Crystal structure of bis­[2-tert-but­oxy-6-fluoro-3-(pyridin-2-yl-κN)pyridin-4-yl-κC4](pentane-2,4-dionato-κ2O,O′)iridium(III)

Park, K.-M.; Kang, Y.

doi:10.1107/S1600536814022934

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 11| November 2014| Pages 427-429

doi:10.1107/S1600536814022934

Open

access

Crystal structure of bis[2-tert-butoxy-6-fluoro-3-(pyridin-2-yl-κN)pyridin-4-yl-κC⁴](pentane-2,4-dionato-κ²O,O′)iridium(III)

Ki-Min Park ^a and Youngjin Kang ^b ^*

^aResearch Institute of Natural Science, Gyeongsang National University, Jinju, 660-701, South Korea, and ^bDivision of Science Education and Department of Chemistry, Kangwon National, University, Chuncheon 220-701, South Korea
^*Correspondence e-mail: kangy@kangwon.ac.kr

Edited by M. Weil, Vienna University of Technology, Austria (Received 6 October 2014; accepted 19 October 2014; online 29 October 2014)

The title molecule, [Ir(C₁₄H₁₄FN₂O)₂(C₅H₇O₂)], is located on a twofold rotation axis, which passes through the Ir^III atom and the central C atom of the pentane-2,4-dionate anion. The Ir^III atom adopts a distorted octahedral coordination geometry, being C,N-chelated by two 2-tert-butoxy-6-fluoro-3-(pyridin-2-yl)pyridin-4-yl ligands and O,O′-chelated by the pentane-2,4-dionato ligand. The bipyridinate ligands, which are perpendicular to each other [dihedral angle between the two least-squares planes = 89.95 (5)°], are arranged in a cis-C,C′ and trans-N,N′ fashion relative to the central metal cation. Intramolecular C—H⋯O and C—H⋯N hydrogen bonds and intermolecular C—H⋯F hydrogen bonds as well as π—π interactions between neighbouring pyridine rings [centroid–centroid distance 3.680 (1) Å] contribute to the stabilization of the molecular and crystal structure, respectively.

Keywords: crystal structure; iridium(III); C₂N₂O₂ coordination set.

CCDC reference: 1029929

1. Chemical context

Iridium(III) compounds with fluorinated main dipyridyl ligands have attracted much attention due to their colour purity and high external quantum efficiency in organic light-emitting diodes (Lee et al., 2009 ; Park et al., 2013 ). In particular, heteroleptic Ir^III compounds have many advantages such as easy tuning of emission energies and photophysical properties by modification of the ancillary ligands (Oh et al., 2013 ). Herein, we report the results of the crystal-structure determination of an iridium(III) compound, [Ir(C₁₄H₁₄FN₂O)₂(C₅H₇O₂)], with acetylacetonate (acac, O,O′) as an ancillary ligand.

2. Structural commentary

The molecular structure of the title compound, Fig. 1, is generated by twofold rotation symmetry. The twofold rotation axis passes through the Ir^III atom and the central C atom (C15) of the acetylacetonate ligand. Therefore, the asymmetric unit consists of one Ir(III) atom on Wyckoff position 4e, one half of the acetylacetonate anion and one 2-tert-butoxy-6-fluoro-3-(pyridin-2-yl)pyridin-4-yl ligand. The Ir^III atom is six-coordinated by the two main C,N-bidentate ligands and one ancillary O,O′-bidentate ligand, forming a distorted octahedral coordination sphere due to the narrow ligand bite angles, which range from 80.36 (7) to 88.65 (8)°. The C,N-bidentate ligands, which are perpendicular to each other [dihedral angle between the least-squares planes = 89.95 (5)°], are arranged in a cis-C,C′ and trans-N,N′ fashion. The Ir—C bond length of 1.9760 (19) Å is shorter than the Ir—N bond length of 2.0344 (16) Å due to the electronegative fluorine substituent (Table 1). The Ir—C, Ir—N, and Ir—O bond lengths are in normal ranges as reported for similar Ir^III compounds, e.g. [Ir(dfpypy)₂(acac); dfpypy is a difuorinated bipyridine] (Kang et al., 2013 ) or Ir(2′,6′-bis(2-methoxyethoxy)-2,3′-bipyridinato-N,C′)(picolinate) (Frey et al., 2014 ). Within the C,N-bidentate ligand of the title compound, the two pyridine rings are approximately co-planar, with a dihedral angle between the rings of 5.77 (9)°.

Table 1
Selected bond lengths (Å)

Ir1—C1	1.9760 (19)	Ir1—O2	2.1393 (15)
Ir1—N1	2.0344 (16)

Figure 1
View of the molecular structure of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level; dashed lines represent intramolecular C—H⋯O and C—H⋯N hydrogen bonds [Symmetry code: (i) − x, y, $[{3\over 2}]$ − z].

3. Supramolecular features

The molecular structure is stabilized by weak intramolecular C—H⋯O and C—H⋯N hydrogen bonds (Table 2). Intermolecular C—H⋯F hydrogen bonds and π—π interactions [Cg1—Cg1ⁱⁱⁱ = 3.680 (1) Å, Cg1 is the centroid of the N1, C6–C10 ring, symmetry code: (iii) −x, 1 − y, 2 − z] contribute to the stabilization of the crystal structure (Fig. 2).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O1	0.95	2.27	2.870 (2)	120
C10—H10⋯O2ⁱ	0.95	2.48	3.089 (2)	122
C10—H10⋯F1ⁱⁱ	0.95	2.41	3.055 (2)	125
C12—H12C⋯N2	0.98	2.29	2.927 (3)	122
C14—H14B⋯N2	0.98	2.59	3.153 (3)	116
Symmetry codes: (i) $[-x, y, -z+{\script{3\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Figure 2
Packing plot of the molecular components in the title compound. Yellow and black dashed lines represent intermolecular C—H⋯F and π–π stacking interactions, respectively. H atoms not involved in intermolecular interactions have been omitted for clarity.

4. Synthesis and crystallization

The title compound was synthesized according to a previous report (Oh et al., 2013). Yellow single crystals were obtained by slow evaporation from a dichloromethane/hexane solution.

5. Refinement

Crystal data, data collection and crystal structure refinement details are summarized in Table 3. All H atoms were positioned geometrically and refined using a riding model, with d(C—H) = 0.95 Å, U_iso(H) = 1.2U_eq(C) for Csp² H atoms, and 0.98 Å, U_iso(H) = 1.5U_eq(C) for methyl protons.

Table 3
Experimental details

Crystal data
Chemical formula	[Ir(C₁₄H₁₄FN₂O)₂(C₅H₇O₂)]
M_r	781.85
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	173
a, b, c (Å)	16.9404 (12), 10.7783 (7), 17.2561 (11)
β (°)	100.001 (1)
V (Å³)	3102.9 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	4.36
Crystal size (mm)	0.16 × 0.12 × 0.09

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996 )
T_min, T_max	0.537, 0.687
No. of measured, independent and observed [I > 2σ(I)] reflections	15125, 3881, 3717
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.017, 0.039, 1.01
No. of reflections	3881
No. of parameters	200
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.59
Computer programs: APEX2 and SAINT (Bruker, 2006 ), SHELXS97, SHELXL97 and SHELXTL (Sheldrick, 2008 ), DIAMOND (Brandenburg, 2005 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1029929

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814022934/wm5075sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814022934/wm5075Isup2.hkl

checkCIF report

Chemical context top

Iridium(III) compounds with fluorinated main dipyridyl ligands have attracted much attention due to their colour purity and high external quantum efficiency in organic light-emitting diodes (Lee et al., 2009; Park et al., 2013). In particular, heteroleptic Ir^III compounds have many advantages such as easy tuning of emission energies and photophysical properties by modification of the ancillary ligands (Oh et al., 2013). Herein, we report the results of the crystal-structure determination of an iridium(III) compound with acetylacetate (acac, O,O') as an ancillary ligand, [Ir(C₁₄H₁₄FN₂O)₂(C₅H₇O₂)].

Structural commentary top

\ The molecular structure of the title compound, Fig. 1, is generated by twofold rotation symmetry. The twofold rotation axis passes through the Ir^III atom and the central C atom (C15) of the acetylacetonate ligand. Therefore, the asymmetric unit consists of one Ir(III) atom on Wyckoff position 4e, one half of the acetylacetonate (acac) anion and one 2-tert-butoxy-6-fluoro-3-(pyridin-2-yl)pyridine-4-yl ligand. The Ir^III atom is six-coordinated by the two main C,N-bidentate ligands and one ancillary O,O'-bidentate ligand, forming a distorted octahedral coordination sphere due to the narrow ligand bite angles, which range from 80.36 (7) to 88.65 (8)°. The C,N-bidentate ligands, which are perpendicular to each other [dihedral angle between the least-squares planes = 89.95 (5)°], are arranged in a cis-C,C' and trans-N,N' fashion. The Ir—C bond length of 1.9760 (19) Å is shorter than the Ir—N bond length of 2.0344 (16) Å due to the electronegative fluorine substituent (Table 1). The Ir—C, Ir—N, and Ir—O bond lengths are in normal ranges as reported for similar Ir^III compounds, e.g. [Ir(dfpypy)₂(acac); dfpypy is a difuorinated bipyridine] (Kang et al., 2013) or Ir(2',6'-bis(2-methoxyethoxy)-2,3'-bipyridinato-N,C')\ (picolinate) (Frey et al., 2014). Within the C,N-bidentate ligand of the title compound, the two pyridine rings are approximately co-planar, with a dihedral angle between the rings of 5.77 (9)°.

Supramolecular features top

The molecular structure is stabilized by weak intramolecular C—H···O and C—H···N hydrogen bonds (Table 2). Intermolecular C—H···F hydrogen bonds and π—π interactions [Cg1—Cg1ⁱⁱⁱ = 3.680 (1) Å, Cg1 is the centroid of the N1, C6–C10 ring, symmetry code: (iii) -x, 1 - y, 2 - z] contribute to the stabilization of the crystal structure (Fig. 2).

Synthesis and crystallization top

The title compound was synthesized according to a previous report (Oh et al., 2013). Yellow single crystals were obtained by slow evaporation from a dichloromethane/hexane solution.

Refinement top

Related literature top

For related literature, see: Frey et al. (2014); Kang et al. (2013); Lee et al. (2009); Oh et al. (2013); Park et al. (2013).

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top

View of the molecular structure of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level; dashed lines represent intramolecular C—H···O and C—H···N hydrogen bonds [Symmetry code: (i) - x, y, 3/2 - z].

Packing plot of the molecular components in the title compound. Yellow and black dashed lines represent intermolecular C—H···F and π–π stacking interactions, respectively. H atoms not involved in intermolecular interactions have been omitted for clarity.

Bis[2-tert-butoxy-6-fluoro-3-(pyridin-2-yl-κN)pyridin-4-yl-κC⁴](pentane-2,4-dionato-κ²O,O')iridium(III) top

Crystal data top

[Ir(C₁₄H₁₄FN₂O)₂(C₅H₇O₂)]	F(000) = 1552
M_r = 781.85	D_x = 1.674 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3721 reflections
a = 16.9404 (12) Å	θ = 2.3–28.3°
b = 10.7783 (7) Å	µ = 4.36 mm⁻¹
c = 17.2561 (11) Å	T = 173 K
β = 100.001 (1)°	Block, yellow
V = 3102.9 (4) Å³	0.16 × 0.12 × 0.09 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	3881 independent reflections
Radiation source: fine-focus sealed tube	3717 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −22→21
T_min = 0.537, T_max = 0.687	k = −14→14
15125 measured reflections	l = −15→23

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.017	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.039	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0163P)² + 5.6671P] where P = (F_o² + 2F_c²)/3
3881 reflections	(Δ/σ)_max = 0.001
200 parameters	Δρ_max = 0.48 e Å⁻³
0 restraints	Δρ_min = −0.59 e Å⁻³

Crystal data top

[Ir(C₁₄H₁₄FN₂O)₂(C₅H₇O₂)]	V = 3102.9 (4) Å³
M_r = 781.85	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 16.9404 (12) Å	µ = 4.36 mm⁻¹
b = 10.7783 (7) Å	T = 173 K
c = 17.2561 (11) Å	0.16 × 0.12 × 0.09 mm
β = 100.001 (1)°

Data collection top

Bruker APEXII CCD diffractometer	3881 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3717 reflections with I > 2σ(I)
T_min = 0.537, T_max = 0.687	R_int = 0.024
15125 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.017	0 restraints
wR(F²) = 0.039	H-atom parameters constrained
S = 1.01	Δρ_max = 0.48 e Å⁻³
3881 reflections	Δρ_min = −0.59 e Å⁻³
200 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ir1	0.0000	0.424606 (10)	0.7500	0.01166 (4)
F1	0.22407 (8)	0.06652 (13)	0.79551 (8)	0.0273 (3)
O1	0.08930 (9)	0.14456 (15)	0.99685 (8)	0.0214 (3)
N1	−0.04307 (9)	0.41821 (15)	0.85288 (10)	0.0135 (3)
N2	0.15918 (10)	0.10711 (16)	0.89537 (10)	0.0180 (4)
C1	0.06958 (11)	0.29314 (18)	0.80481 (11)	0.0126 (4)
C2	0.12693 (11)	0.2228 (2)	0.77450 (12)	0.0169 (4)
H2	0.1371	0.2354	0.7226	0.020*
C3	0.16737 (11)	0.1357 (2)	0.82308 (12)	0.0180 (4)
C4	0.10416 (11)	0.17160 (19)	0.92486 (12)	0.0162 (4)
C5	0.05807 (10)	0.26689 (18)	0.88253 (11)	0.0127 (4)
C6	−0.00488 (11)	0.33982 (18)	0.90962 (11)	0.0129 (4)
C7	−0.02889 (12)	0.33774 (19)	0.98317 (11)	0.0160 (4)
H7	−0.0015	0.2861	1.0237	0.019*
C8	−0.09224 (12)	0.41045 (19)	0.99727 (12)	0.0190 (4)
H8	−0.1080	0.4099	1.0475	0.023*
C9	−0.13243 (12)	0.4840 (2)	0.93726 (12)	0.0205 (4)
H9	−0.1776	0.5317	0.9449	0.025*
C10	−0.10572 (12)	0.4864 (2)	0.86643 (12)	0.0179 (4)
H10	−0.1325	0.5382	0.8256	0.021*
C11	0.13969 (13)	0.06280 (19)	1.05388 (12)	0.0189 (4)
C12	0.14509 (17)	−0.0675 (2)	1.02218 (16)	0.0335 (6)
H12A	0.0912	−0.1032	1.0093	0.050*
H12B	0.1781	−0.1189	1.0621	0.050*
H12C	0.1695	−0.0647	0.9747	0.050*
C13	0.09314 (16)	0.0622 (3)	1.12145 (15)	0.0358 (6)
H13A	0.0397	0.0271	1.1035	0.054*
H13B	0.0879	0.1474	1.1398	0.054*
H13C	0.1217	0.0118	1.1647	0.054*
C14	0.22125 (14)	0.1217 (3)	1.07830 (14)	0.0307 (5)
H14A	0.2148	0.2057	1.0979	0.046*
H14B	0.2487	0.1256	1.0329	0.046*
H14C	0.2530	0.0718	1.1199	0.046*
O2	0.08159 (9)	0.56660 (14)	0.79971 (9)	0.0209 (3)
C15	0.0000	0.7398 (3)	0.7500	0.0318 (8)
H15	0.0000	0.8280	0.7500	0.038*
C16	0.06984 (15)	0.6828 (2)	0.78927 (13)	0.0244 (5)
C17	0.14050 (18)	0.7636 (3)	0.82222 (15)	0.0390 (6)
H17A	0.1846	0.7114	0.8482	0.059*
H17B	0.1248	0.8218	0.8605	0.059*
H17C	0.1579	0.8100	0.7794	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ir1	0.01340 (5)	0.01297 (5)	0.00844 (5)	0.000	0.00137 (4)	0.000
F1	0.0230 (6)	0.0369 (8)	0.0223 (7)	0.0164 (6)	0.0047 (5)	−0.0021 (6)
O1	0.0240 (7)	0.0250 (8)	0.0158 (7)	0.0097 (6)	0.0052 (6)	0.0096 (6)
N1	0.0140 (7)	0.0146 (8)	0.0117 (8)	−0.0011 (6)	0.0017 (6)	−0.0012 (6)
N2	0.0173 (8)	0.0188 (9)	0.0170 (9)	0.0019 (7)	0.0003 (7)	−0.0005 (7)
C1	0.0107 (8)	0.0140 (9)	0.0120 (9)	−0.0023 (7)	−0.0014 (7)	−0.0026 (7)
C2	0.0151 (9)	0.0228 (10)	0.0126 (9)	0.0011 (8)	0.0019 (7)	−0.0020 (8)
C3	0.0133 (9)	0.0212 (11)	0.0188 (10)	0.0029 (8)	0.0009 (7)	−0.0048 (8)
C4	0.0159 (9)	0.0172 (10)	0.0146 (10)	−0.0018 (8)	0.0003 (7)	0.0007 (8)
C5	0.0118 (8)	0.0147 (9)	0.0112 (9)	−0.0015 (7)	0.0007 (7)	−0.0005 (7)
C6	0.0138 (8)	0.0123 (9)	0.0119 (9)	−0.0018 (7)	0.0001 (7)	−0.0003 (7)
C7	0.0190 (9)	0.0161 (10)	0.0128 (10)	−0.0001 (8)	0.0028 (7)	0.0020 (8)
C8	0.0219 (10)	0.0219 (11)	0.0147 (10)	−0.0009 (8)	0.0072 (8)	−0.0003 (8)
C9	0.0199 (10)	0.0243 (11)	0.0188 (10)	0.0061 (9)	0.0072 (8)	−0.0002 (9)
C10	0.0183 (9)	0.0204 (10)	0.0151 (10)	0.0046 (8)	0.0033 (8)	0.0023 (8)
C11	0.0226 (10)	0.0180 (10)	0.0143 (10)	0.0030 (8)	−0.0018 (8)	0.0062 (8)
C12	0.0483 (15)	0.0170 (11)	0.0309 (14)	−0.0015 (11)	−0.0051 (11)	0.0037 (10)
C13	0.0379 (14)	0.0486 (17)	0.0223 (12)	0.0122 (12)	0.0091 (10)	0.0177 (11)
C14	0.0304 (12)	0.0350 (13)	0.0236 (12)	−0.0092 (11)	−0.0041 (10)	−0.0018 (10)
O2	0.0287 (8)	0.0202 (8)	0.0137 (7)	−0.0078 (6)	0.0034 (6)	−0.0029 (6)
C15	0.055 (2)	0.0143 (15)	0.0311 (19)	0.000	0.0203 (16)	0.000
C16	0.0433 (13)	0.0193 (11)	0.0147 (10)	−0.0088 (10)	0.0161 (9)	−0.0042 (8)
C17	0.0612 (17)	0.0295 (14)	0.0271 (14)	−0.0228 (13)	0.0095 (12)	−0.0064 (11)

Geometric parameters (Å, º) top

Ir1—C1ⁱ	1.9760 (19)	C9—C10	1.375 (3)
Ir1—C1	1.9760 (19)	C9—H9	0.9500
Ir1—N1ⁱ	2.0344 (16)	C10—H10	0.9500
Ir1—N1	2.0344 (16)	C11—C14	1.512 (3)
Ir1—O2	2.1393 (15)	C11—C12	1.516 (3)
Ir1—O2ⁱ	2.1393 (14)	C11—C13	1.517 (3)
F1—C3	1.365 (2)	C12—H12A	0.9800
O1—C4	1.342 (2)	C12—H12B	0.9800
O1—C11	1.477 (2)	C12—H12C	0.9800
N1—C10	1.345 (3)	C13—H13A	0.9800
N1—C6	1.368 (2)	C13—H13B	0.9800
N2—C3	1.315 (3)	C13—H13C	0.9800
N2—C4	1.333 (3)	C14—H14A	0.9800
C1—C2	1.403 (3)	C14—H14B	0.9800
C1—C5	1.417 (3)	C14—H14C	0.9800
C2—C3	1.362 (3)	O2—C16	1.276 (3)
C2—H2	0.9500	C15—C16	1.400 (3)
C4—C5	1.414 (3)	C15—C16ⁱ	1.400 (3)
C5—C6	1.465 (3)	C15—H15	0.9500
C6—C7	1.399 (3)	C16—C17	1.509 (3)
C7—C8	1.384 (3)	C17—H17A	0.9800
C7—H7	0.9500	C17—H17B	0.9800
C8—C9	1.385 (3)	C17—H17C	0.9800
C8—H8	0.9500

C1ⁱ—Ir1—C1	88.37 (10)	C10—C9—C8	118.72 (19)
C1ⁱ—Ir1—N1ⁱ	80.36 (7)	C10—C9—H9	120.6
C1—Ir1—N1ⁱ	96.83 (7)	C8—C9—H9	120.6
C1ⁱ—Ir1—N1	96.83 (7)	N1—C10—C9	122.37 (19)
C1—Ir1—N1	80.36 (7)	N1—C10—H10	118.8
N1ⁱ—Ir1—N1	176.12 (9)	C9—C10—H10	118.8
C1ⁱ—Ir1—O2	174.32 (7)	O1—C11—C14	109.26 (17)
C1—Ir1—O2	91.77 (7)	O1—C11—C12	112.12 (18)
N1ⁱ—Ir1—O2	93.98 (6)	C14—C11—C12	112.3 (2)
N1—Ir1—O2	88.80 (6)	O1—C11—C13	101.36 (17)
C1ⁱ—Ir1—O2ⁱ	91.77 (7)	C14—C11—C13	111.1 (2)
C1—Ir1—O2ⁱ	174.32 (7)	C12—C11—C13	110.2 (2)
N1ⁱ—Ir1—O2ⁱ	88.80 (6)	C11—C12—H12A	109.5
N1—Ir1—O2ⁱ	93.98 (6)	C11—C12—H12B	109.5
O2—Ir1—O2ⁱ	88.65 (8)	H12A—C12—H12B	109.5
C4—O1—C11	124.52 (16)	C11—C12—H12C	109.5
C10—N1—C6	120.19 (17)	H12A—C12—H12C	109.5
C10—N1—Ir1	123.15 (14)	H12B—C12—H12C	109.5
C6—N1—Ir1	116.67 (12)	C11—C13—H13A	109.5
C3—N2—C4	115.84 (18)	C11—C13—H13B	109.5
C2—C1—C5	117.59 (18)	H13A—C13—H13B	109.5
C2—C1—Ir1	127.09 (15)	C11—C13—H13C	109.5
C5—C1—Ir1	115.31 (13)	H13A—C13—H13C	109.5
C3—C2—C1	116.74 (18)	H13B—C13—H13C	109.5
C3—C2—H2	121.6	C11—C14—H14A	109.5
C1—C2—H2	121.6	C11—C14—H14B	109.5
N2—C3—C2	128.36 (19)	H14A—C14—H14B	109.5
N2—C3—F1	113.52 (18)	C11—C14—H14C	109.5
C2—C3—F1	118.12 (18)	H14A—C14—H14C	109.5
N2—C4—O1	119.76 (18)	H14B—C14—H14C	109.5
N2—C4—C5	122.80 (18)	C16—O2—Ir1	124.86 (15)
O1—C4—C5	117.42 (17)	C16—C15—C16ⁱ	127.9 (3)
C4—C5—C1	118.65 (17)	C16—C15—H15	116.1
C4—C5—C6	126.30 (17)	C16ⁱ—C15—H15	116.1
C1—C5—C6	114.98 (17)	O2—C16—C15	126.7 (2)
N1—C6—C7	118.92 (17)	O2—C16—C17	114.8 (2)
N1—C6—C5	112.52 (16)	C15—C16—C17	118.5 (2)
C7—C6—C5	128.56 (17)	C16—C17—H17A	109.5
C8—C7—C6	120.46 (18)	C16—C17—H17B	109.5
C8—C7—H7	119.8	H17A—C17—H17B	109.5
C6—C7—H7	119.8	C16—C17—H17C	109.5
C7—C8—C9	119.21 (19)	H17A—C17—H17C	109.5
C7—C8—H8	120.4	H17B—C17—H17C	109.5
C9—C8—H8	120.4

C1ⁱ—Ir1—N1—C10	−89.11 (17)	C2—C1—C5—C4	−0.4 (3)
C1—Ir1—N1—C10	−176.28 (17)	Ir1—C1—C5—C4	178.33 (14)
O2—Ir1—N1—C10	91.72 (16)	C2—C1—C5—C6	−177.59 (17)
O2ⁱ—Ir1—N1—C10	3.15 (16)	Ir1—C1—C5—C6	1.2 (2)
C1ⁱ—Ir1—N1—C6	90.96 (14)	C10—N1—C6—C7	−3.9 (3)
C1—Ir1—N1—C6	3.79 (14)	Ir1—N1—C6—C7	176.01 (14)
O2—Ir1—N1—C6	−88.21 (14)	C10—N1—C6—C5	175.95 (17)
O2ⁱ—Ir1—N1—C6	−176.77 (14)	Ir1—N1—C6—C5	−4.1 (2)
C1ⁱ—Ir1—C1—C2	78.83 (17)	C4—C5—C6—N1	−175.00 (18)
N1ⁱ—Ir1—C1—C2	−1.26 (18)	C1—C5—C6—N1	1.9 (2)
N1—Ir1—C1—C2	176.04 (18)	C4—C5—C6—C7	4.9 (3)
O2—Ir1—C1—C2	−95.48 (17)	C1—C5—C6—C7	−178.21 (19)
C1ⁱ—Ir1—C1—C5	−99.77 (15)	N1—C6—C7—C8	2.4 (3)
N1ⁱ—Ir1—C1—C5	−179.86 (14)	C5—C6—C7—C8	−177.44 (19)
N1—Ir1—C1—C5	−2.56 (13)	C6—C7—C8—C9	1.0 (3)
O2—Ir1—C1—C5	85.92 (14)	C7—C8—C9—C10	−2.8 (3)
C5—C1—C2—C3	−0.6 (3)	C6—N1—C10—C9	2.1 (3)
Ir1—C1—C2—C3	−179.21 (15)	Ir1—N1—C10—C9	−177.85 (16)
C4—N2—C3—C2	0.1 (3)	C8—C9—C10—N1	1.4 (3)
C4—N2—C3—F1	−179.61 (17)	C4—O1—C11—C14	65.0 (3)
C1—C2—C3—N2	0.9 (3)	C4—O1—C11—C12	−60.2 (3)
C1—C2—C3—F1	−179.45 (17)	C4—O1—C11—C13	−177.8 (2)
C3—N2—C4—O1	176.95 (18)	C1—Ir1—O2—C16	−177.15 (16)
C3—N2—C4—C5	−1.3 (3)	N1ⁱ—Ir1—O2—C16	85.88 (16)
C11—O1—C4—N2	11.9 (3)	N1—Ir1—O2—C16	−96.84 (16)
C11—O1—C4—C5	−169.79 (18)	O2ⁱ—Ir1—O2—C16	−2.82 (13)
N2—C4—C5—C1	1.4 (3)	Ir1—O2—C16—C15	6.0 (3)
O1—C4—C5—C1	−176.82 (17)	Ir1—O2—C16—C17	−172.81 (14)
N2—C4—C5—C6	178.27 (18)	C16ⁱ—C15—C16—O2	−3.43 (16)
O1—C4—C5—C6	0.0 (3)	C16ⁱ—C15—C16—C17	175.3 (2)

Symmetry code: (i) −x, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1	0.95	2.27	2.870 (2)	120
C10—H10···O2ⁱ	0.95	2.48	3.089 (2)	122
C10—H10···F1ⁱⁱ	0.95	2.41	3.055 (2)	125
C12—H12C···N2	0.98	2.29	2.927 (3)	122
C14—H14B···N2	0.98	2.59	3.153 (3)	116

Symmetry codes: (i) −x, y, −z+3/2; (ii) x−1/2, y+1/2, z.

Selected bond lengths (Å) top

Ir1—C1	1.9760 (19)	Ir1—O2	2.1393 (15)
Ir1—N1	2.0344 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1	0.95	2.27	2.870 (2)	120.3
C10—H10···O2ⁱ	0.95	2.48	3.089 (2)	121.7
C10—H10···F1ⁱⁱ	0.95	2.41	3.055 (2)	124.5
C12—H12C···N2	0.98	2.29	2.927 (3)	121.7
C14—H14B···N2	0.98	2.59	3.153 (3)	116.4

Symmetry codes: (i) −x, y, −z+3/2; (ii) x−1/2, y+1/2, z.

Experimental details

Crystal data
Chemical formula	[Ir(C₁₄H₁₄FN₂O)₂(C₅H₇O₂)]
M_r	781.85
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	173
a, b, c (Å)	16.9404 (12), 10.7783 (7), 17.2561 (11)
β (°)	100.001 (1)
V (Å³)	3102.9 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.36
Crystal size (mm)	0.16 × 0.12 × 0.09

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.537, 0.687
No. of measured, independent and observed [I > 2σ(I)] reflections	15125, 3881, 3717
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.017, 0.039, 1.01
No. of reflections	3881
No. of parameters	200
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.59

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2005), SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Acknowledgements

This work was supported by the Industrial Strategic Technology Development Program (10039141) funded by MOTIE (Ministry of Trade, Industry & Energy, Korea) and KEIT (Korea Evaluation Institute of Industrial Technology).

References

Brandenburg, K. (2005). DIAMOND. Crystal Impact GbR, Germany. Google Scholar
Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Frey, J., Curchod, B. F. E., Scopelliti, R., Tavernelli, I., Rothlisberger, U., Nazeeruddin, M. K. & Baranoff, E. (2014). Dalton Trans. 43, 5667–5679. Web of Science CSD CrossRef CAS PubMed Google Scholar
Kang, Y., Chang, Y.-L., Lu, J.-S., Ko, S.-B., Rao, Y., Varlan, M., Lu, Z.-H. & Wang, S. (2013). J. Mater. Chem. C, 1, 441–450. Web of Science CSD CrossRef CAS Google Scholar
Lee, S. J., Park, K.-M., Yang, K. & Kang, Y. (2009). Inorg. Chem. 48, 1030–1037. Web of Science CSD CrossRef PubMed CAS Google Scholar
Oh, H., Park, K.-M., Hwang, H., Oh, S., Lee, J. H., Lu, J.-S., Wang, S. & Kang, Y. (2013). Organometallics, 32, 6427–6436. Web of Science CSD CrossRef CAS Google Scholar
Park, J., Oh, H., Oh, S., Kim, J., Park, H. J., Kim, O. Y., Lee, J. Y. & Kang, Y. (2013). Org. Electron. 14, 3228–3233. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 11| November 2014| Pages 427-429

doi:10.1107/S1600536814022934

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)