mer-[3-Phenyl-5-(2-pyridyl-κN)-1,2,4-triazol-1-ido-κN1]bis­(2-quinolylphenyl-κ2C1,N)iridium(III) deuterochloro­form disolvate

Jones, P.G.; Freund, A.; Debeaux, M.; Kowalsky, W.; Johannes, H.-H.

doi:10.1107/S1600536810038596

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Pages m1408-m1409

https://doi.org/10.1107/S1600536810038596

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mer-[3-Phenyl-5-(2-pyridyl-κN)-1,2,4-triazol-1-ido-κN¹]bis(2-quinolylphenyl-κ²C¹,N)iridium(III) deuterochloroform disolvate

Peter G. Jones,^a ^* Andreas Freund,^b Marc Debeaux,^b Wolfgang Kowalsky ^b and Hans-Hermann Johannes ^b

^aInstitut für Anorganische und Analytische Chemie, Technical University of Braunschweig, Postfach 3329, 38023 Braunschweig, Germany, and ^bLabor für Elektrooptik am Institut für Hochfrequenztechnik, Technical University of Braunschweig, Postfach 3329, 38023 Braunschweig, Germany
^*Correspondence e-mail: p.jones@tu-bs.de

(Received 24 September 2010; accepted 27 September 2010; online 13 October 2010)

In the title compound, [Ir(C₁₃H₉N₄)(C₁₅H₁₀N)₂]·2CDCl₃, the coordination at iridium is octahedral, but with narrow ligand bite angles ranging from 74.85 (8) to 83.99 (8)°. The bond lengths at iridium show the expected trans influence, with Ir—N trans to C being appreciably longer than trans to N. The chelate rings are mutually perpendicular to a reasonable approximation [interplanar angles ranging from 77.79 (6) to 83.93 (7)°]. All ligands are approximately planar; the maximum interplanar angles within ligands are ca 12°. One CDCl₃ solvent molecule is severly disordered and was excluded from the refinement.

Related literature

For the preparation of iridium complexes, see: Lamansky et al. (2001 ); Coppo et al. (2004 ). For the photoluminescent properties and color tuning of cyclometalated iridium complexes, see: Grushin et al. (2001 ); You & Park (2005 ); Stagni et al. (2008 ). For general background to organic light-emitting diodes (OLEDs), see: Hertel et al. (2005 ); Holder et al. (2005 ). For two recent related publications from our groups, see: Jones et al. (2010a ,b ).

Experimental

Crystal data

[Ir(C₁₃H₉N₄)(C₁₅H₁₀N)₂]·2CDCl₃
M_r = 1062.67
Triclinic, $[P \overline 1]$
a = 9.1399 (3) Å
b = 12.4430 (5) Å
c = 17.6762 (6) Å
α = 81.493 (4)°
β = 81.509 (4)°
γ = 85.193 (4)°
V = 1962.41 (12) Å³
Z = 2
Mo Kα radiation
μ = 3.86 mm⁻¹
T = 100 K
0.25 × 0.20 × 0.05 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Limited, Yarnton, England.]$ ) T_min = 0.739, T_max = 1.000
78670 measured reflections
9739 independent reflections
8125 reflections with I > 2σ(I)
R_int = 0.062

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.048
S = 0.93
9739 reflections
487 parameters
134 restraints
H-atom parameters constrained
Δρ_max = 1.03 e Å⁻³
Δρ_min = −1.08 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Limited, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Siemens, 1994 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810038596/bt5363sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810038596/bt5363Isup2.hkl

checkCIF report

Comment top

Electrophosphorescent materials based on iridium(III) have been one of the most important developments in the field of organic light-emitting diodes (OLEDs) because both singlet and triplet excitons can be harvested for light emission, giving OLEDs with theoretically 100% internal quantum efficiencies. Furthermore, iridium(III) complexes possess relatively short excited state lifetimes, high quantum efficiencies and remarkable colour tuning by modification of the ligand structures. The simple method of tuning the emission colour is to vary the combination of cyclometallating and ancillary ligands (e.g. acetylacetonate, picolinate or triazolate derivatives) coordinated to the iridium core. These heteroleptic complexes are particularly interesting as emitters for OLED applications. Quinoline-based iridium(III) complexes have proved to be especially efficient materials for red OLEDs. In this regard, we have synthesized and characterized the title compound, a new iridium(III) complex with 2-phenylquinoline as chromophoric ligands and 3-phenyl-5-(2-pyridyl)-1,2,4-triazole as ancillary ligand, and report here its crystal structure.

The structure of the title complex is shown in Fig. 1. It crystallizes with two molecules of deuterochloroform, one of which is severely disordered (see refinement details). The general features of the complex are similar to those of our other recent related structures (Jones et al., 2010a,b). The coordination at iridium is octahedral, whereby the major deviations in angles arise from the restricted bite of the chelating ligands: N1—Ir—C12 79.82 (10), N17—Ir—C28 79.82 (12), N33—Ir—N39 74.85 (8)°. The bond lengths at iridium show the expected trans influence, with Ir—N33 and Ir—N39, 2.129 (2) and 2.196 (2) Å respectively, trans to C being appreciably longer than the mutually trans Ir—N1 2.084 (2) and Ir—N17 2.093 (2) Å. The interplanar angles between the chelate rings amount to 78.8 (1)° from the IrN₂C₂ ring to both IrNC₃ rings, and 83.9 (1)° between the latter. Within the ligands, the interplanar angles between phenyl and quinoline are 11.8 (1) and 12.3 (1)°, whereas in the triazole ligand the pyridyl and phenyl rings subtend angles of 1.8 (1) and 11.0 (1)° respectively to the triazole ring.

Related literature top

For the preparation of iridium complexes, see: Lamansky et al. (2001); Coppo et al. (2004). For the photoluminescent properties and color tuning of cyclometalated iridium complexes, see: Grushin et al. (2001); You & Park (2005); Stagni et al. (2008). For general background to organic light-emitting diodes (OLEDs), see: Hertel et al. (2005); Holder et al. (2005). For two recent related publications from our groups, see: Jones et al. (2010a,b).

Experimental top

A mixture of bis(2-phenylquinoline)-iridium(III)-µ-chloro bridged dimer complex (230 mg, 180 µmol), 3-phenyl-5-(2-pyridyl)-1,2,4-triazole (100 mg, 450 µmol) and potassium tert-butoxide (50 mg, 450 µmol) in dry dichloromethane (10 ml) and dry ethanol (3 ml) was stirred overnight at room temperature under nitrogen atmosphere. The solvent was removed under reduced pressure and the residue was purified via flash chromatography on silica gel (eluent: dichloromethane/acetone = 20:1, R_f = 0.31) to yield a red solid (115 mg, 39%). m.p. 326 °C.

¹H NMR (CDCl₃, 600 MHz): δ 8.13 (d, J = 9.0 Hz, 1H), 8.04–8.00 (m, 3H), 7.93–7.86 (m, 6H), 7.77 (d, J = 7.7 Hz, 1H), 7.52–7.47 (m, 3H), 7.29 (d, J = 8.9 Hz, 1H), 7.23 (dd, J = 7.6, 7.6 Hz, 2H), 7.18–7.14 (m, 2H), 7.11 (ddd, J = 7.9, 6.9, 1.0 Hz, 1H), 7.07–7.03 (m, 2H), 7.01 (dd, J = 7.3, 7.3 Hz, 1H), 6.95 (ddd, J = 7.2, 5.7, 1.3 Hz, 1H), 6.78–6.74 (m, 3H), 6.67 (dd, J = 7.0, 7.0 Hz, 1H), 6.46 (d, J = 7.5 Hz, 1H) p.p.m..

¹³C NMR (CDCl₃, 150 MHz): δ 170.95, 170.01, 164.55, 162.54, 156.82, 151.88, 149.90, 148.24, 147.54, 146.98, 146.73, 146.61, 138.78, 138.31, 137.61, 136.01, 134.22, 133.17, 131.33, 130.06, 129.57, 129.47, 128.48, 128.14, 127.87, 127.49, 127.46, 127.26, 127.14, 126.53, 126.21, 126.05, 125.98, 125.54, 125.48, 123.23, 121.76, 121.65, 120.71, 116.99, 116.54 p.p.m..

EI—MS: m/z (%) = 822 (28) [M]^+., 601 (46) [M–C13H9N4]^+., 470 (4), 205 (100).

IR: = 3045 (w), 1604 (s), 1579 (m), 1544 (m), 1513 (m), 1460 (m), 1447 (m), 1421 (m), 1335 (m), 1288 (m), 1275 (m), 1242 (w), 1146 (m), 1070 (w), 1026 (m), 828 (m), 789 (m), 760 (versus), 724 (s), 695 (s), 640 (w), 569 (w), 539 (w) cm^-1.

UV/Vis (CH₂Cl₂): λ (ε) = 446 (br. 4500), 337 (23600), 269 (58500), 227 (40300) nm.

Single crystals were obtained by evaporation from CDCl₃ in an NMR tube.

Structure description top

For the preparation of iridium complexes, see: Lamansky et al. (2001); Coppo et al. (2004). For the photoluminescent properties and color tuning of cyclometalated iridium complexes, see: Grushin et al. (2001); You & Park (2005); Stagni et al. (2008). For general background to organic light-emitting diodes (OLEDs), see: Hertel et al. (2005); Holder et al. (2005). For two recent related publications from our groups, see: Jones et al. (2010a,b).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

Fig. 1. Structure of the title compound in the crystal. Ellipsoids represent 50% probability levels. Solvent molecules and hydrogen atoms are omitted for clarity.

mer-[3-Phenyl-5-(2-pyridyl-κN)-1,2,4-triazol-1-ido- κN¹]bis(2-quinolylphenyl-κ²C¹,N)iridium(III) deuterochloroform disolvate top

Crystal data top

[Ir(C₁₃H₉N₄)(C₁₅H₁₀N)₂]·2CDCl₃	Z = 2
M_r = 1062.67	F(000) = 1044
Triclinic, P1	D_x = 1.798 Mg m⁻³
a = 9.1399 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.4430 (5) Å	Cell parameters from 26610 reflections
c = 17.6762 (6) Å	θ = 2.2–30.8°
α = 81.493 (4)°	µ = 3.86 mm⁻¹
β = 81.509 (4)°	T = 100 K
γ = 85.193 (4)°	Tablet, orange
V = 1962.41 (12) Å³	0.25 × 0.20 × 0.05 mm

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	9739 independent reflections
Radiation source: Enhance (Mo) X-ray Source	8125 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.062
Detector resolution: 16.1419 pixels mm^-1	θ_max = 28.3°, θ_min = 2.2°
ω–scan	h = −12→12
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −16→16
T_min = 0.739, T_max = 1.000	l = −23→23
78670 measured reflections

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.048	H-atom parameters constrained
S = 0.93	w = 1/[σ²(F_o²) + (0.019P)²] where P = (F_o² + 2F_c²)/3
9739 reflections	(Δ/σ)_max = 0.003
487 parameters	Δρ_max = 1.03 e Å⁻³
134 restraints	Δρ_min = −1.08 e Å⁻³

Crystal data top

[Ir(C₁₃H₉N₄)(C₁₅H₁₀N)₂]·2CDCl₃	γ = 85.193 (4)°
M_r = 1062.67	V = 1962.41 (12) Å³
Triclinic, P1	Z = 2
a = 9.1399 (3) Å	Mo Kα radiation
b = 12.4430 (5) Å	µ = 3.86 mm⁻¹
c = 17.6762 (6) Å	T = 100 K
α = 81.493 (4)°	0.25 × 0.20 × 0.05 mm
β = 81.509 (4)°

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	9739 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	8125 reflections with I > 2σ(I)
T_min = 0.739, T_max = 1.000	R_int = 0.062
78670 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	134 restraints
wR(F²) = 0.048	H-atom parameters constrained
S = 0.93	Δρ_max = 1.03 e Å⁻³
9739 reflections	Δρ_min = −1.08 e Å⁻³
487 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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

8.0107 (0.0039) x - 5.0559 (0.0100) y + 1.0694 (0.0169) z = 0.3793 (0.0119)

* 0.0612 (0.0010) Ir * -0.0747 (0.0014) N1 * 0.0495 (0.0016) C2 * 0.0270 (0.0017) C11 * -0.0630 (0.0014) C12

Rms deviation of fitted atoms = 0.0574

3.5166 (0.0086) x + 11.8000 (0.0045) y + 4.6463 (0.0182) z = 11.4217 (0.0048)

Angle to previous plane (with approximate e.s.d.) = 83.93 (0.07)

* -0.0639 (0.0011) Ir * 0.0668 (0.0016) C28 * -0.0280 (0.0019) C27 * -0.0526 (0.0019) C18 * 0.0777 (0.0015) N17

Rms deviation of fitted atoms = 0.0602

2.1808 (0.0086) x + 0.5392 (0.0092) y + 17.4903 (0.0021) z = 5.6802 (0.0088)

Angle to previous plane (with approximate e.s.d.) = 78.84 (0.08)

* -0.0035 (0.0009) Ir * 0.0040 (0.0013) N33 * -0.0019 (0.0016) C37 * -0.0031 (0.0016) C38 * 0.0045 (0.0014) N39

Rms deviation of fitted atoms = 0.0035

8.0107 (0.0039) x - 5.0559 (0.0100) y + 1.0694 (0.0169) z = 0.3793 (0.0119)

Angle to previous plane (with approximate e.s.d.) = 78.79 (0.08)

* 0.0612 (0.0010) Ir * -0.0747 (0.0014) N1 * 0.0495 (0.0016) C2 * 0.0270 (0.0017) C11 * -0.0630 (0.0014) C12

Rms deviation of fitted atoms = 0.0574

8.1366 (0.0044) x - 4.6169 (0.0120) y + 2.7467 (0.0185) z = 1.1577 (0.0155)

Angle to previous plane (with approximate e.s.d.) = 5.58 (0.11)

* -0.0062 (0.0018) C11 * 0.0042 (0.0018) C12 * 0.0004 (0.0019) C13 * -0.0031 (0.0020) C14 * 0.0011 (0.0020) C15 * 0.0036 (0.0019) C16

Rms deviation of fitted atoms = 0.0036

- 7.1556 (0.0029) x + 6.8670 (0.0050) y - 1.5139 (0.0120) z = 1.5526 (0.0051)

Angle to previous plane (with approximate e.s.d.) = 11.79 (0.10)

* -0.0880 (0.0018) N1 * 0.0273 (0.0020) C2 * 0.0689 (0.0021) C3 * 0.0094 (0.0021) C4 * -0.0354 (0.0024) C5 * -0.0377 (0.0021) C6 * -0.0110 (0.0022) C7 * 0.0624 (0.0021) C8 * 0.0474 (0.0020) C9 * -0.0432 (0.0022) C10

Rms deviation of fitted atoms = 0.0491

3.8481 (0.0098) x + 11.4658 (0.0058) y + 6.3281 (0.0208) z = 11.7536 (0.0044)

Angle to previous plane (with approximate e.s.d.) = 77.79 (0.06)

* -0.0067 (0.0020) C28 * 0.0001 (0.0020) C29 * 0.0072 (0.0023) C30 * -0.0080 (0.0025) C31 * 0.0013 (0.0023) C32 * 0.0060 (0.0021) C27

Rms deviation of fitted atoms = 0.0058

2.0501 (0.0054) x + 12.1910 (0.0019) y + 5.3371 (0.0154) z = 11.4565 (0.0058)

Angle to previous plane (with approximate e.s.d.) = 12.28 (0.08)

* -0.0704 (0.0021) N17 * 0.0393 (0.0024) C18 * 0.0498 (0.0028) C19 * -0.0036 (0.0029) C20 * -0.0280 (0.0030) C21 * -0.0253 (0.0030) C22 * 0.0012 (0.0029) C23 * 0.0474 (0.0026) C24 * 0.0300 (0.0024) C25 * -0.0404 (0.0026) C26

Rms deviation of fitted atoms = 0.0390

2.0139 (0.0103) x + 0.5046 (0.0150) y + 17.5147 (0.0030) z = 5.5443 (0.0128)

Angle to previous plane (with approximate e.s.d.) = 78.01 (0.09)

* 0.0047 (0.0018) C38 * 0.0079 (0.0017) N39 * -0.0141 (0.0019) C40 * 0.0073 (0.0022) C41 * 0.0051 (0.0023) C42 * -0.0109 (0.0020) C43

Rms deviation of fitted atoms = 0.0090

2.2942 (0.0112) x + 0.5668 (0.0154) y + 17.4708 (0.0033) z = 5.7456 (0.0097)

Angle to previous plane (with approximate e.s.d.) = 1.81 (0.06)

* -0.0023 (0.0014) N33 * 0.0007 (0.0014) N34 * 0.0010 (0.0015) C35 * -0.0024 (0.0015) N36 * 0.0029 (0.0015) C37

Rms deviation of fitted atoms = 0.0020

3.5283 (0.0116) x - 0.8562 (0.0173) y + 16.6404 (0.0084) z = 5.4129 (0.0060)

Angle to previous plane (with approximate e.s.d.) = 11.00 (0.10)

* -0.0031 (0.0021) C44 * 0.0013 (0.0022) C45 * -0.0006 (0.0025) C46 * 0.0019 (0.0027) C47 * -0.0038 (0.0027) C48 * 0.0044 (0.0024) C49

Rms deviation of fitted atoms = 0.0029

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
Ir	0.479659 (11)	0.724128 (9)	0.242431 (7)	0.01435 (3)
N1	0.5063 (2)	0.76795 (18)	0.12298 (13)	0.0164 (5)
C2	0.5821 (3)	0.8582 (2)	0.09770 (16)	0.0183 (6)
C3	0.6254 (3)	0.8918 (2)	0.01826 (17)	0.0241 (7)
H3	0.6797	0.9550	0.0022	0.029*
C4	0.5898 (3)	0.8342 (2)	−0.03560 (17)	0.0250 (7)
H4	0.6227	0.8551	−0.0889	0.030*
C5	0.5035 (3)	0.7430 (2)	−0.01136 (16)	0.0224 (6)
C6	0.4578 (3)	0.6834 (3)	−0.06484 (17)	0.0274 (7)
H6	0.4897	0.7018	−0.1185	0.033*
C7	0.3680 (3)	0.5992 (3)	−0.03966 (18)	0.0283 (7)
H7	0.3403	0.5578	−0.0757	0.034*
C8	0.3166 (3)	0.5737 (2)	0.03924 (17)	0.0253 (7)
H8	0.2504	0.5173	0.0559	0.030*
C9	0.3608 (3)	0.6295 (2)	0.09300 (16)	0.0198 (6)
H9	0.3251	0.6114	0.1463	0.024*
C10	0.4586 (3)	0.7129 (2)	0.06896 (16)	0.0184 (6)
C11	0.6096 (3)	0.9190 (2)	0.15802 (16)	0.0189 (6)
C12	0.5580 (3)	0.8711 (2)	0.23424 (17)	0.0190 (6)
C13	0.5710 (3)	0.9308 (2)	0.29458 (17)	0.0226 (6)
H13	0.5371	0.9019	0.3464	0.027*
C14	0.6325 (3)	1.0308 (2)	0.27935 (19)	0.0284 (7)
H14	0.6397	1.0695	0.3210	0.034*
C15	0.6835 (3)	1.0757 (2)	0.20527 (19)	0.0293 (7)
H15	0.7257	1.1444	0.1961	0.035*
C16	0.6729 (3)	1.0201 (2)	0.14405 (18)	0.0261 (7)
H16	0.7085	1.0504	0.0928	0.031*
N17	0.4354 (3)	0.70179 (19)	0.36314 (13)	0.0239 (6)
C18	0.2901 (3)	0.7236 (3)	0.38966 (19)	0.0348 (8)
C19	0.2355 (5)	0.6990 (3)	0.4688 (2)	0.0534 (11)
H19	0.1330	0.7126	0.4857	0.064*
C20	0.3248 (5)	0.6572 (3)	0.5199 (2)	0.0562 (11)
H20	0.2855	0.6390	0.5727	0.067*
C21	0.4788 (5)	0.6398 (3)	0.49591 (18)	0.0439 (9)
C22	0.5786 (5)	0.6009 (3)	0.5471 (2)	0.0589 (11)
H22	0.5423	0.5823	0.6002	0.071*
C23	0.7259 (5)	0.5885 (3)	0.5236 (2)	0.0557 (11)
H23	0.7916	0.5607	0.5598	0.067*
C24	0.7820 (4)	0.6177 (3)	0.4441 (2)	0.0431 (9)
H24	0.8857	0.6111	0.4275	0.052*
C25	0.6862 (3)	0.6555 (2)	0.39132 (17)	0.0298 (7)
H25	0.7237	0.6753	0.3385	0.036*
C26	0.5336 (4)	0.6647 (2)	0.41575 (17)	0.0290 (7)
C27	0.1995 (3)	0.7753 (3)	0.3323 (2)	0.0338 (8)
C28	0.2731 (3)	0.7910 (2)	0.25696 (19)	0.0266 (7)
C29	0.1941 (3)	0.8497 (2)	0.1998 (2)	0.0354 (8)
H29	0.2412	0.8625	0.1480	0.043*
C30	0.0488 (4)	0.8890 (3)	0.2181 (3)	0.0552 (12)
H30	−0.0021	0.9291	0.1788	0.066*
C31	−0.0228 (4)	0.8707 (3)	0.2923 (3)	0.0645 (14)
H31	−0.1232	0.8965	0.3039	0.077*
C32	0.0508 (4)	0.8153 (3)	0.3494 (3)	0.0541 (11)
H32	0.0019	0.8036	0.4010	0.065*
N33	0.4299 (2)	0.55788 (18)	0.25419 (12)	0.0145 (5)
N34	0.3042 (2)	0.50125 (18)	0.27271 (13)	0.0185 (5)
C35	0.3547 (3)	0.3969 (2)	0.26948 (14)	0.0169 (6)
N36	0.5032 (2)	0.38198 (18)	0.25027 (12)	0.0169 (5)
C37	0.5433 (3)	0.4844 (2)	0.24198 (14)	0.0148 (5)
C38	0.6914 (3)	0.5248 (2)	0.22220 (15)	0.0167 (6)
N39	0.6947 (2)	0.63400 (18)	0.21885 (12)	0.0153 (5)
C40	0.8272 (3)	0.6779 (2)	0.20110 (16)	0.0205 (6)
H40	0.8300	0.7547	0.1968	0.025*
C41	0.9589 (3)	0.6165 (3)	0.18894 (19)	0.0317 (8)
H41	1.0507	0.6500	0.1783	0.038*
C42	0.9549 (3)	0.5056 (3)	0.19247 (19)	0.0334 (8)
H42	1.0443	0.4616	0.1840	0.040*
C43	0.8196 (3)	0.4583 (2)	0.20849 (17)	0.0254 (7)
H43	0.8147	0.3820	0.2100	0.030*
C44	0.2545 (3)	0.3068 (2)	0.28691 (16)	0.0215 (6)
C45	0.3072 (3)	0.2027 (2)	0.27066 (17)	0.0258 (7)
H45	0.4076	0.1904	0.2490	0.031*
C46	0.2140 (4)	0.1174 (3)	0.2859 (2)	0.0387 (8)
H46	0.2504	0.0470	0.2744	0.046*
C47	0.0680 (4)	0.1350 (3)	0.3179 (2)	0.0477 (10)
H47	0.0040	0.0767	0.3288	0.057*
C48	0.0154 (4)	0.2382 (3)	0.3340 (2)	0.0472 (10)
H48	−0.0852	0.2503	0.3554	0.057*
C49	0.1075 (3)	0.3236 (3)	0.31940 (18)	0.0330 (8)
H49	0.0706	0.3936	0.3315	0.040*
C98	0.9808 (4)	1.2544 (3)	0.0450 (2)	0.0480 (10)
H98	0.8770	1.2866	0.0552	0.058*
Cl1	1.03734 (9)	1.19846 (8)	0.13387 (6)	0.0509 (2)
Cl2	0.98185 (9)	1.15510 (8)	−0.01637 (6)	0.0519 (3)
Cl3	1.09404 (12)	1.35913 (7)	0.00000 (6)	0.0619 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ir	0.01027 (5)	0.01557 (6)	0.01753 (5)	−0.00124 (4)	0.00080 (4)	−0.00580 (4)
N1	0.0137 (11)	0.0170 (12)	0.0190 (12)	0.0011 (9)	−0.0057 (9)	−0.0016 (10)
C2	0.0145 (14)	0.0177 (15)	0.0219 (15)	0.0030 (11)	−0.0063 (11)	0.0011 (12)
C3	0.0183 (15)	0.0236 (17)	0.0286 (17)	0.0005 (12)	−0.0045 (12)	0.0029 (13)
C4	0.0206 (15)	0.0322 (18)	0.0177 (15)	0.0092 (13)	−0.0024 (12)	0.0046 (13)
C5	0.0157 (14)	0.0289 (17)	0.0224 (15)	0.0077 (12)	−0.0059 (12)	−0.0047 (13)
C6	0.0237 (16)	0.0372 (19)	0.0218 (16)	0.0120 (14)	−0.0072 (12)	−0.0090 (14)
C7	0.0260 (16)	0.0340 (19)	0.0292 (17)	0.0109 (14)	−0.0132 (13)	−0.0161 (15)
C8	0.0193 (15)	0.0284 (17)	0.0321 (17)	0.0038 (13)	−0.0108 (13)	−0.0130 (14)
C9	0.0155 (14)	0.0219 (16)	0.0228 (15)	0.0031 (11)	−0.0061 (11)	−0.0044 (12)
C10	0.0130 (13)	0.0232 (16)	0.0199 (15)	0.0075 (11)	−0.0074 (11)	−0.0057 (12)
C11	0.0114 (13)	0.0179 (15)	0.0274 (16)	0.0023 (11)	−0.0055 (11)	−0.0018 (12)
C12	0.0089 (13)	0.0183 (15)	0.0309 (17)	0.0003 (11)	−0.0028 (11)	−0.0075 (13)
C13	0.0194 (15)	0.0226 (16)	0.0266 (16)	−0.0023 (12)	−0.0029 (12)	−0.0053 (13)
C14	0.0262 (16)	0.0241 (17)	0.0389 (19)	−0.0049 (13)	−0.0101 (14)	−0.0099 (15)
C15	0.0266 (16)	0.0153 (16)	0.048 (2)	−0.0090 (13)	−0.0103 (15)	−0.0008 (14)
C16	0.0210 (15)	0.0228 (16)	0.0330 (18)	−0.0039 (13)	−0.0059 (13)	0.0048 (13)
N17	0.0315 (14)	0.0215 (14)	0.0196 (13)	−0.0124 (11)	0.0068 (10)	−0.0094 (11)
C18	0.0363 (18)	0.0285 (19)	0.0391 (19)	−0.0156 (14)	0.0231 (15)	−0.0230 (15)
C19	0.065 (3)	0.047 (2)	0.046 (2)	−0.025 (2)	0.0348 (19)	−0.027 (2)
C20	0.090 (3)	0.044 (2)	0.031 (2)	−0.031 (2)	0.036 (2)	−0.0190 (18)
C21	0.090 (3)	0.029 (2)	0.0147 (16)	−0.0232 (19)	0.0005 (17)	−0.0069 (15)
C22	0.118 (3)	0.043 (2)	0.0192 (19)	−0.027 (3)	−0.008 (2)	−0.0038 (17)
C23	0.118 (3)	0.031 (2)	0.029 (2)	−0.013 (2)	−0.045 (2)	0.0019 (17)
C24	0.065 (2)	0.036 (2)	0.036 (2)	−0.0128 (18)	−0.0306 (18)	0.0001 (16)
C25	0.049 (2)	0.0257 (17)	0.0184 (16)	−0.0096 (15)	−0.0127 (14)	−0.0035 (13)
C26	0.051 (2)	0.0201 (17)	0.0175 (15)	−0.0127 (15)	0.0003 (14)	−0.0084 (13)
C27	0.0210 (16)	0.0265 (18)	0.057 (2)	−0.0097 (13)	0.0094 (15)	−0.0267 (16)
C28	0.0155 (14)	0.0172 (16)	0.051 (2)	−0.0057 (12)	0.0017 (13)	−0.0216 (15)
C29	0.0188 (15)	0.0224 (17)	0.073 (3)	0.0013 (13)	−0.0158 (16)	−0.0240 (17)
C30	0.0200 (18)	0.036 (2)	0.124 (4)	0.0090 (16)	−0.026 (2)	−0.047 (2)
C31	0.0127 (18)	0.047 (3)	0.145 (4)	0.0018 (16)	−0.002 (2)	−0.062 (3)
C32	0.0250 (18)	0.042 (2)	0.099 (3)	−0.0172 (16)	0.0256 (19)	−0.050 (2)
N33	0.0144 (11)	0.0160 (12)	0.0132 (12)	−0.0018 (9)	0.0017 (9)	−0.0056 (9)
N34	0.0170 (12)	0.0172 (12)	0.0210 (13)	−0.0051 (10)	0.0037 (10)	−0.0062 (10)
C35	0.0227 (14)	0.0170 (14)	0.0109 (13)	−0.0033 (11)	0.0006 (11)	−0.0035 (11)
N36	0.0207 (12)	0.0162 (12)	0.0146 (12)	−0.0002 (9)	−0.0048 (9)	−0.0029 (10)
C37	0.0161 (13)	0.0180 (14)	0.0109 (13)	0.0006 (11)	−0.0036 (10)	−0.0029 (11)
C38	0.0171 (13)	0.0203 (15)	0.0147 (14)	−0.0013 (11)	−0.0057 (11)	−0.0057 (11)
N39	0.0111 (11)	0.0204 (13)	0.0156 (12)	−0.0015 (9)	−0.0023 (9)	−0.0055 (10)
C40	0.0149 (14)	0.0237 (16)	0.0245 (16)	−0.0026 (12)	−0.0010 (12)	−0.0093 (13)
C41	0.0124 (14)	0.0341 (19)	0.051 (2)	−0.0007 (13)	−0.0025 (14)	−0.0148 (17)
C42	0.0149 (15)	0.035 (2)	0.053 (2)	0.0089 (13)	−0.0069 (14)	−0.0177 (17)
C43	0.0198 (15)	0.0235 (17)	0.0356 (18)	0.0044 (12)	−0.0091 (13)	−0.0111 (14)
C44	0.0268 (15)	0.0195 (15)	0.0182 (15)	−0.0054 (12)	−0.0002 (12)	−0.0035 (12)
C45	0.0299 (16)	0.0197 (16)	0.0274 (17)	−0.0029 (13)	−0.0007 (13)	−0.0049 (13)
C46	0.048 (2)	0.0209 (18)	0.046 (2)	−0.0094 (15)	0.0068 (17)	−0.0090 (16)
C47	0.052 (2)	0.029 (2)	0.060 (3)	−0.0240 (17)	0.0233 (19)	−0.0152 (18)
C48	0.045 (2)	0.037 (2)	0.057 (2)	−0.0215 (17)	0.0272 (18)	−0.0181 (19)
C49	0.0357 (18)	0.0235 (17)	0.038 (2)	−0.0119 (14)	0.0150 (15)	−0.0113 (15)
C98	0.0281 (19)	0.041 (2)	0.079 (3)	0.0085 (16)	−0.0137 (19)	−0.021 (2)
Cl1	0.0316 (5)	0.0592 (6)	0.0578 (6)	−0.0033 (4)	0.0045 (4)	−0.0049 (5)
Cl2	0.0398 (5)	0.0402 (6)	0.0808 (8)	−0.0097 (4)	−0.0109 (5)	−0.0188 (5)
Cl3	0.0956 (8)	0.0249 (5)	0.0750 (8)	−0.0077 (5)	−0.0487 (6)	0.0000 (5)

Geometric parameters (Å, º) top

Ir—C28	1.995 (3)	N36—C37	1.336 (3)
Ir—C12	1.997 (3)	C37—C38	1.460 (3)
Ir—N1	2.084 (2)	C38—N39	1.354 (3)
Ir—N17	2.093 (2)	C38—C43	1.389 (4)
Ir—N33	2.129 (2)	N39—C40	1.346 (3)
Ir—N39	2.196 (2)	C40—C41	1.378 (4)
N1—C2	1.353 (3)	C41—C42	1.375 (4)
N1—C10	1.392 (3)	C42—C43	1.388 (4)
C2—C3	1.412 (4)	C44—C49	1.393 (4)
C2—C11	1.457 (4)	C44—C45	1.398 (4)
C3—C4	1.363 (4)	C45—C46	1.387 (4)
C4—C5	1.414 (4)	C46—C47	1.384 (4)
C5—C6	1.413 (4)	C47—C48	1.387 (4)
C5—C10	1.421 (4)	C48—C49	1.381 (4)
C6—C7	1.367 (4)	C98—Cl1	1.753 (4)
C7—C8	1.403 (4)	C98—Cl3	1.755 (4)
C8—C9	1.380 (4)	C98—Cl2	1.760 (3)
C9—C10	1.403 (4)	C3—H3	0.9500
C11—C16	1.402 (4)	C4—H4	0.9500
C11—C12	1.419 (4)	C6—H6	0.9500
C12—C13	1.411 (4)	C7—H7	0.9500
C13—C14	1.382 (4)	C8—H8	0.9500
C14—C15	1.375 (4)	C9—H9	0.9500
C15—C16	1.387 (4)	C13—H13	0.9500
N17—C18	1.361 (4)	C14—H14	0.9500
N17—C26	1.391 (4)	C15—H15	0.9500
C18—C19	1.411 (5)	C16—H16	0.9500
C18—C27	1.447 (5)	C19—H19	0.9500
C19—C20	1.328 (5)	C20—H20	0.9500
C20—C21	1.417 (5)	C22—H22	0.9500
C21—C22	1.387 (5)	C23—H23	0.9500
C21—C26	1.429 (4)	C24—H24	0.9500
C22—C23	1.352 (5)	C25—H25	0.9500
C23—C24	1.428 (5)	C29—H29	0.9500
C24—C25	1.379 (4)	C30—H30	0.9500
C25—C26	1.398 (4)	C31—H31	0.9500
C27—C28	1.394 (4)	C32—H32	0.9500
C27—C32	1.413 (4)	C40—H40	0.9500
C28—C29	1.408 (4)	C41—H41	0.9500
C29—C30	1.386 (4)	C42—H42	0.9500
C30—C31	1.372 (6)	C43—H43	0.9500
C31—C32	1.365 (6)	C45—H45	0.9500
N33—C37	1.339 (3)	C46—H46	0.9500
N33—N34	1.371 (3)	C47—H47	0.9500
N34—C35	1.347 (3)	C48—H48	0.9500
C35—N36	1.354 (3)	C49—H49	0.9500
C35—C44	1.476 (4)	C98—H98	1.0000

C28—Ir—C12	89.81 (10)	N39—C38—C43	122.0 (2)
C28—Ir—N1	93.57 (11)	N39—C38—C37	114.3 (2)
C12—Ir—N1	79.82 (10)	C43—C38—C37	123.7 (3)
C28—Ir—N17	79.82 (12)	C40—N39—C38	118.0 (2)
C12—Ir—N17	95.05 (10)	C40—N39—Ir	125.77 (18)
N1—Ir—N17	171.70 (9)	C38—N39—Ir	116.20 (16)
C28—Ir—N33	98.69 (10)	N39—C40—C41	123.0 (3)
C12—Ir—N33	171.11 (9)	C42—C41—C40	118.7 (3)
N1—Ir—N33	102.08 (8)	C41—C42—C43	119.6 (3)
N17—Ir—N33	83.99 (8)	C42—C43—C38	118.6 (3)
C28—Ir—N39	172.20 (9)	C49—C44—C45	119.2 (3)
C12—Ir—N39	96.86 (9)	C49—C44—C35	121.0 (3)
N1—Ir—N39	83.69 (8)	C45—C44—C35	119.9 (3)
N17—Ir—N39	103.50 (9)	C46—C45—C44	120.6 (3)
N33—Ir—N39	74.85 (8)	C47—C46—C45	119.8 (3)
C2—N1—C10	118.8 (2)	C46—C47—C48	119.7 (3)
C2—N1—Ir	114.28 (18)	C49—C48—C47	120.9 (3)
C10—N1—Ir	126.87 (19)	C48—C49—C44	119.9 (3)
N1—C2—C3	121.6 (3)	Cl1—C98—Cl3	110.20 (18)
N1—C2—C11	115.0 (2)	Cl1—C98—Cl2	111.88 (19)
C3—C2—C11	123.3 (3)	Cl3—C98—Cl2	110.3 (2)
C4—C3—C2	120.4 (3)	C4—C3—H3	119.8
C3—C4—C5	119.4 (3)	C2—C3—H3	119.8
C6—C5—C4	121.7 (3)	C3—C4—H4	120.3
C6—C5—C10	119.5 (3)	C5—C4—H4	120.3
C4—C5—C10	118.8 (3)	C7—C6—H6	119.9
C7—C6—C5	120.2 (3)	C5—C6—H6	119.9
C6—C7—C8	120.2 (3)	C6—C7—H7	119.9
C9—C8—C7	120.9 (3)	C8—C7—H7	119.9
C8—C9—C10	120.0 (3)	C9—C8—H8	119.6
N1—C10—C9	120.3 (2)	C7—C8—H8	119.6
N1—C10—C5	120.6 (3)	C8—C9—H9	120.0
C9—C10—C5	119.0 (3)	C10—C9—H9	120.0
C16—C11—C12	121.1 (3)	C14—C13—H13	119.5
C16—C11—C2	124.3 (3)	C12—C13—H13	119.5
C12—C11—C2	114.5 (2)	C15—C14—H14	119.2
C13—C12—C11	116.9 (3)	C13—C14—H14	119.2
C13—C12—Ir	128.0 (2)	C14—C15—H15	120.2
C11—C12—Ir	115.1 (2)	C16—C15—H15	120.2
C14—C13—C12	120.9 (3)	C15—C16—H16	120.1
C15—C14—C13	121.5 (3)	C11—C16—H16	120.1
C14—C15—C16	119.7 (3)	C20—C19—H19	119.4
C15—C16—C11	119.9 (3)	C18—C19—H19	119.4
C18—N17—C26	119.3 (3)	C19—C20—H20	120.0
C18—N17—Ir	112.8 (2)	C21—C20—H20	120.0
C26—N17—Ir	127.88 (19)	C23—C22—H22	119.0
N17—C18—C19	120.8 (3)	C21—C22—H22	119.0
N17—C18—C27	115.7 (3)	C22—C23—H23	120.2
C19—C18—C27	123.5 (3)	C24—C23—H23	120.2
C20—C19—C18	121.2 (4)	C25—C24—H24	119.9
C19—C20—C21	120.0 (3)	C23—C24—H24	119.9
C22—C21—C20	122.7 (4)	C24—C25—H25	120.1
C22—C21—C26	118.7 (4)	C26—C25—H25	120.1
C20—C21—C26	118.6 (3)	C30—C29—H29	119.5
C23—C22—C21	122.0 (4)	C28—C29—H29	119.5
C22—C23—C24	119.5 (3)	C31—C30—H30	119.6
C25—C24—C23	120.2 (4)	C29—C30—H30	119.6
C24—C25—C26	119.9 (3)	C32—C31—H31	120.1
N17—C26—C25	120.6 (3)	C30—C31—H31	120.1
N17—C26—C21	119.8 (3)	C31—C32—H32	119.9
C25—C26—C21	119.6 (3)	C27—C32—H32	119.9
C28—C27—C32	120.7 (3)	N39—C40—H40	118.5
C28—C27—C18	114.9 (3)	C41—C40—H40	118.5
C32—C27—C18	124.2 (3)	C42—C41—H41	120.7
C27—C28—C29	117.3 (3)	C40—C41—H41	120.7
C27—C28—Ir	115.4 (2)	C41—C42—H42	120.2
C29—C28—Ir	127.3 (2)	C43—C42—H42	120.2
C30—C29—C28	120.9 (4)	C42—C43—H43	120.7
C31—C30—C29	120.9 (4)	C38—C43—H43	120.7
C32—C31—C30	119.8 (3)	C46—C45—H45	119.7
C31—C32—C27	120.3 (4)	C44—C45—H45	119.7
C37—N33—N34	106.6 (2)	C47—C46—H46	120.1
C37—N33—Ir	117.48 (17)	C45—C46—H46	120.1
N34—N33—Ir	135.89 (16)	C46—C47—H47	120.1
C35—N34—N33	103.7 (2)	C48—C47—H47	120.1
N34—C35—N36	114.8 (2)	C49—C48—H48	119.6
N34—C35—C44	121.9 (2)	C47—C48—H48	119.6
N36—C35—C44	123.3 (2)	C48—C49—H49	120.1
C37—N36—C35	100.9 (2)	C44—C49—H49	120.1
N36—C37—N33	113.9 (2)	Cl1—C98—H98	108.1
N36—C37—C38	128.8 (2)	Cl3—C98—H98	108.1
N33—C37—C38	117.2 (2)	Cl2—C98—H98	108.1

Experimental details

Crystal data
Chemical formula	[Ir(C₁₃H₉N₄)(C₁₅H₁₀N)₂]·2CDCl₃
M_r	1062.67
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	9.1399 (3), 12.4430 (5), 17.6762 (6)
α, β, γ (°)	81.493 (4), 81.509 (4), 85.193 (4)
V (Å³)	1962.41 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.86
Crystal size (mm)	0.25 × 0.20 × 0.05

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.739, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	78670, 9739, 8125
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.048, 0.93
No. of reflections	9739
No. of parameters	487
No. of restraints	134
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.03, −1.08

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), XP (Siemens, 1994), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Acknowledgements

The authors thank the Bundesministerium für Bildung und Forschung (BMBF 01 BD 0687) for financial support.

References

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