metal-organic compounds
(5-Methylpyrazine-2-carboxylato-κ2N1,O)bis[2-(4-methylpyridin-2-yl-κN)-3,5-bis(trifluoromethyl)phenyl-κC1]iridium(III) chloroform hemisolvate
aDepartment of Chemistry Education and Department of Chemical Materials, Graduate School, Pusan National University, Busan 609-735, Republic of Korea, and bDepartment of Chemistry, Chungnam National University, Daejeon 305-764, Republic of Korea
*Correspondence e-mail: skkang@cnu.ac.kr
In the title complex, [Ir(C14H8F6N)2(C6H5N2O2)]·0.5CHCl3, the IrIII atom adopts a distorted octahedral geometry, being coordinated by three N atoms (arranged meridionally), two C atoms and one O atom of three bidentate ligands. The complex molecules pack with no specific intermolecular interactions between them. The SQUEEZE procedure in PLATON [Spek (2009). Acta Cryst. D65, 148–155] was used to model a disordered chloroform solvent molecule; the calculated unit-cell data allow for the presence of half of this molecule in the asymmetric unit.
CCDC reference: 978885
Related literature
For phosphorescent Ir complexes, see: Chen et al. (2010). For phosphorescent Ir complexes in OLED, see: Chang et al. (2013); Park et al. (2013); Seo et al. (2010).
Experimental
Crystal data
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Data collection: SMART (Bruker, 2002); cell SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).
Supporting information
CCDC reference: 978885
10.1107/S1600536813034727/tk5282sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536813034727/tk5282Isup2.hkl
Synthesis of 2-(2,4-bis(trifluoromethyl)phenyl)-4-methylpyridine (dCF3pmpy): A Suzuki coupling reaction between 2-bromo-4-methylpyridine and 2,4-bis(trifluoromethyl)phenylboronic acid using tetrakis(triphenylphosphine)palladium(0) as a catalyst yielded 2-(2,4-bis(trifluoromethyl)phenyl)-4-methylpyridine in freshly distilled THF under nitrogen atmosphere.
Synthesis of title complex: The cyclometalated iridium(III) µ-chloro-bridged dimer, [(dCF3pmpy)2Ir(µ-Cl)]2 was prepared from the reaction of the iridium(III) trichloride trihydrate and dCF3pmpy in a solution of 2-ethoxyethanol/water (3:1 v/v). The prepared iridium(III) dimer (0.25 g, 0.15 mmol), sodium carbonate (0.16 g, 1.5 mmol) and 2.2 equivalents 5-methylpyrazine-2-carboxylic acid (mprz) (0.45 g, 0.3 mmol) were dissolved in 2-ethoxyethanol (20 ml) and the mixture was heated at 130 °C for 24 h. The mixture extracted with dichloromethane (3 × 50 ml) and dried over anhydrous magnesium sulfate. The crude product was flash chromatographed on silica gel using dichloromethane/methanol as an
to afford the title iridium(III) complex. Yield: 0.17 g (60%). The yellow crystals were obtained from its n-hexane/chloroform solution by slow evaporation at room temperature.All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93-0.96 Å, and with Uiso(H) = 1.2Ueq(C) for aromatic and 1.5Ueq(C) for methyl H atoms. There is a disordered chloroform solvent molecule which was difficult to model. Therefore, the SQUEEZE command of PLATON (Spek 2009) was used to model the electron density in the void regions. There is one cavity of 165 Å3 per
This cavity contains approximately 58 electrons which were assigned to one solvent chloroform (CHCl3) molecule. With Z = 2, the Ir complex has a 0.5 solvent chloroform equivalent. The reported and cell characteristics take into account the presence of the solvent molecule. The maximum and minimum residual electron density peaks of 1.21 and -0.90 eÅ-3, respectively, were located at 1.16 and 0.84 Å from the F39 and Ir1 atoms, respectively.Phosphorescent cyclometalated iridium(III) complexes have attracted significant attention with respect to their enormous potential in a range of photonic applications (Chen et al., 2010). For example, these iridium(III) complexes can be used as light emitting phosphors in an emitting layer in organic light-emitting diodes (OLEDs) since the emission wavelength of the iridium(III) complexes are tunable from red to blue by changing the electronic nature of the coordinated ligands (Chang et al., 2013; Park et al., 2013; Seo et al., 2010). In this study, we prepared a green emitting Ir(dCF3pmpy)2(mprz) complex where dCF3pmpy is 2-(2,4-bis(triflouromethyl)phenyl)-4-methylpyridine and mprz is 5-methylpyrazine-2-carboxylic acid and studied its single-crystal X-ray structure. The title compound showed an emission at 517 nm in a dichloromethane solution. The HOMO and LUMO energy levels were obtained -6.04 eV and -3.42 eV from the electrochemical properties, respectively.
In (I), Fig. 1, the IrIII atom is coordinated by three N atoms, two C atoms, and one O atom of three bidentate ligands in a distorted octahedral geometry. The angles around Ir atoms are in the range of 77.10 (8) – 99.81 (10)°. The Ir—C bond distances of 1.993 (3) – 1.999 (3) Å are shorter than the Ir—N distances of 2.028 (2) – 2.035 (2) Å due to the stronger trans influence of the benzene ring compared to the pyridine ring (Table 1). The dihedral angle between the benzene and pyridine rings in the bidentate dCF3pmpy ligands are 16.97 (14) – 16.98 (9)°.
Phosphorescent cyclometalated iridium(III) complexes have attracted significant attention with respect to their enormous potential in a range of photonic applications (Chen et al., 2010). For example, these iridium(III) complexes can be used as light emitting phosphors in an emitting layer in organic light-emitting diodes (OLEDs) since the emission wavelength of the iridium(III) complexes are tunable from red to blue by changing the electronic nature of the coordinated ligands (Chang et al., 2013; Park et al., 2013; Seo et al., 2010). In this study, we prepared a green emitting Ir(dCF3pmpy)2(mprz) complex where dCF3pmpy is 2-(2,4-bis(triflouromethyl)phenyl)-4-methylpyridine and mprz is 5-methylpyrazine-2-carboxylic acid and studied its single-crystal X-ray structure. The title compound showed an emission at 517 nm in a dichloromethane solution. The HOMO and LUMO energy levels were obtained -6.04 eV and -3.42 eV from the electrochemical properties, respectively.
In (I), Fig. 1, the IrIII atom is coordinated by three N atoms, two C atoms, and one O atom of three bidentate ligands in a distorted octahedral geometry. The angles around Ir atoms are in the range of 77.10 (8) – 99.81 (10)°. The Ir—C bond distances of 1.993 (3) – 1.999 (3) Å are shorter than the Ir—N distances of 2.028 (2) – 2.035 (2) Å due to the stronger trans influence of the benzene ring compared to the pyridine ring (Table 1). The dihedral angle between the benzene and pyridine rings in the bidentate dCF3pmpy ligands are 16.97 (14) – 16.98 (9)°.
For phosphorescent Ir complexes, see: Chen et al. (2010). For phosphorescent Ir complexes in OLED, see: Chang et al. (2013); Park et al. (2013); Seo et al. (2010).
Synthesis of 2-(2,4-bis(trifluoromethyl)phenyl)-4-methylpyridine (dCF3pmpy): A Suzuki coupling reaction between 2-bromo-4-methylpyridine and 2,4-bis(trifluoromethyl)phenylboronic acid using tetrakis(triphenylphosphine)palladium(0) as a catalyst yielded 2-(2,4-bis(trifluoromethyl)phenyl)-4-methylpyridine in freshly distilled THF under nitrogen atmosphere.
Synthesis of title complex: The cyclometalated iridium(III) µ-chloro-bridged dimer, [(dCF3pmpy)2Ir(µ-Cl)]2 was prepared from the reaction of the iridium(III) trichloride trihydrate and dCF3pmpy in a solution of 2-ethoxyethanol/water (3:1 v/v). The prepared iridium(III) dimer (0.25 g, 0.15 mmol), sodium carbonate (0.16 g, 1.5 mmol) and 2.2 equivalents 5-methylpyrazine-2-carboxylic acid (mprz) (0.45 g, 0.3 mmol) were dissolved in 2-ethoxyethanol (20 ml) and the mixture was heated at 130 °C for 24 h. The mixture extracted with dichloromethane (3 × 50 ml) and dried over anhydrous magnesium sulfate. The crude product was flash chromatographed on silica gel using dichloromethane/methanol as an
to afford the title iridium(III) complex. Yield: 0.17 g (60%). The yellow crystals were obtained from its n-hexane/chloroform solution by slow evaporation at room temperature. detailsAll H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93-0.96 Å, and with Uiso(H) = 1.2Ueq(C) for aromatic and 1.5Ueq(C) for methyl H atoms. There is a disordered chloroform solvent molecule which was difficult to model. Therefore, the SQUEEZE command of PLATON (Spek 2009) was used to model the electron density in the void regions. There is one cavity of 165 Å3 per
This cavity contains approximately 58 electrons which were assigned to one solvent chloroform (CHCl3) molecule. With Z = 2, the Ir complex has a 0.5 solvent chloroform equivalent. The reported and cell characteristics take into account the presence of the solvent molecule. The maximum and minimum residual electron density peaks of 1.21 and -0.90 eÅ-3, respectively, were located at 1.16 and 0.84 Å from the F39 and Ir1 atoms, respectively.Data collection: SMART (Bruker, 2002); cell
SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).Fig. 1. Molecular structure of the title compound, showing the atom-numbering scheme and 30% probability ellipsoids. The chloroform molecule is not shown. |
[Ir(C14H8F6N)2(C6H5N2O2)]·0.5CHCl3 | Z = 2 |
Mr = 997.43 | F(000) = 966 |
Triclinic, P1 | Dx = 1.881 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 11.0949 (3) Å | Cell parameters from 9024 reflections |
b = 12.3669 (4) Å | θ = 2.5–28.3° |
c = 14.2892 (4) Å | µ = 4.01 mm−1 |
α = 94.399 (3)° | T = 296 K |
β = 110.888 (1)° | Block, yellow |
γ = 102.695 (2)° | 0.36 × 0.27 × 0.26 mm |
V = 1760.93 (9) Å3 |
Bruker SMART CCD area-detector diffractometer | 8016 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.069 |
φ and ω scans | θmax = 28.3°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −14→14 |
Tmin = 0.284, Tmax = 0.351 | k = −16→16 |
46539 measured reflections | l = −19→19 |
8709 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.025 | H-atom parameters not refined |
wR(F2) = 0.064 | w = 1/[σ2(Fo2) + (0.040P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
8709 reflections | Δρmax = 1.22 e Å−3 |
481 parameters | Δρmin = −0.90 e Å−3 |
[Ir(C14H8F6N)2(C6H5N2O2)]·0.5CHCl3 | γ = 102.695 (2)° |
Mr = 997.43 | V = 1760.93 (9) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.0949 (3) Å | Mo Kα radiation |
b = 12.3669 (4) Å | µ = 4.01 mm−1 |
c = 14.2892 (4) Å | T = 296 K |
α = 94.399 (3)° | 0.36 × 0.27 × 0.26 mm |
β = 110.888 (1)° |
Bruker SMART CCD area-detector diffractometer | 8709 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 8016 reflections with I > 2σ(I) |
Tmin = 0.284, Tmax = 0.351 | Rint = 0.069 |
46539 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.064 | H-atom parameters not refined |
S = 1.04 | Δρmax = 1.22 e Å−3 |
8709 reflections | Δρmin = −0.90 e Å−3 |
481 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Ir1 | 0.03883 (2) | 0.25529 (2) | 0.20131 (2) | 0.02728 (4) | |
N2 | 0.1883 (2) | 0.40036 (17) | 0.26029 (17) | 0.0284 (4) | |
C3 | 0.1693 (3) | 0.5036 (2) | 0.2518 (2) | 0.0333 (6) | |
H3 | 0.0824 | 0.5112 | 0.2313 | 0.04* | |
C4 | 0.2723 (3) | 0.5980 (2) | 0.2721 (2) | 0.0387 (6) | |
H4 | 0.2554 | 0.6683 | 0.2681 | 0.046* | |
C5 | 0.4014 (3) | 0.5881 (2) | 0.2986 (3) | 0.0418 (7) | |
C6 | 0.4208 (3) | 0.4820 (2) | 0.3097 (2) | 0.0383 (6) | |
H6 | 0.5068 | 0.473 | 0.3277 | 0.046* | |
C7 | 0.3165 (3) | 0.3897 (2) | 0.2949 (2) | 0.0290 (5) | |
C8 | 0.3232 (3) | 0.2723 (2) | 0.3049 (2) | 0.0290 (5) | |
C9 | 0.1971 (3) | 0.1931 (2) | 0.2568 (2) | 0.0297 (5) | |
C10 | 0.1925 (3) | 0.0790 (2) | 0.2549 (2) | 0.0358 (6) | |
H10 | 0.1109 | 0.0255 | 0.2215 | 0.043* | |
C11 | 0.3056 (3) | 0.0440 (2) | 0.3011 (3) | 0.0381 (6) | |
C12 | 0.4279 (3) | 0.1215 (3) | 0.3550 (3) | 0.0410 (7) | |
H12 | 0.5031 | 0.0973 | 0.3891 | 0.049* | |
C13 | 0.4371 (3) | 0.2356 (2) | 0.3577 (2) | 0.0349 (6) | |
C14 | 0.5175 (4) | 0.6877 (3) | 0.3150 (5) | 0.0797 (15) | |
H14A | 0.4921 | 0.7315 | 0.2621 | 0.12* | |
H14B | 0.5924 | 0.6618 | 0.3137 | 0.12* | |
H14C | 0.5419 | 0.7334 | 0.3798 | 0.12* | |
C15 | 0.2965 (4) | −0.0789 (3) | 0.2947 (3) | 0.0525 (9) | |
F16 | 0.1865 (3) | −0.13855 (19) | 0.3003 (3) | 0.0883 (9) | |
F17 | 0.3047 (5) | −0.1224 (2) | 0.2134 (3) | 0.1211 (14) | |
F18 | 0.3937 (3) | −0.1016 (2) | 0.3709 (3) | 0.1000 (10) | |
C19 | 0.5741 (3) | 0.3107 (3) | 0.4222 (3) | 0.0493 (8) | |
F20 | 0.6443 (2) | 0.35089 (19) | 0.3678 (2) | 0.0669 (6) | |
F21 | 0.5699 (2) | 0.40044 (19) | 0.47936 (17) | 0.0694 (6) | |
F22 | 0.6487 (2) | 0.2576 (2) | 0.4880 (2) | 0.0780 (8) | |
N23 | −0.0887 (2) | 0.09914 (19) | 0.14990 (18) | 0.0316 (5) | |
C24 | −0.1141 (3) | 0.0403 (3) | 0.0586 (2) | 0.0440 (7) | |
H24 | −0.0939 | 0.0788 | 0.0104 | 0.053* | |
C25 | −0.1684 (3) | −0.0741 (3) | 0.0334 (3) | 0.0475 (8) | |
H25 | −0.1842 | −0.1115 | −0.0306 | 0.057* | |
C26 | −0.1994 (3) | −0.1336 (3) | 0.1039 (3) | 0.0447 (7) | |
C27 | −0.1780 (3) | −0.0718 (2) | 0.1968 (3) | 0.0411 (7) | |
H27 | −0.1999 | −0.1091 | 0.245 | 0.049* | |
C28 | −0.1243 (3) | 0.0451 (2) | 0.2193 (2) | 0.0318 (5) | |
C29 | −0.0885 (3) | 0.1206 (2) | 0.3161 (2) | 0.0307 (5) | |
C30 | −0.0002 (3) | 0.2272 (2) | 0.3244 (2) | 0.0284 (5) | |
C31 | 0.0482 (3) | 0.3046 (2) | 0.4146 (2) | 0.0339 (6) | |
H31 | 0.1077 | 0.3735 | 0.4216 | 0.041* | |
C32 | 0.0082 (3) | 0.2796 (2) | 0.4939 (2) | 0.0373 (6) | |
C33 | −0.0821 (3) | 0.1794 (3) | 0.4843 (2) | 0.0390 (6) | |
H33 | −0.1104 | 0.1649 | 0.5371 | 0.047* | |
C34 | −0.1315 (3) | 0.0999 (2) | 0.3966 (2) | 0.0343 (6) | |
C35 | −0.2524 (4) | −0.2593 (3) | 0.0832 (4) | 0.0676 (11) | |
H35A | −0.1801 | −0.2927 | 0.1125 | 0.101* | |
H35B | −0.2933 | −0.2853 | 0.0111 | 0.101* | |
H35C | −0.3176 | −0.2803 | 0.1127 | 0.101* | |
C36 | 0.0617 (4) | 0.3628 (3) | 0.5896 (3) | 0.0562 (9) | |
F37 | 0.1506 (5) | 0.4477 (3) | 0.5970 (3) | 0.173 (2) | |
F38 | −0.0266 (4) | 0.4019 (5) | 0.6057 (4) | 0.185 (3) | |
F39 | 0.1054 (7) | 0.3199 (3) | 0.6689 (2) | 0.197 (3) | |
C40 | −0.2349 (3) | −0.0040 (3) | 0.3935 (3) | 0.0456 (7) | |
F41 | −0.34179 (19) | −0.03214 (18) | 0.30647 (17) | 0.0587 (5) | |
F42 | −0.2824 (2) | 0.0087 (2) | 0.46604 (18) | 0.0708 (7) | |
F43 | −0.1863 (2) | −0.09515 (17) | 0.40656 (19) | 0.0639 (6) | |
N44 | −0.1189 (2) | 0.33246 (19) | 0.13102 (18) | 0.0319 (5) | |
C45 | −0.2095 (3) | 0.3571 (2) | 0.1648 (2) | 0.0374 (6) | |
H45 | −0.2079 | 0.34 | 0.2274 | 0.045* | |
C46 | −0.3056 (3) | 0.4073 (3) | 0.1089 (2) | 0.0435 (7) | |
N47 | −0.3107 (3) | 0.4348 (3) | 0.0193 (2) | 0.0580 (8) | |
C48 | −0.2181 (4) | 0.4116 (4) | −0.0121 (3) | 0.0585 (10) | |
H48 | −0.2178 | 0.4315 | −0.0735 | 0.07* | |
C49 | −0.1226 (3) | 0.3600 (3) | 0.0412 (2) | 0.0397 (6) | |
C50 | −0.4071 (4) | 0.4341 (4) | 0.1458 (3) | 0.0615 (10) | |
H50A | −0.3628 | 0.4778 | 0.213 | 0.092* | |
H50B | −0.4663 | 0.3655 | 0.1475 | 0.092* | |
H50C | −0.4576 | 0.4763 | 0.1009 | 0.092* | |
C51 | −0.0206 (3) | 0.3327 (3) | 0.0033 (2) | 0.0431 (7) | |
O52 | 0.0579 (2) | 0.28101 (18) | 0.05964 (16) | 0.0395 (4) | |
O53 | −0.0184 (3) | 0.3611 (3) | −0.0767 (2) | 0.0648 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ir1 | 0.02945 (6) | 0.02304 (6) | 0.03234 (6) | 0.00983 (4) | 0.01330 (4) | 0.00644 (4) |
N2 | 0.0359 (11) | 0.0205 (9) | 0.0327 (11) | 0.0110 (8) | 0.0149 (9) | 0.0077 (8) |
C3 | 0.0389 (14) | 0.0251 (12) | 0.0409 (15) | 0.0156 (11) | 0.0162 (12) | 0.0088 (11) |
C4 | 0.0483 (16) | 0.0229 (12) | 0.0493 (17) | 0.0149 (12) | 0.0201 (14) | 0.0088 (12) |
C5 | 0.0453 (16) | 0.0235 (13) | 0.0612 (19) | 0.0071 (11) | 0.0263 (15) | 0.0099 (12) |
C6 | 0.0369 (14) | 0.0271 (13) | 0.0560 (18) | 0.0100 (11) | 0.0222 (13) | 0.0093 (12) |
C7 | 0.0353 (13) | 0.0233 (11) | 0.0343 (13) | 0.0112 (10) | 0.0178 (11) | 0.0069 (10) |
C8 | 0.0340 (13) | 0.0240 (11) | 0.0355 (13) | 0.0107 (10) | 0.0185 (11) | 0.0081 (10) |
C9 | 0.0336 (13) | 0.0249 (12) | 0.0361 (14) | 0.0117 (10) | 0.0168 (11) | 0.0088 (10) |
C10 | 0.0370 (14) | 0.0227 (12) | 0.0522 (17) | 0.0102 (10) | 0.0209 (13) | 0.0079 (11) |
C11 | 0.0422 (15) | 0.0260 (13) | 0.0557 (18) | 0.0140 (11) | 0.0255 (14) | 0.0138 (12) |
C12 | 0.0397 (15) | 0.0357 (15) | 0.0559 (19) | 0.0194 (12) | 0.0201 (14) | 0.0181 (13) |
C13 | 0.0361 (14) | 0.0310 (13) | 0.0416 (15) | 0.0125 (11) | 0.0165 (12) | 0.0113 (11) |
C14 | 0.057 (2) | 0.0304 (17) | 0.159 (5) | 0.0059 (16) | 0.053 (3) | 0.021 (2) |
C15 | 0.060 (2) | 0.0298 (15) | 0.085 (3) | 0.0231 (14) | 0.0397 (19) | 0.0184 (16) |
F16 | 0.0793 (17) | 0.0376 (11) | 0.170 (3) | 0.0179 (11) | 0.0682 (19) | 0.0377 (15) |
F17 | 0.245 (4) | 0.0408 (13) | 0.141 (3) | 0.059 (2) | 0.134 (3) | 0.0245 (15) |
F18 | 0.098 (2) | 0.0503 (14) | 0.146 (3) | 0.0419 (14) | 0.0219 (19) | 0.0427 (16) |
C19 | 0.0427 (17) | 0.0423 (17) | 0.057 (2) | 0.0148 (14) | 0.0092 (15) | 0.0157 (15) |
F20 | 0.0406 (11) | 0.0589 (13) | 0.1015 (18) | 0.0074 (9) | 0.0287 (11) | 0.0243 (12) |
F21 | 0.0719 (15) | 0.0548 (13) | 0.0567 (13) | 0.0155 (11) | −0.0001 (11) | −0.0062 (10) |
F22 | 0.0555 (13) | 0.0632 (14) | 0.0864 (17) | 0.0184 (11) | −0.0105 (12) | 0.0251 (12) |
N23 | 0.0298 (11) | 0.0281 (11) | 0.0356 (12) | 0.0076 (9) | 0.0119 (9) | 0.0017 (9) |
C24 | 0.0470 (17) | 0.0455 (17) | 0.0396 (16) | 0.0099 (14) | 0.0193 (14) | 0.0002 (13) |
C25 | 0.0469 (17) | 0.0432 (17) | 0.0467 (18) | 0.0044 (14) | 0.0198 (14) | −0.0115 (14) |
C26 | 0.0421 (16) | 0.0297 (14) | 0.060 (2) | 0.0055 (12) | 0.0210 (15) | −0.0028 (13) |
C27 | 0.0418 (16) | 0.0294 (14) | 0.0532 (18) | 0.0073 (12) | 0.0213 (14) | 0.0042 (12) |
C28 | 0.0264 (12) | 0.0291 (13) | 0.0388 (14) | 0.0080 (10) | 0.0115 (11) | 0.0036 (11) |
C29 | 0.0287 (12) | 0.0287 (12) | 0.0351 (14) | 0.0107 (10) | 0.0106 (10) | 0.0062 (10) |
C30 | 0.0285 (12) | 0.0265 (12) | 0.0318 (13) | 0.0113 (10) | 0.0107 (10) | 0.0078 (10) |
C31 | 0.0374 (14) | 0.0285 (13) | 0.0371 (14) | 0.0085 (11) | 0.0157 (12) | 0.0056 (11) |
C32 | 0.0392 (15) | 0.0385 (15) | 0.0340 (14) | 0.0109 (12) | 0.0137 (12) | 0.0040 (11) |
C33 | 0.0416 (15) | 0.0409 (15) | 0.0418 (16) | 0.0127 (12) | 0.0226 (13) | 0.0113 (12) |
C34 | 0.0310 (13) | 0.0356 (14) | 0.0402 (15) | 0.0104 (11) | 0.0160 (11) | 0.0134 (11) |
C35 | 0.079 (3) | 0.0299 (16) | 0.091 (3) | 0.0001 (17) | 0.042 (2) | −0.0109 (17) |
C36 | 0.070 (2) | 0.053 (2) | 0.0418 (19) | 0.0057 (18) | 0.0253 (17) | −0.0032 (15) |
F37 | 0.222 (5) | 0.134 (3) | 0.100 (2) | −0.107 (3) | 0.098 (3) | −0.074 (2) |
F38 | 0.127 (3) | 0.227 (5) | 0.164 (4) | 0.057 (3) | 0.037 (3) | −0.126 (4) |
F39 | 0.375 (8) | 0.101 (3) | 0.0358 (15) | 0.055 (4) | −0.003 (3) | −0.0066 (16) |
C40 | 0.0473 (17) | 0.0408 (16) | 0.0519 (19) | 0.0063 (13) | 0.0257 (15) | 0.0100 (14) |
F41 | 0.0373 (10) | 0.0578 (12) | 0.0718 (14) | −0.0018 (9) | 0.0198 (10) | 0.0047 (10) |
F42 | 0.0751 (15) | 0.0686 (14) | 0.0758 (15) | −0.0053 (12) | 0.0525 (13) | 0.0081 (12) |
F43 | 0.0744 (15) | 0.0389 (11) | 0.0836 (16) | 0.0148 (10) | 0.0338 (12) | 0.0250 (10) |
N44 | 0.0320 (11) | 0.0318 (11) | 0.0343 (12) | 0.0114 (9) | 0.0133 (9) | 0.0081 (9) |
C45 | 0.0378 (14) | 0.0402 (15) | 0.0371 (15) | 0.0145 (12) | 0.0149 (12) | 0.0081 (12) |
C46 | 0.0395 (16) | 0.0484 (18) | 0.0451 (17) | 0.0198 (13) | 0.0143 (13) | 0.0079 (14) |
N47 | 0.0589 (18) | 0.082 (2) | 0.0509 (17) | 0.0445 (18) | 0.0234 (15) | 0.0273 (16) |
C48 | 0.064 (2) | 0.083 (3) | 0.049 (2) | 0.044 (2) | 0.0262 (18) | 0.0326 (19) |
C49 | 0.0426 (16) | 0.0434 (16) | 0.0371 (15) | 0.0166 (13) | 0.0158 (13) | 0.0119 (12) |
C50 | 0.054 (2) | 0.087 (3) | 0.059 (2) | 0.042 (2) | 0.0242 (18) | 0.017 (2) |
C51 | 0.0473 (17) | 0.0476 (17) | 0.0416 (16) | 0.0182 (14) | 0.0211 (14) | 0.0133 (13) |
O52 | 0.0465 (12) | 0.0419 (11) | 0.0398 (11) | 0.0198 (9) | 0.0224 (9) | 0.0114 (9) |
O53 | 0.0802 (19) | 0.094 (2) | 0.0504 (14) | 0.0460 (16) | 0.0411 (14) | 0.0379 (14) |
Ir1—C30 | 1.993 (3) | C25—H25 | 0.93 |
Ir1—C9 | 1.999 (3) | C26—C27 | 1.395 (5) |
Ir1—N23 | 2.028 (2) | C26—C35 | 1.502 (4) |
Ir1—N2 | 2.035 (2) | C27—C28 | 1.400 (4) |
Ir1—N44 | 2.147 (2) | C27—H27 | 0.93 |
Ir1—O52 | 2.149 (2) | C28—C29 | 1.480 (4) |
N2—C3 | 1.347 (3) | C29—C34 | 1.413 (4) |
N2—C7 | 1.370 (3) | C29—C30 | 1.427 (4) |
C3—C4 | 1.371 (4) | C30—C31 | 1.400 (4) |
C3—H3 | 0.93 | C31—C32 | 1.388 (4) |
C4—C5 | 1.381 (4) | C31—H31 | 0.93 |
C4—H4 | 0.93 | C32—C33 | 1.374 (4) |
C5—C6 | 1.388 (4) | C32—C36 | 1.490 (4) |
C5—C14 | 1.509 (4) | C33—C34 | 1.388 (4) |
C6—C7 | 1.377 (4) | C33—H33 | 0.93 |
C6—H6 | 0.93 | C34—C40 | 1.508 (4) |
C7—C8 | 1.485 (3) | C35—H35A | 0.96 |
C8—C9 | 1.414 (4) | C35—H35B | 0.96 |
C8—C13 | 1.414 (4) | C35—H35C | 0.96 |
C9—C10 | 1.398 (3) | C36—F37 | 1.241 (5) |
C10—C11 | 1.376 (4) | C36—F38 | 1.264 (5) |
C10—H10 | 0.93 | C36—F39 | 1.270 (5) |
C11—C12 | 1.386 (4) | C40—F41 | 1.332 (4) |
C11—C15 | 1.493 (4) | C40—F42 | 1.334 (4) |
C12—C13 | 1.389 (4) | C40—F43 | 1.351 (4) |
C12—H12 | 0.93 | N44—C45 | 1.339 (4) |
C13—C19 | 1.507 (4) | N44—C49 | 1.342 (4) |
C14—H14A | 0.96 | C45—C46 | 1.386 (4) |
C14—H14B | 0.96 | C45—H45 | 0.93 |
C14—H14C | 0.96 | C46—N47 | 1.334 (4) |
C15—F17 | 1.285 (5) | C46—C50 | 1.489 (5) |
C15—F16 | 1.312 (4) | N47—C48 | 1.333 (5) |
C15—F18 | 1.330 (5) | C48—C49 | 1.381 (4) |
C19—F20 | 1.333 (4) | C48—H48 | 0.93 |
C19—F22 | 1.334 (4) | C49—C51 | 1.504 (4) |
C19—F21 | 1.346 (4) | C50—H50A | 0.96 |
N23—C24 | 1.347 (4) | C50—H50B | 0.96 |
N23—C28 | 1.361 (4) | C50—H50C | 0.96 |
C24—C25 | 1.373 (5) | C51—O53 | 1.228 (4) |
C24—H24 | 0.93 | C51—O52 | 1.280 (4) |
C25—C26 | 1.387 (5) | ||
C30—Ir1—C9 | 88.44 (11) | C24—C25—C26 | 119.6 (3) |
C30—Ir1—N23 | 79.81 (10) | C24—C25—H25 | 120.2 |
C9—Ir1—N23 | 92.01 (10) | C26—C25—H25 | 120.2 |
C30—Ir1—N2 | 99.81 (10) | C25—C26—C27 | 117.2 (3) |
C9—Ir1—N2 | 79.63 (10) | C25—C26—C35 | 122.3 (3) |
N23—Ir1—N2 | 171.64 (8) | C27—C26—C35 | 120.4 (3) |
C30—Ir1—N44 | 97.99 (10) | C26—C27—C28 | 121.5 (3) |
C9—Ir1—N44 | 173.03 (9) | C26—C27—H27 | 119.2 |
N23—Ir1—N44 | 91.77 (9) | C28—C27—H27 | 119.2 |
N2—Ir1—N44 | 96.54 (9) | N23—C28—C27 | 119.2 (3) |
C30—Ir1—O52 | 173.79 (9) | N23—C28—C29 | 112.9 (2) |
C9—Ir1—O52 | 96.65 (9) | C27—C28—C29 | 127.7 (3) |
N23—Ir1—O52 | 96.41 (9) | C34—C29—C30 | 118.8 (2) |
N2—Ir1—O52 | 84.65 (9) | C34—C29—C28 | 128.4 (2) |
N44—Ir1—O52 | 77.10 (8) | C30—C29—C28 | 112.8 (2) |
C3—N2—C7 | 118.7 (2) | C31—C30—C29 | 118.9 (2) |
C3—N2—Ir1 | 123.82 (19) | C31—C30—Ir1 | 125.1 (2) |
C7—N2—Ir1 | 116.56 (16) | C29—C30—Ir1 | 115.97 (19) |
N2—C3—C4 | 122.8 (3) | C32—C31—C30 | 120.7 (3) |
N2—C3—H3 | 118.6 | C32—C31—H31 | 119.7 |
C4—C3—H3 | 118.6 | C30—C31—H31 | 119.7 |
C3—C4—C5 | 119.5 (3) | C33—C32—C31 | 120.6 (3) |
C3—C4—H4 | 120.2 | C33—C32—C36 | 119.5 (3) |
C5—C4—H4 | 120.2 | C31—C32—C36 | 119.8 (3) |
C4—C5—C6 | 117.3 (3) | C32—C33—C34 | 120.5 (3) |
C4—C5—C14 | 121.9 (3) | C32—C33—H33 | 119.7 |
C6—C5—C14 | 120.8 (3) | C34—C33—H33 | 119.7 |
C7—C6—C5 | 121.9 (3) | C33—C34—C29 | 120.3 (3) |
C7—C6—H6 | 119.1 | C33—C34—C40 | 115.4 (3) |
C5—C6—H6 | 119.1 | C29—C34—C40 | 124.3 (3) |
N2—C7—C6 | 119.4 (2) | C26—C35—H35A | 109.5 |
N2—C7—C8 | 113.0 (2) | C26—C35—H35B | 109.5 |
C6—C7—C8 | 127.5 (2) | H35A—C35—H35B | 109.5 |
C9—C8—C13 | 119.7 (2) | C26—C35—H35C | 109.5 |
C9—C8—C7 | 112.8 (2) | H35A—C35—H35C | 109.5 |
C13—C8—C7 | 127.4 (2) | H35B—C35—H35C | 109.5 |
C10—C9—C8 | 117.9 (2) | F37—C36—F38 | 104.0 (5) |
C10—C9—Ir1 | 125.5 (2) | F37—C36—F39 | 106.9 (5) |
C8—C9—Ir1 | 116.52 (18) | F38—C36—F39 | 101.3 (5) |
C11—C10—C9 | 121.6 (3) | F37—C36—C32 | 116.6 (3) |
C11—C10—H10 | 119.2 | F38—C36—C32 | 113.4 (4) |
C9—C10—H10 | 119.2 | F39—C36—C32 | 113.1 (3) |
C10—C11—C12 | 120.7 (3) | F41—C40—F42 | 105.4 (3) |
C10—C11—C15 | 119.7 (3) | F41—C40—F43 | 106.7 (3) |
C12—C11—C15 | 119.6 (3) | F42—C40—F43 | 105.9 (3) |
C11—C12—C13 | 119.4 (3) | F41—C40—C34 | 113.2 (3) |
C11—C12—H12 | 120.3 | F42—C40—C34 | 112.4 (3) |
C13—C12—H12 | 120.3 | F43—C40—C34 | 112.8 (3) |
C12—C13—C8 | 120.3 (3) | C45—N44—C49 | 117.6 (2) |
C12—C13—C19 | 114.0 (3) | C45—N44—Ir1 | 129.33 (19) |
C8—C13—C19 | 125.7 (2) | C49—N44—Ir1 | 113.06 (19) |
C5—C14—H14A | 109.5 | N44—C45—C46 | 121.8 (3) |
C5—C14—H14B | 109.5 | N44—C45—H45 | 119.1 |
H14A—C14—H14B | 109.5 | C46—C45—H45 | 119.1 |
C5—C14—H14C | 109.5 | N47—C46—C45 | 121.2 (3) |
H14A—C14—H14C | 109.5 | N47—C46—C50 | 116.8 (3) |
H14B—C14—H14C | 109.5 | C45—C46—C50 | 121.9 (3) |
F17—C15—F16 | 107.5 (4) | C48—N47—C46 | 116.1 (3) |
F17—C15—F18 | 105.2 (3) | N47—C48—C49 | 123.9 (3) |
F16—C15—F18 | 103.8 (3) | N47—C48—H48 | 118.1 |
F17—C15—C11 | 113.1 (3) | C49—C48—H48 | 118.1 |
F16—C15—C11 | 113.5 (3) | N44—C49—C48 | 119.4 (3) |
F18—C15—C11 | 112.8 (3) | N44—C49—C51 | 117.7 (3) |
F20—C19—F22 | 106.2 (3) | C48—C49—C51 | 123.0 (3) |
F20—C19—F21 | 106.5 (3) | C46—C50—H50A | 109.5 |
F22—C19—F21 | 105.2 (3) | C46—C50—H50B | 109.5 |
F20—C19—C13 | 113.1 (3) | H50A—C50—H50B | 109.5 |
F22—C19—C13 | 112.3 (3) | C46—C50—H50C | 109.5 |
F21—C19—C13 | 112.9 (3) | H50A—C50—H50C | 109.5 |
C24—N23—C28 | 119.3 (2) | H50B—C50—H50C | 109.5 |
C24—N23—Ir1 | 122.1 (2) | O53—C51—O52 | 125.7 (3) |
C28—N23—Ir1 | 116.99 (18) | O53—C51—C49 | 118.9 (3) |
N23—C24—C25 | 123.0 (3) | O52—C51—C49 | 115.4 (3) |
N23—C24—H24 | 118.5 | C51—O52—Ir1 | 116.56 (19) |
C25—C24—H24 | 118.5 |
Ir1—C30 | 1.993 (3) | Ir1—N2 | 2.035 (2) |
Ir1—C9 | 1.999 (3) | Ir1—N44 | 2.147 (2) |
Ir1—N23 | 2.028 (2) | Ir1—O52 | 2.149 (2) |
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