond length is found to be 2.13 Å. Intermolecular C—H···O hydrogen bond (Desiraju, 1996) and C—H···C hydrogen bond are present in the structure; while the C···O distances are within the range of 3.039 (9)–3.486 (10) Å, C—H···O are found to be within the range of 110–168°. The compound forms a hydrogen-bonded chain in which the O5 water uses two H atom to serve as a donor to the O atoms of adjacent molecules, these weaker interactions giving rise to a three-dimensional framework structure.

Experimental

The complex was synthesized according literature (see Periana et al., 2002). In a round-bottom flask equipped with a reflux condenser vented to an oil bubble, 5 g of IrCl₃ (H₂O)_x (54.34% of Ir, 14.13 mmol), 50 ml of 2, 5-pentadione (48.75 mmol) and 5 g of NaHCO₃(59.5 mmol) were added. The mixture was heated to gentle reflux with stirring for 48 h. During this time, a yellow solid precipitated. The reaction mixture was cooled to room temperature and the solid was collected as crude product. The yellow solid was dissolved in 200 ml H2O at room temperature under vigorous stirring and was filtered. Solution was concentrated under vacuo to give 3.15 g (43.6%) complex as yellow microcrystalline. The compound was crystallized from water to obtain crystals suitable for X-ray structure analysis. 1HNMR (CD3OD,p.p.m.):5.54(s, 2H, CH), 5.49(s, 1H, CH), 1.96(s, 12H, CH3), 1.83(s, 6H, CH3). 13CNMR (dmso,p.p.m.): 208.4(s, C-acac, C=O), 186.1(s, O-acac, C=O), 102.6(s, O-acac, CH), 48.6(s, C-acac, CH), 31.6(s, C-acac, CH3, 26.6(s, O-acac, CH3). Anal. Calcd: Ir, 37.95; C, 35.54; H, 4.93. Found: Ir, 37.90; C, 35.48; H, 4.87.