Crystal structure of bis-[2-tert-but-oxy-6-fluoro-3-(pyridin-2-yl-κN)pyridin-4-yl-κC (4)](pentane-2,4-dionato-κ(2) O,O')iridium(III).

The title mol-ecule, [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 octa-hedral coordination geometry, being C,N-chelated by two 2-tert-but-oxy-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. Intra-molecular C-H⋯O and C-H⋯N hydrogen bonds and inter-molecular C-H⋯F hydrogen bonds as well as π-π inter-actions between neighbouring pyridine rings [centroid-centroid distance 3.680 (1) Å] contribute to the stabilization of the mol-ecular and crystal structure, respectively.

Chemical context

Iridium(III) compounds with fluorinated main dipyridyl ligands have attracted much attention due to then class="Chemical">ir colour purity and high external quantum efficiency in organic light-emitting diodes (Lee et al., 2009 ▶; Park et al., 2013 ▶). In particular, heteroleptic IrIII 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.

Structural commentary

The mol­ecular structure of the title compound, Fig. 1 ▶, is generated by twofold rotation symmetry. The twofold rotation axis passes through the n class="Chemical">IrIII 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 IrIII 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 IrIII 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)°.

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,  − z].

Table 1

Selected bond lengths ()

Ir1C1	1.9760(19)	Ir1O2	2.1393(15)
Ir1N1	2.0344(16)

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 n class="Chemical">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 (, )

DHA	DH	HA	D A	DHA
C7H7O1	0.95	2.27	2.870(2)	120
C10H10O2i	0.95	2.48	3.089(2)	122
C10H10F1ii	0.95	2.41	3.055(2)	125
C12H12CN2	0.98	2.29	2.927(3)	122
C14H14BN2	0.98	2.59	3.153(3)	116

Symmetry codes: (i) ; (ii) .

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.

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.

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 Csp 2 n class="Disease">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 ()	16.9404(12), 10.7783(7), 17.2561(11)
()	100.001(1)
V (3)	3102.9(4)
Z	4
Radiation type	Mo K
(mm1)	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 > 2(I)] reflections	15125, 3881, 3717
R int	0.024
(sin /)max (1)	0.668
Refinement
R[F 2 > 2(F 2)], wR(F 2), S	0.017, 0.039, 1.01
No. of reflections	3881
No. of parameters	200
H-atom treatment	H-atom parameters constrained
max, min (e 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 ▶).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814022934/wm5075sup1.cif

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

CCDC reference: 1029929

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Ir(C14H14FN2O)2(C5H7O2)]	F(000) = 1552
Mr = 781.85	Dx = 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

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

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(Fo2) + (0.0163P)2 + 5.6671P] where P = (Fo2 + 2Fc2)/3
3881 reflections	(Δ/σ)max = 0.001
200 parameters	Δρmax = 0.48 e Å−3
0 restraints	Δρmin = −0.59 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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