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Acta Crystallogr Sect E Struct Rep Online. 2011 September 1; 67(Pt 9): m1199–m1200.
Published online 2011 August 6. doi:  10.1107/S1600536811030856
PMCID: PMC3200786
Copyright © Kim et al. 2011
Bis[3,5-difluoro-2-(4-methyl­pyridin-2-yl)phenyl-κ2 C 1,N](picolinato-κ2 N,O)iridium(III) chloro­form monosolvate
Young-Inn Kim,a Hoe-Joo Seo,b Seong-Jae Yun,b Young-Kwang Song,a In-Chan Kim,b and Sung Kwon Kangc*
aDepartment of Chemistry Education and Interdisciplinary Program of Advanced Information and Display Materials, Pusan National University, Busan 609-735, Republic of Korea
bDepartment of Chemistry, Pusan National University, Busan 609-735, Republic of Korea
cDepartment of Chemistry, Chungnam National University, Daejeon 305-764, Republic of Korea
Correspondence e-mail: skkang/at/cnu.ac.kr
Received July 26, 2011; Accepted August 1, 2011.
This is an open-access article distributed under the terms of the Creative Commons Attribution Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Abstract
In the title complex, [Ir(C12H8F2N)2(C6H4NO2)]·CHCl3, two similar mol­ecules of each component comprise the asymmetric unit. The independent complex mol­ecules are linked by inter­molecular π–π inter­actions [centroid–centroid distance = 3.830 (4) Å]. The IrIII ion adopts a distorted octa­hedral geometry, being coordinated by three N atoms, two C atoms, and one O atom of three bidentate ligands, with the N atoms arranged meridionally.
Related literature
For general background to luminescent Ir complexes, see: Ulbricht et al. (2009 [triangle]); Chi & Chou (2010 [triangle]). For phenyl­pyridine Ir complexes, see: Lyu et al. (2006 [triangle]); Nazeeruddin et al. (2003 [triangle]); Seo et al. (2010 [triangle]); Sasabe & Kido (2011 [triangle]); Aoki et al. (2011 [triangle]). For phospho­rescent Ir complexes, see: Takizawa et al. (2006 [triangle]); Xu et al. (2009 [triangle]). For the Suzuki coupling reaction, see: Miyaura & Suzuki (1995 [triangle]).
An external file that holds a picture, illustration, etc. Object name is e-67-m1199-scheme1.jpg Object name is e-67-m1199-scheme1.jpg
Crystal data
  • [Ir(C12H8F2N)2(C6H4NO2)]·CHCl3
  • M r = 842.06
  • Triclinic, An external file that holds a picture, illustration, etc. Object name is e-67-m1199-efi1.jpg
  • a = 13.421 (2) Å
  • b = 15.020 (5) Å
  • c = 16.291 (5) Å
  • α = 85.61 (4)°
  • β = 68.85 (5)°
  • γ = 89.26 (3)°
  • V = 3053.6 (18) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 4.69 mm−1
  • T = 170 K
  • 0.14 × 0.13 × 0.09 mm
Data collection
  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2002 [triangle]) T min = 0.502, T max = 0.665
  • 54485 measured reflections
  • 11349 independent reflections
  • 9557 reflections with I > 2σ(I)
  • R int = 0.038
Refinement
  • R[F 2 > 2σ(F 2)] = 0.033
  • wR(F 2) = 0.090
  • S = 1.03
  • 11349 reflections
  • 797 parameters
  • H-atom parameters constrained
  • Δρmax = 2.76 e Å−3
  • Δρmin = −1.28 e Å−3
Data collection: SMART (Bruker, 2002 [triangle]); cell refinement: SAINT (Bruker, 2002 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).
​
Table 1
Table 1
Selected geometric parameters (Å, °)
Supplementary Material
Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811030856/tk2773sup1.cif
Click here to view.(33K, cif)
Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811030856/tk2773Isup2.hkl
Click here to view.(544K, hkl)
Additional supplementary materials: crystallographic information; 3D view; checkCIF report
Acknowledgments
This work was supported by the National Research Foundation of Korea (NRF) Grant funded by the Ministry of Education, Science and Technology (No. 2010–0017080).
supplementary crystallographic information
Comment
There has been a growing interest in luminescent iridium complexes (Ulbricht et al., 2009) because of their high quantum efficiency and tunable emission energy (Chi & Chou, 2010). Especially, 2-phenylpyridine-based cyclometallated iridium(III) complexes have been reported (Lyu et al., 2006; Nazeeruddin et al., 2003; Seo et al., 2010; Sasabe et al., 2011; Aoki et al., 2011) and proved to be excellent candidates for organic light-emitting diodes (OLEDs) in full color display by doping red, green to blue iridium(III) phosphors in host matrix. But pure blue emissive materials with high phosphorescence efficiency are still rare comparing to red and green ones. Recently, blue phosphorescent iridium(III) complexes bearing 2-(fluoro substituted phenyl)-4-methylpyridine were reported (Takizawa et al., 2006; Xu et al., 2009) and their photophysical properties were discussed. Herein, we prepared a blue emissive titled complex and its structure is reported.
In (I), two similar complex molecules and two chloroform comprise the asymmetric unit, which are linked by the intermolecular π-π interactions (centroid-centroid distance = 3.830 (4) Å) between the aromatic rings of the discrete units (Fig. 1 and Table 1). The IrIII ion adopts a distorted octahedral geometry, being coordinated by three N atoms, two C atoms, and one O atom of three bidentate ligands. The angles around Ir atoms are in the range of 76.70 (16) – 99.14 (19) °. The Ir—C bond distances of 1.979 (5) – 1.995 (6) Å are shorter than the Ir—N distances of 2.019 (4) -2.125 (5) Å due to the stronger trans influence of the phenyl ring compared to the pyridine ring (Table 1). The N atoms of each dfpmpy ligand adopt a meridional arrangement.
Experimental
Synthesis of 2-(2,4-difluorophenyl)-4-methylpyridine (dfpmpy): dfpmpy was prepared by Suzuki coupling reaction using 2,4-difluorophenylboronic acid and the appropriate 2-bromo-4-methylpyridine(Miyaura & Suzuki, 1995). 2-Bromo-4-methylpyridine, 2,4-difluorophenylboronic acid and tetrakis(triphenylphosphine)palladium(0) were dissolved to 50 ml of THF. After 30 ml of aqueous 2M Na2CO3 was delivered, the reaction mixture was heated at 343 K for 24 h. The crude product was flash chromatographed on silica gel using n-hexane/ethyl acetate as an eluent.
Synthesis of title complex: Cyclometallated iridium(III) µ-chloro-bridged dimer, [(dfpmpy)2Ir(µ-Cl)]2, was prepared from the reaction of IrCl3 3H2O with dfpmpy in a 3:1 mixture of 2-ethoxyethanol and water at 398 K for 24 h. The dimeric iridium(III) complex, sodium carbonate and picolinic acid were dissolved 2-ethoxyethanol, and the mixture was heated at 403 K for 24 h. The mixture extracted with dichloromethane and dried over anhydrous magnesium sulfate. The crude product was flash chromatographed on silica gel using dichloromethane/methanol as an eluent. The yellow crystals were grown from its ethanol/chloroform solution by slow evaporation at room temperature.
Refinement
All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 - 0.98 Å, and with Uiso(H) = 1.2Ueq(C) for aromatic- and chloroform-H atoms, and 1.5Ueq(C) for methyl-H atoms. The maximum and minimum residual electron density peaks were located at 0.84 and 0.87 Å from the Ir2 and Cl1 atoms, respectively.
Figures
Fig. 1.
Fig. 1.
Molecular structures of the four independent molecules in (I), showing the atom-numbering scheme and 30% probability ellipsoids. The complex molecules are linked by π-π interactions (dashed lines). H atoms have been omitted for clarity. (more ...)
Crystal data
[Ir(C12H8F2N)2(C6H4NO2)]·CHCl3Z = 4
Mr = 842.06F(000) = 1632
Triclinic, P1Dx = 1.832 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 13.421 (2) ÅCell parameters from 8556 reflections
b = 15.020 (5) Åθ = 2.4–28.2°
c = 16.291 (5) ŵ = 4.69 mm−1
α = 85.61 (4)°T = 170 K
β = 68.85 (5)°Block, yellow
γ = 89.26 (3)°0.14 × 0.13 × 0.09 mm
V = 3053.6 (18) Å3
Data collection
Bruker SMART CCD area-detector diffractometer9557 reflections with I > 2σ(I)
[var phi] and ω scansRint = 0.038
Absorption correction: multi-scan (SADABS; Bruker, 2002)θmax = 25.5°, θmin = 1.6°
Tmin = 0.502, Tmax = 0.665h = −16→16
54485 measured reflectionsk = −18→18
11349 independent reflectionsl = −19→19
Refinement
Refinement on F20 restraints
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.033w = 1/[σ2(Fo2) + (0.0433P)2 + 10.7327P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.090(Δ/σ)max = 0.002
S = 1.03Δρmax = 2.76 e Å−3
11349 reflectionsΔρmin = −1.28 e Å−3
797 parameters
Special details
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.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
xyzUiso*/Ueq
Ir10.401921 (17)0.127006 (13)0.272846 (13)0.03178 (7)
N10.2687 (3)0.1283 (3)0.3844 (3)0.0308 (9)
C20.2679 (4)0.1269 (4)0.4673 (4)0.0362 (12)
H20.3330.12650.47550.043*
C30.1764 (5)0.1260 (4)0.5397 (4)0.0410 (13)
H30.17970.12380.59590.049*
C40.0787 (5)0.1285 (4)0.5295 (4)0.0435 (14)
C50.0793 (5)0.1313 (4)0.4446 (4)0.0442 (14)
H50.01460.13320.43570.053*
C60.1727 (4)0.1316 (4)0.3727 (4)0.0349 (12)
C70.1850 (5)0.1371 (4)0.2791 (4)0.0385 (13)
C80.2903 (5)0.1417 (4)0.2189 (4)0.0376 (13)
C90.3059 (6)0.1527 (4)0.1297 (4)0.0522 (17)
H90.37470.15850.08790.063*
C100.2206 (7)0.1552 (5)0.1035 (5)0.064 (2)
C110.1183 (7)0.1485 (5)0.1598 (5)0.065 (2)
H110.06150.14970.13990.078*
C120.1027 (5)0.1400 (5)0.2474 (5)0.0528 (17)
C13−0.0236 (5)0.1297 (5)0.6073 (5)0.0603 (19)
H13A−0.07790.15720.5890.09*
H13B−0.01310.16320.65150.09*
H13C−0.04520.06970.63120.09*
F140.0006 (3)0.1328 (3)0.3045 (3)0.0715 (12)
F150.2387 (4)0.1630 (4)0.0157 (3)0.0980 (19)
N160.5221 (4)0.1191 (3)0.1547 (3)0.0371 (11)
C170.5798 (6)0.1900 (4)0.1074 (4)0.0537 (17)
H170.56730.24540.13080.064*
C180.6564 (6)0.1834 (4)0.0259 (4)0.0582 (19)
H180.69660.2335−0.00460.07*
C190.6744 (5)0.1021 (5)−0.0113 (4)0.0497 (16)
C200.6134 (5)0.0297 (4)0.0377 (4)0.0441 (14)
H200.6232−0.02570.01420.053*
C210.5383 (5)0.0381 (4)0.1208 (4)0.0361 (12)
C220.4690 (4)−0.0320 (4)0.1802 (4)0.0343 (12)
C230.3943 (4)−0.0029 (3)0.2598 (4)0.0317 (11)
C240.3277 (4)−0.0667 (4)0.3210 (4)0.0347 (12)
H240.2779−0.04970.37370.042*
C250.3361 (4)−0.1545 (4)0.3030 (4)0.0377 (13)
C260.4064 (5)−0.1847 (4)0.2266 (4)0.0457 (15)
H260.4093−0.24480.21580.055*
C270.4721 (5)−0.1219 (4)0.1668 (4)0.0433 (14)
C280.7599 (6)0.0929 (5)−0.1003 (4)0.0618 (19)
H28A0.77880.1508−0.13130.093*
H28B0.73370.0557−0.13370.093*
H28C0.82180.0663−0.09280.093*
F290.5416 (3)−0.1517 (2)0.0920 (3)0.0639 (11)
F300.2726 (3)−0.2159 (2)0.3643 (3)0.0501 (9)
N310.5127 (3)0.1215 (3)0.3388 (3)0.0306 (10)
C320.5541 (4)0.0478 (4)0.3645 (4)0.0368 (13)
H320.5367−0.00760.35110.044*
C330.6221 (5)0.0523 (4)0.4105 (4)0.0450 (14)
H330.650.00030.42790.054*
C340.6486 (5)0.1338 (4)0.4307 (5)0.0468 (15)
H340.69310.13770.46280.056*
C350.6076 (4)0.2094 (4)0.4025 (4)0.0422 (14)
H350.62560.26540.41410.051*
C360.5403 (4)0.2019 (4)0.3572 (4)0.0349 (12)
C370.4926 (4)0.2819 (4)0.3238 (4)0.0368 (13)
O380.4333 (3)0.2655 (2)0.2815 (3)0.0375 (9)
O390.5156 (3)0.3572 (3)0.3383 (3)0.0510 (11)
Ir20.178581 (16)0.386356 (13)0.679992 (13)0.02913 (7)
N400.1713 (3)0.3834 (3)0.5569 (3)0.0268 (9)
C410.2550 (4)0.3808 (4)0.4814 (3)0.0335 (12)
H410.3230.37980.48420.04*
C420.2466 (4)0.3797 (4)0.4009 (4)0.0346 (12)
H420.30780.37860.35040.042*
C430.1472 (4)0.3803 (4)0.3943 (4)0.0336 (12)
C440.0600 (4)0.3812 (4)0.4718 (3)0.0328 (12)
H44−0.00840.38070.46980.039*
C450.0721 (4)0.3830 (3)0.5524 (3)0.0291 (11)
C46−0.0133 (4)0.3818 (3)0.6390 (3)0.0310 (11)
C470.0211 (4)0.3779 (3)0.7112 (3)0.0320 (11)
C48−0.0575 (5)0.3710 (4)0.7972 (4)0.0379 (13)
H48−0.0380.36740.84660.045*
C49−0.1628 (5)0.3698 (4)0.8062 (4)0.0435 (15)
C50−0.1982 (5)0.3752 (4)0.7375 (4)0.0421 (14)
H50−0.27070.37460.74650.051*
C51−0.1219 (4)0.3814 (4)0.6550 (4)0.0356 (12)
C520.1340 (5)0.3769 (4)0.3067 (3)0.0411 (13)
H52A0.11720.43530.28750.062*
H52B0.07710.33590.31280.062*
H52C0.19930.35750.2640.062*
F53−0.1575 (2)0.3876 (3)0.5867 (2)0.0478 (9)
F54−0.2367 (3)0.3645 (3)0.8902 (2)0.0608 (11)
N550.1675 (4)0.3956 (3)0.8060 (3)0.0356 (10)
C560.1626 (6)0.3235 (4)0.8620 (4)0.0542 (18)
H560.16840.26690.84150.065*
C570.1492 (7)0.3319 (5)0.9481 (4)0.061 (2)
H570.14670.28090.9850.073*
C580.1394 (5)0.4150 (4)0.9813 (4)0.0456 (15)
C590.1410 (5)0.4881 (4)0.9246 (4)0.0419 (14)
H590.1330.54490.94510.05*
C600.1545 (4)0.4783 (4)0.8368 (4)0.0347 (12)
C610.1553 (4)0.5487 (3)0.7692 (3)0.0317 (11)
C620.1638 (4)0.5172 (3)0.6865 (3)0.0283 (11)
C630.1660 (4)0.5807 (3)0.6188 (3)0.0307 (11)
H630.17370.56290.56340.037*
C640.1567 (4)0.6694 (4)0.6339 (4)0.0357 (12)
C650.1465 (4)0.7018 (4)0.7143 (4)0.0383 (13)
H650.13950.76240.72320.046*
C660.1475 (5)0.6394 (4)0.7791 (4)0.0385 (13)
C670.1316 (6)0.4252 (5)1.0748 (4)0.0583 (18)
H67A0.20060.4411.0750.088*
H67B0.10750.36981.10960.088*
H67C0.08180.47121.09920.088*
F680.1375 (3)0.6708 (2)0.8579 (2)0.0564 (10)
F690.1581 (3)0.7303 (2)0.5682 (2)0.0477 (8)
N700.3477 (4)0.3839 (3)0.6406 (3)0.0310 (10)
C710.4140 (5)0.4543 (4)0.6265 (4)0.0366 (12)
H710.38590.51140.63190.044*
C720.5216 (5)0.4444 (4)0.6044 (4)0.0420 (14)
H720.56570.49440.59530.05*
C730.5651 (5)0.3603 (4)0.5958 (4)0.0425 (14)
H730.63830.35280.58010.051*
C740.4968 (5)0.2875 (4)0.6110 (4)0.0420 (14)
H740.52360.230.6060.05*
C750.3891 (4)0.3013 (4)0.6337 (3)0.0331 (12)
C760.3098 (5)0.2256 (4)0.6528 (4)0.0387 (13)
O770.2124 (3)0.2462 (2)0.6793 (3)0.0362 (9)
O780.3444 (4)0.1485 (3)0.6427 (3)0.0525 (12)
C790.8189 (8)−0.0330 (6)0.1973 (6)0.081 (3)
H790.7683−0.05320.25610.097*
Cl10.9438 (3)−0.0490 (3)0.1971 (3)0.185 (2)
Cl20.7860 (4)−0.0820 (2)0.1244 (3)0.1664 (19)
Cl30.8030 (2)0.08722 (18)0.1801 (2)0.1093 (9)
C830.4763 (7)0.5241 (6)0.8416 (5)0.074 (2)
H830.47980.55490.78540.089*
Cl40.4398 (3)0.41077 (18)0.84317 (19)0.1220 (12)
Cl50.5977 (2)0.5333 (3)0.8509 (3)0.1506 (16)
Cl60.37928 (17)0.57276 (14)0.92568 (17)0.0890 (8)
Atomic displacement parameters (Å2)
U11U22U33U12U13U23
Ir10.03765 (12)0.02222 (11)0.03306 (12)0.00448 (8)−0.00911 (9)−0.00650 (8)
N10.032 (2)0.025 (2)0.036 (2)0.0037 (18)−0.0122 (19)−0.0071 (18)
C20.031 (3)0.037 (3)0.042 (3)−0.001 (2)−0.013 (2)−0.012 (2)
C30.040 (3)0.045 (3)0.037 (3)−0.001 (3)−0.011 (3)−0.013 (3)
C40.036 (3)0.042 (3)0.049 (4)0.001 (3)−0.009 (3)−0.011 (3)
C50.038 (3)0.043 (4)0.053 (4)0.009 (3)−0.018 (3)−0.011 (3)
C60.038 (3)0.026 (3)0.044 (3)0.010 (2)−0.018 (3)−0.012 (2)
C70.050 (3)0.032 (3)0.042 (3)0.016 (3)−0.026 (3)−0.008 (2)
C80.048 (3)0.027 (3)0.040 (3)0.012 (2)−0.017 (3)−0.010 (2)
C90.067 (4)0.047 (4)0.044 (4)0.026 (3)−0.022 (3)−0.006 (3)
C100.090 (6)0.067 (5)0.044 (4)0.050 (4)−0.034 (4)−0.013 (3)
C110.080 (5)0.072 (5)0.062 (5)0.041 (4)−0.046 (4)−0.019 (4)
C120.050 (4)0.052 (4)0.063 (4)0.021 (3)−0.028 (3)−0.010 (3)
C130.043 (4)0.081 (5)0.050 (4)0.004 (3)−0.006 (3)−0.016 (4)
F140.054 (2)0.099 (4)0.076 (3)0.026 (2)−0.039 (2)−0.019 (2)
F150.120 (4)0.141 (5)0.047 (2)0.079 (4)−0.048 (3)−0.020 (3)
N160.045 (3)0.026 (2)0.033 (2)0.005 (2)−0.005 (2)−0.0022 (19)
C170.073 (5)0.026 (3)0.048 (4)0.000 (3)−0.003 (3)−0.005 (3)
C180.073 (5)0.033 (3)0.046 (4)−0.003 (3)0.003 (3)0.004 (3)
C190.054 (4)0.049 (4)0.038 (3)0.012 (3)−0.007 (3)−0.003 (3)
C200.050 (4)0.036 (3)0.043 (3)0.010 (3)−0.012 (3)−0.010 (3)
C210.044 (3)0.028 (3)0.035 (3)0.007 (2)−0.013 (2)−0.004 (2)
C220.042 (3)0.026 (3)0.036 (3)0.006 (2)−0.014 (2)−0.008 (2)
C230.035 (3)0.025 (3)0.039 (3)0.006 (2)−0.018 (2)−0.005 (2)
C240.033 (3)0.033 (3)0.041 (3)0.003 (2)−0.017 (2)−0.003 (2)
C250.036 (3)0.029 (3)0.050 (3)0.001 (2)−0.018 (3)−0.002 (2)
C260.056 (4)0.027 (3)0.059 (4)−0.001 (3)−0.026 (3)−0.006 (3)
C270.051 (4)0.034 (3)0.042 (3)0.007 (3)−0.012 (3)−0.013 (3)
C280.058 (4)0.069 (5)0.042 (4)0.013 (4)0.002 (3)−0.007 (3)
F290.085 (3)0.034 (2)0.054 (2)0.0088 (19)0.000 (2)−0.0191 (17)
F300.0468 (19)0.0295 (18)0.067 (2)−0.0055 (15)−0.0135 (18)0.0043 (16)
N310.026 (2)0.026 (2)0.036 (2)0.0017 (17)−0.0054 (19)−0.0080 (18)
C320.033 (3)0.027 (3)0.046 (3)0.000 (2)−0.008 (2)−0.005 (2)
C330.044 (3)0.033 (3)0.059 (4)0.003 (3)−0.020 (3)−0.007 (3)
C340.043 (3)0.041 (4)0.063 (4)0.000 (3)−0.025 (3)−0.007 (3)
C350.035 (3)0.035 (3)0.055 (4)−0.003 (2)−0.013 (3)−0.013 (3)
C360.032 (3)0.027 (3)0.038 (3)−0.002 (2)−0.002 (2)−0.008 (2)
C370.036 (3)0.028 (3)0.039 (3)0.001 (2)−0.003 (2)−0.006 (2)
O380.045 (2)0.0223 (19)0.044 (2)0.0054 (16)−0.0135 (19)−0.0068 (16)
O390.054 (3)0.025 (2)0.075 (3)0.0007 (18)−0.023 (2)−0.013 (2)
Ir20.03736 (12)0.02252 (11)0.02688 (11)0.00286 (8)−0.01019 (9)−0.00546 (8)
N400.028 (2)0.024 (2)0.027 (2)0.0011 (17)−0.0083 (18)−0.0061 (17)
C410.027 (3)0.038 (3)0.033 (3)0.005 (2)−0.007 (2)−0.006 (2)
C420.034 (3)0.035 (3)0.030 (3)0.007 (2)−0.006 (2)−0.008 (2)
C430.037 (3)0.029 (3)0.033 (3)0.002 (2)−0.009 (2)−0.008 (2)
C440.028 (3)0.035 (3)0.034 (3)−0.002 (2)−0.009 (2)−0.006 (2)
C450.033 (3)0.023 (3)0.031 (3)0.002 (2)−0.009 (2)−0.007 (2)
C460.033 (3)0.024 (3)0.033 (3)−0.001 (2)−0.006 (2)−0.005 (2)
C470.037 (3)0.025 (3)0.030 (3)−0.001 (2)−0.007 (2)−0.006 (2)
C480.046 (3)0.036 (3)0.024 (3)0.000 (2)−0.004 (2)−0.001 (2)
C490.046 (3)0.034 (3)0.033 (3)−0.006 (3)0.006 (3)−0.001 (2)
C500.032 (3)0.042 (3)0.041 (3)−0.009 (2)0.000 (3)−0.005 (3)
C510.037 (3)0.031 (3)0.036 (3)−0.004 (2)−0.008 (2)−0.009 (2)
C520.044 (3)0.049 (4)0.029 (3)0.002 (3)−0.012 (3)−0.008 (3)
F530.0309 (17)0.065 (2)0.046 (2)−0.0045 (16)−0.0109 (15)−0.0087 (17)
F540.052 (2)0.069 (3)0.037 (2)−0.0077 (19)0.0119 (17)−0.0018 (18)
N550.048 (3)0.030 (2)0.030 (2)0.002 (2)−0.015 (2)−0.0056 (19)
C560.092 (5)0.033 (3)0.042 (4)0.016 (3)−0.029 (4)−0.005 (3)
C570.107 (6)0.042 (4)0.033 (3)0.015 (4)−0.027 (4)0.004 (3)
C580.057 (4)0.048 (4)0.035 (3)0.011 (3)−0.020 (3)−0.009 (3)
C590.051 (3)0.037 (3)0.038 (3)0.010 (3)−0.016 (3)−0.013 (3)
C600.038 (3)0.032 (3)0.034 (3)0.007 (2)−0.014 (2)−0.007 (2)
C610.038 (3)0.027 (3)0.031 (3)0.003 (2)−0.014 (2)−0.005 (2)
C620.025 (2)0.026 (3)0.033 (3)0.002 (2)−0.010 (2)−0.006 (2)
C630.031 (3)0.030 (3)0.033 (3)0.001 (2)−0.013 (2)−0.004 (2)
C640.034 (3)0.028 (3)0.047 (3)−0.002 (2)−0.019 (3)0.004 (2)
C650.041 (3)0.024 (3)0.049 (3)0.007 (2)−0.013 (3)−0.012 (2)
C660.046 (3)0.033 (3)0.039 (3)0.005 (2)−0.018 (3)−0.012 (2)
C670.076 (5)0.066 (5)0.034 (3)0.010 (4)−0.021 (3)−0.005 (3)
F680.097 (3)0.0344 (19)0.044 (2)0.0106 (19)−0.031 (2)−0.0183 (16)
F690.065 (2)0.0322 (18)0.049 (2)−0.0002 (16)−0.0263 (18)0.0072 (15)
N700.041 (2)0.025 (2)0.031 (2)0.0046 (19)−0.017 (2)−0.0096 (18)
C710.046 (3)0.029 (3)0.037 (3)0.003 (2)−0.017 (3)−0.005 (2)
C720.044 (3)0.037 (3)0.045 (3)−0.001 (3)−0.016 (3)−0.004 (3)
C730.042 (3)0.039 (3)0.051 (4)0.006 (3)−0.021 (3)−0.009 (3)
C740.052 (4)0.036 (3)0.044 (3)0.011 (3)−0.024 (3)−0.011 (3)
C750.046 (3)0.028 (3)0.030 (3)0.008 (2)−0.019 (2)−0.007 (2)
C760.057 (4)0.025 (3)0.042 (3)0.005 (3)−0.027 (3)−0.007 (2)
O770.045 (2)0.0233 (19)0.043 (2)0.0042 (16)−0.0189 (18)−0.0066 (16)
O780.058 (3)0.022 (2)0.088 (3)0.0081 (19)−0.038 (3)−0.011 (2)
C790.091 (6)0.090 (7)0.063 (5)−0.001 (5)−0.031 (5)−0.002 (5)
Cl10.087 (2)0.228 (5)0.236 (5)−0.040 (2)−0.076 (3)0.114 (4)
Cl20.284 (5)0.097 (2)0.201 (4)0.040 (3)−0.184 (4)−0.033 (2)
Cl30.110 (2)0.0724 (16)0.135 (2)0.0002 (14)−0.0281 (18)−0.0211 (16)
C830.078 (5)0.077 (6)0.052 (4)0.034 (4)−0.009 (4)0.002 (4)
Cl40.196 (3)0.0697 (16)0.0861 (17)0.0454 (18)−0.0315 (19)−0.0221 (13)
Cl50.0673 (16)0.206 (4)0.156 (3)0.018 (2)−0.0303 (18)0.067 (3)
Cl60.0665 (12)0.0554 (12)0.1098 (18)0.0003 (9)0.0135 (12)−0.0212 (11)
Geometric parameters (Å, °)
Ir1—C231.987 (5)Ir2—N702.125 (5)
Ir1—C81.995 (6)Ir2—O772.148 (4)
Ir1—N162.027 (5)N40—C411.336 (6)
Ir1—N12.040 (4)N40—C451.360 (7)
Ir1—N312.123 (5)C41—C421.358 (8)
Ir1—O382.153 (4)C41—H410.93
N1—C21.345 (7)C42—C431.377 (8)
N1—C61.369 (7)C42—H420.93
C2—C31.361 (8)C43—C441.378 (7)
C2—H20.93C43—C521.504 (8)
C3—C41.380 (8)C44—C451.383 (7)
C3—H30.93C44—H440.93
C4—C51.379 (9)C45—C461.460 (7)
C4—C131.495 (8)C46—C511.385 (8)
C5—C61.372 (8)C46—C471.407 (8)
C5—H50.93C47—C481.414 (7)
C6—C71.470 (8)C48—C491.367 (9)
C7—C121.377 (9)C48—H480.93
C7—C81.398 (8)C49—C501.361 (9)
C8—C91.389 (8)C49—F541.368 (6)
C9—C101.357 (10)C50—C511.362 (8)
C9—H90.93C50—H500.93
C10—C111.348 (11)C51—F531.357 (7)
C10—F151.357 (8)C52—H52A0.96
C11—C121.361 (10)C52—H52B0.96
C11—H110.93C52—H52C0.96
C12—F141.351 (8)N55—C561.347 (7)
C13—H13A0.96N55—C601.362 (7)
C13—H13B0.96C56—C571.364 (9)
C13—H13C0.96C56—H560.93
N16—C171.339 (7)C57—C581.385 (9)
N16—C211.356 (7)C57—H570.93
C17—C181.364 (9)C58—C591.375 (8)
C17—H170.93C58—C671.508 (8)
C18—C191.384 (9)C59—C601.395 (8)
C18—H180.93C59—H590.93
C19—C201.381 (9)C60—C611.464 (7)
C19—C281.506 (8)C61—C661.381 (8)
C20—C211.380 (8)C61—C621.429 (7)
C20—H200.93C62—C631.395 (7)
C21—C221.460 (8)C63—C641.369 (8)
C22—C271.382 (8)C63—H630.93
C22—C231.420 (8)C64—F691.347 (6)
C23—C241.394 (8)C64—C651.392 (8)
C24—C251.367 (8)C65—C661.361 (8)
C24—H240.93C65—H650.93
C25—F301.356 (6)C66—F681.362 (6)
C25—C261.369 (9)C67—H67A0.96
C26—C271.370 (9)C67—H67B0.96
C26—H260.93C67—H67C0.96
C27—F291.346 (7)N70—C711.343 (7)
C28—H28A0.96N70—C751.348 (7)
C28—H28B0.96C71—C721.366 (8)
C28—H28C0.96C71—H710.93
N31—C321.339 (7)C72—C731.380 (8)
N31—C361.354 (7)C72—H720.93
C32—C331.379 (8)C73—C741.384 (9)
C32—H320.93C73—H730.93
C33—C341.375 (8)C74—C751.375 (8)
C33—H330.93C74—H740.93
C34—C351.375 (9)C75—C761.504 (8)
C34—H340.93C76—O781.242 (7)
C35—C361.368 (8)C76—O771.263 (7)
C35—H350.93C79—Cl21.634 (10)
C36—C371.511 (8)C79—Cl11.690 (10)
C37—O391.237 (7)C79—Cl31.828 (10)
C37—O381.265 (7)C79—H790.98
Ir2—C621.979 (5)C83—Cl51.698 (10)
Ir2—C471.991 (5)C83—Cl61.716 (8)
Ir2—N552.019 (4)C83—Cl41.774 (10)
Ir2—N402.046 (4)C83—H830.98
C23—Ir1—C886.8 (2)C62—Ir2—N7096.78 (18)
C23—Ir1—N1680.4 (2)C47—Ir2—N70174.52 (18)
C8—Ir1—N1693.4 (2)N55—Ir2—N7089.37 (18)
C23—Ir1—N195.6 (2)N40—Ir2—N7097.20 (17)
C8—Ir1—N180.2 (2)C62—Ir2—O77172.13 (18)
N16—Ir1—N1172.69 (19)C47—Ir2—O7798.49 (18)
C23—Ir1—N3197.73 (19)N55—Ir2—O7794.91 (17)
C8—Ir1—N31174.22 (19)N40—Ir2—O7789.09 (16)
N16—Ir1—N3190.89 (18)N70—Ir2—O7776.80 (16)
N1—Ir1—N3195.75 (17)C41—N40—C45117.7 (4)
C23—Ir1—O38172.21 (18)C41—N40—Ir2125.8 (3)
C8—Ir1—O3899.14 (19)C45—N40—Ir2116.5 (3)
N16—Ir1—O3894.13 (17)N40—C41—C42123.9 (5)
N1—Ir1—O3890.39 (16)N40—C41—H41118.1
N31—Ir1—O3876.70 (16)C42—C41—H41118.1
C2—N1—C6118.1 (5)C41—C42—C43119.7 (5)
C2—N1—Ir1125.5 (4)C41—C42—H42120.2
C6—N1—Ir1116.4 (4)C43—C42—H42120.2
N1—C2—C3123.2 (5)C42—C43—C44117.1 (5)
N1—C2—H2118.4C42—C43—C52121.5 (5)
C3—C2—H2118.4C44—C43—C52121.4 (5)
C2—C3—C4119.8 (6)C43—C44—C45121.4 (5)
C2—C3—H3120.1C43—C44—H44119.3
C4—C3—H3120.1C45—C44—H44119.3
C5—C4—C3117.2 (6)N40—C45—C44120.3 (5)
C5—C4—C13121.4 (6)N40—C45—C46113.0 (5)
C3—C4—C13121.4 (6)C44—C45—C46126.7 (5)
C6—C5—C4121.8 (6)C51—C46—C47118.9 (5)
C6—C5—H5119.1C51—C46—C45126.0 (5)
C4—C5—H5119.1C47—C46—C45115.1 (5)
N1—C6—C5120.0 (5)C46—C47—C48118.1 (5)
N1—C6—C7112.5 (5)C46—C47—Ir2115.3 (4)
C5—C6—C7127.5 (5)C48—C47—Ir2126.6 (4)
C12—C7—C8118.9 (6)C49—C48—C47118.7 (5)
C12—C7—C6125.5 (6)C49—C48—H48120.7
C8—C7—C6115.6 (5)C47—C48—H48120.7
C9—C8—C7117.6 (6)C50—C49—C48124.4 (5)
C9—C8—Ir1127.4 (5)C50—C49—F54118.4 (6)
C7—C8—Ir1115.0 (4)C48—C49—F54117.1 (6)
C10—C9—C8120.0 (7)C49—C50—C51116.5 (5)
C10—C9—H9120C49—C50—H50121.8
C8—C9—H9120C51—C50—H50121.8
C11—C10—C9123.7 (7)F53—C51—C50116.3 (5)
C11—C10—F15117.7 (7)F53—C51—C46120.2 (5)
C9—C10—F15118.5 (7)C50—C51—C46123.4 (6)
C10—C11—C12116.4 (7)C43—C52—H52A109.5
C10—C11—H11121.8C43—C52—H52B109.5
C12—C11—H11121.8H52A—C52—H52B109.5
F14—C12—C11117.0 (6)C43—C52—H52C109.5
F14—C12—C7119.7 (6)H52A—C52—H52C109.5
C11—C12—C7123.3 (7)H52B—C52—H52C109.5
C4—C13—H13A109.5C56—N55—C60119.3 (5)
C4—C13—H13B109.5C56—N55—Ir2122.9 (4)
H13A—C13—H13B109.5C60—N55—Ir2117.5 (4)
C4—C13—H13C109.5N55—C56—C57121.5 (6)
H13A—C13—H13C109.5N55—C56—H56119.3
H13B—C13—H13C109.5C57—C56—H56119.3
C17—N16—C21119.6 (5)C56—C57—C58121.0 (6)
C17—N16—Ir1123.3 (4)C56—C57—H57119.5
C21—N16—Ir1116.9 (4)C58—C57—H57119.5
N16—C17—C18122.0 (6)C59—C58—C57117.3 (6)
N16—C17—H17119C59—C58—C67121.3 (6)
C18—C17—H17119C57—C58—C67121.3 (6)
C17—C18—C19120.0 (6)C58—C59—C60120.9 (6)
C17—C18—H18120C58—C59—H59119.6
C19—C18—H18120C60—C59—H59119.6
C20—C19—C18117.5 (6)N55—C60—C59119.9 (5)
C20—C19—C28121.6 (6)N55—C60—C61112.6 (5)
C18—C19—C28120.9 (6)C59—C60—C61127.5 (5)
C21—C20—C19121.1 (6)C66—C61—C62119.1 (5)
C21—C20—H20119.5C66—C61—C60126.4 (5)
C19—C20—H20119.5C62—C61—C60114.5 (5)
N16—C21—C20119.8 (5)C63—C62—C61117.5 (5)
N16—C21—C22112.9 (5)C63—C62—Ir2127.3 (4)
C20—C21—C22127.3 (5)C61—C62—Ir2115.1 (4)
C27—C22—C23118.6 (5)C64—C63—C62120.0 (5)
C27—C22—C21126.3 (5)C64—C63—H63120
C23—C22—C21115.1 (5)C62—C63—H63120
C24—C23—C22118.3 (5)F69—C64—C63119.5 (5)
C24—C23—Ir1127.1 (4)F69—C64—C65116.8 (5)
C22—C23—Ir1114.6 (4)C63—C64—C65123.6 (5)
C25—C24—C23119.6 (5)C66—C65—C64115.8 (5)
C25—C24—H24120.2C66—C65—H65122.1
C23—C24—H24120.2C64—C65—H65122.1
F30—C25—C24118.8 (5)C65—C66—F68116.0 (5)
F30—C25—C26117.5 (5)C65—C66—C61123.9 (5)
C24—C25—C26123.7 (5)F68—C66—C61120.1 (5)
C25—C26—C27116.5 (5)C58—C67—H67A109.5
C25—C26—H26121.7C58—C67—H67B109.5
C27—C26—H26121.7H67A—C67—H67B109.5
F29—C27—C26116.5 (5)C58—C67—H67C109.5
F29—C27—C22120.2 (5)H67A—C67—H67C109.5
C26—C27—C22123.3 (6)H67B—C67—H67C109.5
C19—C28—H28A109.5C71—N70—C75118.6 (5)
C19—C28—H28B109.5C71—N70—Ir2126.9 (4)
H28A—C28—H28B109.5C75—N70—Ir2114.4 (4)
C19—C28—H28C109.5N70—C71—C72121.8 (5)
H28A—C28—H28C109.5N70—C71—H71119.1
H28B—C28—H28C109.5C72—C71—H71119.1
C32—N31—C36118.8 (5)C71—C72—C73120.0 (6)
C32—N31—Ir1126.6 (4)C71—C72—H72120
C36—N31—Ir1114.6 (4)C73—C72—H72120
N31—C32—C33121.3 (5)C72—C73—C74118.3 (6)
N31—C32—H32119.3C72—C73—H73120.8
C33—C32—H32119.3C74—C73—H73120.8
C34—C33—C32119.9 (6)C75—C74—C73119.2 (5)
C34—C33—H33120C75—C74—H74120.4
C32—C33—H33120C73—C74—H74120.4
C33—C34—C35118.5 (6)N70—C75—C74122.0 (5)
C33—C34—H34120.8N70—C75—C76115.7 (5)
C35—C34—H34120.8C74—C75—C76122.3 (5)
C36—C35—C34119.7 (6)O78—C76—O77125.3 (6)
C36—C35—H35120.2O78—C76—C75118.2 (5)
C34—C35—H35120.2O77—C76—C75116.4 (5)
N31—C36—C35121.8 (5)C76—O77—Ir2116.4 (3)
N31—C36—C37115.6 (5)Cl2—C79—Cl1117.3 (6)
C35—C36—C37122.6 (5)Cl2—C79—Cl3108.0 (5)
O39—C37—O38125.5 (5)Cl1—C79—Cl3107.3 (5)
O39—C37—C36118.4 (5)Cl2—C79—H79108
O38—C37—C36116.1 (5)Cl1—C79—H79108
C37—O38—Ir1116.8 (3)Cl3—C79—H79108
C62—Ir2—C4788.1 (2)Cl5—C83—Cl6111.0 (5)
C62—Ir2—N5580.3 (2)Cl5—C83—Cl4111.4 (5)
C47—Ir2—N5593.9 (2)Cl6—C83—Cl4108.7 (5)
C62—Ir2—N4096.29 (19)Cl5—C83—H83108.6
C47—Ir2—N4079.8 (2)Cl6—C83—H83108.6
N55—Ir2—N40172.96 (17)Cl4—C83—H83108.6
Footnotes
Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2773).
References
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