(Acetyl­acetonato-κ2 O,O′)bis­[5-meth­oxy-2-(naphth[1,2-d][1,3]oxazol-2-yl)phenyl-κ2 C 1,N]iridium(III)

Song Li; Guo-Jie Yin; Shi-Min Wang; Yuan-Yuan Zhou

doi:10.1107/S1600536811035690

. 2011 Sep 14;67(Pt 10):m1343. doi: 10.1107/S1600536811035690

(Acetylacetonato-κ² O,O′)bis[5-methoxy-2-(naphth[1,2-d][1,3]oxazol-2-yl)phenyl-κ² C ¹,N]iridium(III)

Song Li ^a, Guo-Jie Yin ^b,^*, Shi-Min Wang ^c, Yuan-Yuan Zhou ^d

PMCID: PMC3201473 PMID: 22065644

Abstract

In the title compound, [Ir(C₁₈H₁₂NO₂)₂(C₅H₇O₂)], the Ir atom is O,O′-chelated by the acetylacetonate group and C,N-chelated by the 2-arylnaphth[1,2-d]oxazole groups. The six-coordinate metal atom displays a distorted octahedral geometry. Intramolecular C—H⋯O hydrogen bonds occur. In the crystal, intermolecular C—H⋯O hydrogen bonds link the molecules into columns parallel to the b axis.

Related literature

For the syntheses and reactions of some 2-arylnaphth[1,2-d]oxazole derivatives, see: Abbady (1979 ▶). For the syntheses and characterization of phosphorescent cyclometalated iridium complexes, see: Lamansky et al. (2001 ▶).

Experimental

Crystal data

[Ir(C₁₈H₁₂NO₂)₂(C₅H₇O₂)]
M _r = 839.88
Monoclinic,
a = 16.618 (3) Å
b = 11.455 (2) Å
c = 18.993 (4) Å
β = 114.01 (3)°
V = 3302.5 (13) Å³
Z = 4
Mo Kα radiation
μ = 4.10 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T _min = 0.373, T _max = 0.495
40039 measured reflections
7866 independent reflections
7275 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.093
S = 1.04
7866 reflections
452 parameters
H-atom parameters not refined
Δρ_max = 1.19 e Å⁻³
Δρ_min = −0.79 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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 datablock(s) global, I. DOI: 10.1107/S1600536811035690/rz2632sup1.cif

e-67-m1343-sup1.cif^{(32.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811035690/rz2632Isup2.hkl

e-67-m1343-Isup2.hkl^{(384.8KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Ir1—C1	1.997 (4)
Ir1—C19	2.004 (4)
Ir1—N1	2.088 (3)
Ir1—N2	2.109 (3)
Ir1—O6	2.144 (3)
Ir1—O5	2.156 (3)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15A⋯O6	0.93	2.24	3.077 (5)	150
C33—H33A⋯O5	0.93	2.22	3.137 (6)	170
C23—H23A⋯O6ⁱ	0.93	2.54	3.419 (6)	157
C27—H27A⋯O2ⁱⁱ	0.93	2.55	3.206 (6)	128

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

supplementary crystallographic information

Comment

According to the study of Lamansky's group in 2001 (Lamansky et al., 2001), the luminous wavelength of complexes would change as the the conjugated system of (C—N) changed. Therefore, the arylnaphthoxazoles ligand was choosed to regulate luminous wavelength of phosphorescent materials, leading to get better electrophosphorescent materials.

The title complex is a mononuclear iridium(III) complex (Fig. 1), in which the environment around the Ir^III ion is a distorted octahedral coordination geometry, the coordination conformation of the C, N and O atoms of the ligands adopt the cis-, trans- and cis- respectively, which is consistent with the similar reported complexes (Lamansky et al., 2001). It can be illustrated from the figure that the carbon-metal bond is formed between Ir^III ion and the carbon atom on the benzene ring rather than the C atom on the naphthalene ring. It shows from Table 1 that the increase of the bond distance from Ir—C to Ir—N and Ir—O is caused by the increase of the covalent component between the coordination atoms from C to N and O of which the electronegativity decreases gradually. Moreover, there are two five-membered rings formed (Ir1/C1/C6/C7/N1 and Ir1/C19/C24/C25/N2), the average deviation of which are 0.0186 Å and 0.0387 Å, and the dihedral angle they form with their adjacent benzene rings (C1–C6) and (C19–C24) are 3.5 (2)° and 4.9 (3)° respectively. The dihedral angle with their adjacent oxazole heterocycle (N1/O1/C7–17) and (N2/O3/C25–35) are 9.0 (2)° and 8.0 (2)° respectively. The molecular comformation is stabilized by intramolecular C—H···O hydrogen bonds (Table 2). In the crystal structure, intermolecular C—H···O hydrogen bonds (Table 2) link molecules into columns parallel to the b axis.

Experimental

The ligand 2-arylnaphth[1,2-d]oxazole was prepared according to the literature (Abbady, 1979). The ligand (0.61 g, 2.2 mmol) and IrCl₃.3H₂O (0.35 g, 1 mmol) were added to 20 ml 2-ethoxyethanol:H₂O (3:1, v/v) solution under inert gas atmosphere at 393 K for 24 h, and then the intermediate product, acetylacetonate (10 ml) and Na₂CO₃ (1.06 g, 10 mmol) were refluxed for 12 h. After cooling to room temperature, the coloured precipitate was filtered and washed with ethanol and water. The crude product was flash chromatographed using a silica/dichloromethane column to yield ca. 40% of the pure title compound after solvent evaporation and drying.