Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807059314/bg2132sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807059314/bg2132Isup2.hkl |
CCDC reference: 672738
IrCl3.3H2O (0.1784 g, 0.51 mmol), ppy (0.20 ml, 1.29 mmol), 2-ethoxyethanol (9 ml) and water (3 ml) were heated to 120°C for 24 h under nitrogen atmosphere. After cooling to the room temperature, the precipitate was collected by filtration, washed with water and methanol, and then dried in vacuum. The obtained chloro-bridged dimmer(0.1604 g, 0.15 mmol) was mixed with dMbpy (0.0690 g, 0.375 mmol) in methanol/dichloromethane (30 ml, 1: 1, v:v). The mixture was refluxed under nitrogen atmosphere in the dark for 4 h. The title compound was achieved after metathesis with KPF6 and subsequent recrystalllization from dichloromethane /petroleum ether at room temperature.
All H-atoms bound to carbon were refined using a riding model with d(C—H) = 0.93 Å, Uiso = 1.2Ueq (C) for aromatic and 0.96 Å, Uiso = 1.5Ueq (C) for CH3 atoms.
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
Fig. 1. Molecular diagram of (I). Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. |
[Ir(C11H8N)2(C12H12N2)]PF6 | F(000) = 1624 |
Mr = 829.77 | Dx = 1.760 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 5760 reflections |
a = 12.5020 (9) Å | θ = 1.9–26.0° |
b = 13.0490 (9) Å | µ = 4.38 mm−1 |
c = 19.1980 (13) Å | T = 293 K |
V = 3131.9 (4) Å3 | Block, orange |
Z = 4 | 0.40 × 0.30 × 0.25 mm |
Bruker APEX CCD area-detector diffractometer | 6124 independent reflections |
Radiation source: fine-focus sealed tube | 5760 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.091 |
ω scans | θmax = 26.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −15→11 |
Tmin = 0.23, Tmax = 0.33 | k = −16→15 |
17622 measured reflections | l = −23→23 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.028 | H-atom parameters constrained |
wR(F2) = 0.067 | w = 1/[σ2(Fo2) + (0.0242P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max = 0.002 |
6124 reflections | Δρmax = 1.23 e Å−3 |
415 parameters | Δρmin = −0.76 e Å−3 |
2 restraints | Absolute structure: Flack (1983), 2663 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.024 (6) |
[Ir(C11H8N)2(C12H12N2)]PF6 | V = 3131.9 (4) Å3 |
Mr = 829.77 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 12.5020 (9) Å | µ = 4.38 mm−1 |
b = 13.0490 (9) Å | T = 293 K |
c = 19.1980 (13) Å | 0.40 × 0.30 × 0.25 mm |
Bruker APEX CCD area-detector diffractometer | 6124 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 5760 reflections with I > 2σ(I) |
Tmin = 0.23, Tmax = 0.33 | Rint = 0.091 |
17622 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | H-atom parameters constrained |
wR(F2) = 0.067 | Δρmax = 1.23 e Å−3 |
S = 1.00 | Δρmin = −0.76 e Å−3 |
6124 reflections | Absolute structure: Flack (1983), 2663 Friedel pairs |
415 parameters | Absolute structure parameter: −0.024 (6) |
2 restraints |
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 | ||
C1 | 0.1848 (6) | 0.2841 (4) | 0.1679 (3) | 0.0461 (15) | |
H1A | 0.2140 | 0.2778 | 0.1218 | 0.069* | |
H1B | 0.1125 | 0.3085 | 0.1649 | 0.069* | |
H1C | 0.1856 | 0.2184 | 0.1903 | 0.069* | |
C2 | 0.2504 (5) | 0.3581 (3) | 0.2091 (3) | 0.0320 (11) | |
C3 | 0.3407 (5) | 0.4050 (3) | 0.1812 (3) | 0.0338 (13) | |
H3 | 0.3645 | 0.3872 | 0.1369 | 0.041* | |
C4 | 0.3951 (5) | 0.4787 (4) | 0.2197 (2) | 0.0304 (11) | |
H4 | 0.4525 | 0.5125 | 0.1992 | 0.037* | |
C5 | 0.2253 (4) | 0.3823 (4) | 0.2777 (2) | 0.0316 (10) | |
H5 | 0.1666 | 0.3513 | 0.2987 | 0.038* | |
C6 | 0.2863 (5) | 0.4520 (3) | 0.3154 (3) | 0.0286 (11) | |
C7 | 0.2724 (5) | 0.4692 (3) | 0.3914 (2) | 0.0278 (11) | |
C8 | 0.2012 (5) | 0.4148 (3) | 0.4314 (3) | 0.0333 (12) | |
H8 | 0.1543 | 0.3689 | 0.4105 | 0.040* | |
C9 | 0.1995 (5) | 0.4285 (4) | 0.5034 (3) | 0.0355 (12) | |
C10 | 0.1245 (6) | 0.3676 (4) | 0.5485 (3) | 0.0529 (16) | |
H10A | 0.0820 | 0.3233 | 0.5197 | 0.079* | |
H10B | 0.0785 | 0.4135 | 0.5736 | 0.079* | |
H10C | 0.1650 | 0.3273 | 0.5808 | 0.079* | |
C11 | 0.2697 (5) | 0.4990 (4) | 0.5313 (3) | 0.0329 (12) | |
H11 | 0.2725 | 0.5088 | 0.5792 | 0.039* | |
C12 | 0.3352 (5) | 0.5546 (4) | 0.4882 (3) | 0.0328 (12) | |
H12 | 0.3796 | 0.6039 | 0.5080 | 0.039* | |
C13 | 0.5736 (4) | 0.5377 (3) | 0.3615 (2) | 0.0182 (9) | |
C14 | 0.5925 (5) | 0.4774 (4) | 0.4166 (3) | 0.0341 (12) | |
H14 | 0.5406 | 0.4716 | 0.4511 | 0.041* | |
C15 | 0.6874 (5) | 0.4234 (4) | 0.4238 (3) | 0.0426 (14) | |
H15 | 0.6992 | 0.3818 | 0.4624 | 0.051* | |
C16 | 0.7637 (6) | 0.4329 (4) | 0.3725 (3) | 0.0466 (15) | |
H16 | 0.8275 | 0.3966 | 0.3758 | 0.056* | |
C17 | 0.7454 (5) | 0.4959 (4) | 0.3164 (3) | 0.0418 (14) | |
H17 | 0.7972 | 0.5037 | 0.2820 | 0.050* | |
C18 | 0.6484 (5) | 0.5480 (3) | 0.3118 (3) | 0.0321 (12) | |
C19 | 0.6201 (4) | 0.6180 (3) | 0.2552 (2) | 0.0279 (10) | |
C20 | 0.6786 (4) | 0.6309 (4) | 0.1943 (3) | 0.0356 (11) | |
H20 | 0.7420 | 0.5947 | 0.1878 | 0.043* | |
C21 | 0.6428 (5) | 0.6974 (4) | 0.1434 (3) | 0.0387 (13) | |
H21 | 0.6801 | 0.7030 | 0.1017 | 0.046* | |
C22 | 0.5525 (5) | 0.7551 (3) | 0.1539 (3) | 0.0349 (12) | |
H22 | 0.5308 | 0.8013 | 0.1198 | 0.042* | |
C23 | 0.4933 (5) | 0.7456 (3) | 0.2146 (3) | 0.0334 (12) | |
H23 | 0.4331 | 0.7864 | 0.2212 | 0.040* | |
C24 | 0.5684 (5) | 0.7350 (3) | 0.4616 (2) | 0.0347 (11) | |
H24 | 0.6222 | 0.6863 | 0.4569 | 0.042* | |
C25 | 0.5753 (6) | 0.8112 (4) | 0.5126 (3) | 0.0447 (14) | |
H25 | 0.6333 | 0.8112 | 0.5429 | 0.054* | |
C26 | 0.4980 (6) | 0.8867 (4) | 0.5192 (3) | 0.0516 (16) | |
H26 | 0.5039 | 0.9366 | 0.5535 | 0.062* | |
C27 | 0.4131 (5) | 0.8868 (4) | 0.4746 (3) | 0.0464 (14) | |
H27 | 0.3616 | 0.9380 | 0.4781 | 0.056* | |
C28 | 0.4024 (5) | 0.8114 (3) | 0.4238 (3) | 0.0318 (12) | |
C29 | 0.3096 (5) | 0.8056 (3) | 0.3772 (3) | 0.0322 (12) | |
C30 | 0.2232 (5) | 0.8739 (4) | 0.3743 (3) | 0.0388 (12) | |
H30 | 0.2226 | 0.9311 | 0.4032 | 0.047* | |
C31 | 0.1400 (5) | 0.8576 (4) | 0.3299 (3) | 0.0436 (14) | |
H31 | 0.0824 | 0.9027 | 0.3288 | 0.052* | |
C32 | 0.1422 (5) | 0.7725 (4) | 0.2858 (3) | 0.0388 (13) | |
H32 | 0.0868 | 0.7600 | 0.2546 | 0.047* | |
C33 | 0.2283 (5) | 0.7078 (4) | 0.2899 (3) | 0.0346 (12) | |
H33 | 0.2297 | 0.6513 | 0.2605 | 0.042* | |
C34 | 0.3108 (4) | 0.7211 (3) | 0.33388 (19) | 0.0153 (8) | |
N1 | 0.4759 (5) | 0.7335 (3) | 0.4164 (2) | 0.0429 (12) | |
N2 | 0.5231 (4) | 0.6748 (3) | 0.2667 (2) | 0.0422 (12) | |
N3 | 0.3680 (4) | 0.5028 (3) | 0.28533 (19) | 0.0248 (9) | |
N4 | 0.3385 (4) | 0.5413 (3) | 0.4192 (2) | 0.0288 (10) | |
F1 | 0.4993 (4) | 0.4697 (2) | 0.59377 (19) | 0.0600 (10) | |
F2 | 0.6177 (3) | 0.3393 (3) | 0.5834 (2) | 0.0649 (11) | |
F3 | 0.5000 (4) | 0.2318 (2) | 0.6330 (2) | 0.0630 (11) | |
F4 | 0.3804 (3) | 0.3588 (2) | 0.64277 (18) | 0.0543 (9) | |
F5 | 0.4532 (3) | 0.3242 (2) | 0.53746 (18) | 0.0540 (9) | |
F6 | 0.5454 (3) | 0.3770 (3) | 0.68888 (18) | 0.0674 (10) | |
P1 | 0.49880 (14) | 0.35010 (11) | 0.61308 (8) | 0.0411 (4) | |
Ir1 | 0.436483 (15) | 0.622344 (12) | 0.347270 (9) | 0.02485 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.049 (4) | 0.042 (3) | 0.047 (4) | −0.007 (3) | −0.006 (3) | −0.008 (2) |
C2 | 0.039 (3) | 0.023 (2) | 0.035 (3) | 0.004 (2) | −0.010 (2) | −0.0002 (19) |
C3 | 0.044 (4) | 0.028 (2) | 0.029 (2) | 0.005 (2) | −0.001 (2) | −0.0014 (19) |
C4 | 0.033 (3) | 0.033 (2) | 0.025 (2) | 0.006 (2) | 0.004 (2) | 0.000 (2) |
C5 | 0.034 (3) | 0.026 (2) | 0.035 (2) | −0.002 (2) | 0.003 (2) | 0.003 (2) |
C6 | 0.033 (3) | 0.022 (2) | 0.030 (3) | 0.002 (2) | 0.001 (2) | 0.0015 (18) |
C7 | 0.034 (3) | 0.023 (2) | 0.027 (2) | 0.004 (2) | −0.001 (2) | −0.0007 (19) |
C8 | 0.035 (3) | 0.029 (2) | 0.036 (3) | −0.003 (2) | 0.009 (3) | −0.0042 (19) |
C9 | 0.040 (3) | 0.035 (2) | 0.031 (3) | −0.002 (2) | 0.008 (3) | 0.006 (2) |
C10 | 0.064 (4) | 0.054 (3) | 0.041 (3) | −0.015 (4) | 0.016 (3) | −0.001 (3) |
C11 | 0.037 (3) | 0.036 (3) | 0.027 (3) | 0.007 (2) | 0.006 (2) | 0.000 (2) |
C12 | 0.035 (3) | 0.031 (2) | 0.032 (3) | 0.005 (2) | −0.001 (2) | −0.003 (2) |
C13 | 0.021 (2) | 0.0129 (16) | 0.021 (2) | −0.0011 (17) | −0.0028 (19) | 0.0044 (14) |
C14 | 0.033 (3) | 0.037 (3) | 0.033 (3) | 0.001 (2) | 0.000 (2) | 0.000 (2) |
C15 | 0.045 (4) | 0.035 (3) | 0.048 (3) | 0.009 (3) | −0.007 (3) | 0.010 (2) |
C16 | 0.039 (4) | 0.049 (3) | 0.052 (4) | 0.014 (3) | 0.002 (3) | 0.006 (3) |
C17 | 0.027 (3) | 0.039 (3) | 0.059 (4) | 0.007 (2) | 0.008 (3) | −0.001 (3) |
C18 | 0.034 (3) | 0.021 (2) | 0.041 (3) | −0.002 (2) | 0.000 (2) | −0.005 (2) |
C19 | 0.027 (3) | 0.026 (2) | 0.031 (2) | 0.001 (2) | 0.001 (2) | −0.003 (2) |
C20 | 0.029 (3) | 0.034 (2) | 0.044 (3) | −0.002 (3) | 0.002 (2) | −0.002 (2) |
C21 | 0.042 (3) | 0.044 (3) | 0.031 (3) | −0.011 (2) | 0.005 (3) | −0.001 (2) |
C22 | 0.042 (3) | 0.032 (2) | 0.031 (2) | −0.011 (2) | −0.001 (3) | 0.003 (2) |
C23 | 0.039 (3) | 0.025 (2) | 0.036 (3) | −0.003 (2) | −0.003 (3) | 0.002 (2) |
C24 | 0.037 (3) | 0.035 (2) | 0.032 (2) | −0.007 (3) | 0.002 (3) | 0.004 (2) |
C25 | 0.047 (4) | 0.047 (3) | 0.040 (3) | −0.013 (3) | −0.009 (3) | −0.003 (2) |
C26 | 0.065 (4) | 0.043 (3) | 0.047 (3) | −0.007 (3) | −0.005 (3) | −0.018 (3) |
C27 | 0.051 (4) | 0.038 (3) | 0.050 (3) | −0.003 (3) | 0.004 (3) | −0.013 (3) |
C28 | 0.037 (3) | 0.020 (2) | 0.038 (3) | −0.005 (2) | 0.002 (2) | −0.0036 (19) |
C29 | 0.035 (3) | 0.029 (2) | 0.033 (3) | −0.002 (2) | 0.006 (3) | 0.002 (2) |
C30 | 0.041 (3) | 0.027 (2) | 0.049 (3) | 0.004 (3) | 0.006 (3) | −0.005 (2) |
C31 | 0.044 (3) | 0.034 (3) | 0.053 (3) | 0.013 (2) | 0.001 (3) | −0.002 (2) |
C32 | 0.033 (3) | 0.043 (3) | 0.041 (3) | 0.003 (3) | −0.005 (3) | 0.001 (2) |
C33 | 0.040 (3) | 0.029 (2) | 0.034 (3) | 0.002 (2) | 0.006 (3) | −0.003 (2) |
C34 | 0.017 (2) | 0.0129 (16) | 0.016 (2) | 0.0023 (16) | −0.0015 (18) | 0.0001 (14) |
N1 | 0.040 (3) | 0.048 (3) | 0.040 (3) | −0.011 (2) | 0.001 (2) | 0.001 (2) |
N2 | 0.046 (3) | 0.045 (2) | 0.036 (3) | −0.005 (2) | 0.005 (2) | 0.005 (2) |
N3 | 0.030 (2) | 0.0235 (18) | 0.0209 (19) | 0.0058 (17) | −0.0023 (18) | −0.0002 (15) |
N4 | 0.032 (3) | 0.028 (2) | 0.027 (2) | 0.0002 (18) | 0.0017 (19) | 0.0008 (17) |
F1 | 0.069 (3) | 0.0475 (18) | 0.063 (2) | −0.014 (2) | −0.014 (2) | 0.0061 (17) |
F2 | 0.040 (2) | 0.092 (3) | 0.063 (2) | −0.003 (2) | 0.001 (2) | 0.022 (2) |
F3 | 0.060 (3) | 0.0452 (18) | 0.084 (3) | 0.0122 (19) | 0.008 (2) | 0.0185 (18) |
F4 | 0.042 (2) | 0.0624 (19) | 0.059 (2) | 0.0111 (17) | 0.0087 (18) | 0.0111 (18) |
F5 | 0.058 (3) | 0.0576 (18) | 0.0465 (19) | 0.0029 (18) | −0.0040 (19) | −0.0062 (16) |
F6 | 0.065 (3) | 0.098 (3) | 0.0390 (18) | 0.005 (3) | −0.0112 (18) | 0.005 (2) |
P1 | 0.0371 (9) | 0.0471 (9) | 0.0390 (8) | 0.0008 (7) | −0.0013 (7) | 0.0073 (6) |
Ir1 | 0.02670 (10) | 0.02314 (9) | 0.02473 (9) | −0.00017 (8) | 0.00159 (8) | 0.00069 (7) |
C1—C2 | 1.495 (7) | C20—C21 | 1.381 (7) |
C1—H1A | 0.9600 | C20—H20 | 0.9300 |
C1—H1B | 0.9600 | C21—C22 | 1.372 (8) |
C1—H1C | 0.9600 | C21—H21 | 0.9300 |
C2—C5 | 1.390 (7) | C22—C23 | 1.388 (8) |
C2—C3 | 1.390 (8) | C22—H22 | 0.9300 |
C3—C4 | 1.390 (7) | C23—N2 | 1.411 (6) |
C3—H3 | 0.9300 | C23—H23 | 0.9300 |
C4—N3 | 1.342 (6) | C24—C25 | 1.397 (7) |
C4—H4 | 0.9300 | C24—N1 | 1.447 (7) |
C5—C6 | 1.391 (7) | C24—H24 | 0.9300 |
C5—H5 | 0.9300 | C25—C26 | 1.386 (9) |
C6—N3 | 1.347 (7) | C25—H25 | 0.9300 |
C6—C7 | 1.486 (7) | C26—C27 | 1.364 (9) |
C7—N4 | 1.361 (6) | C26—H26 | 0.9300 |
C7—C8 | 1.373 (7) | C27—C28 | 1.392 (7) |
C8—C9 | 1.393 (7) | C27—H27 | 0.9300 |
C8—H8 | 0.9300 | C28—N1 | 1.378 (8) |
C9—C11 | 1.380 (8) | C28—C29 | 1.468 (8) |
C9—C10 | 1.503 (7) | C29—C34 | 1.380 (6) |
C10—H10A | 0.9600 | C29—C30 | 1.402 (8) |
C10—H10B | 0.9600 | C30—C31 | 1.362 (9) |
C10—H10C | 0.9600 | C30—H30 | 0.9300 |
C11—C12 | 1.372 (7) | C31—C32 | 1.396 (7) |
C11—H11 | 0.9300 | C31—H31 | 0.9300 |
C12—N4 | 1.337 (6) | C32—C33 | 1.369 (8) |
C12—H12 | 0.9300 | C32—H32 | 0.9300 |
C13—C14 | 1.340 (6) | C33—C34 | 1.344 (6) |
C13—C18 | 1.342 (7) | C33—H33 | 0.9300 |
C13—Ir1 | 2.057 (4) | C34—Ir1 | 2.049 (4) |
C14—C15 | 1.386 (8) | N1—Ir1 | 2.026 (5) |
C14—H14 | 0.9300 | N2—Ir1 | 2.009 (5) |
C15—C16 | 1.377 (9) | N3—Ir1 | 2.140 (4) |
C15—H15 | 0.9300 | N4—Ir1 | 2.127 (4) |
C16—C17 | 1.374 (8) | F1—P1 | 1.604 (4) |
C16—H16 | 0.9300 | F2—P1 | 1.599 (4) |
C17—C18 | 1.394 (8) | F3—P1 | 1.590 (3) |
C17—H17 | 0.9300 | F4—P1 | 1.590 (4) |
C18—C19 | 1.463 (7) | F5—P1 | 1.596 (4) |
C19—C20 | 1.389 (7) | F6—P1 | 1.607 (4) |
C19—N2 | 1.438 (6) | ||
C2—C1—H1A | 109.5 | C25—C24—N1 | 118.6 (6) |
C2—C1—H1B | 109.5 | C25—C24—H24 | 120.7 |
H1A—C1—H1B | 109.5 | N1—C24—H24 | 120.7 |
C2—C1—H1C | 109.5 | C26—C25—C24 | 121.8 (6) |
H1A—C1—H1C | 109.5 | C26—C25—H25 | 119.1 |
H1B—C1—H1C | 109.5 | C24—C25—H25 | 119.1 |
C5—C2—C3 | 116.7 (5) | C27—C26—C25 | 119.1 (5) |
C5—C2—C1 | 121.6 (5) | C27—C26—H26 | 120.5 |
C3—C2—C1 | 121.8 (5) | C25—C26—H26 | 120.5 |
C4—C3—C2 | 119.8 (5) | C26—C27—C28 | 120.9 (6) |
C4—C3—H3 | 120.1 | C26—C27—H27 | 119.6 |
C2—C3—H3 | 120.1 | C28—C27—H27 | 119.6 |
N3—C4—C3 | 122.5 (5) | N1—C28—C27 | 122.1 (6) |
N3—C4—H4 | 118.7 | N1—C28—C29 | 115.2 (4) |
C3—C4—H4 | 118.7 | C27—C28—C29 | 122.6 (5) |
C2—C5—C6 | 121.1 (5) | C34—C29—C30 | 119.5 (5) |
C2—C5—H5 | 119.4 | C34—C29—C28 | 113.6 (5) |
C6—C5—H5 | 119.4 | C30—C29—C28 | 126.9 (5) |
N3—C6—C5 | 121.0 (4) | C31—C30—C29 | 120.9 (5) |
N3—C6—C7 | 115.8 (4) | C31—C30—H30 | 119.5 |
C5—C6—C7 | 123.0 (5) | C29—C30—H30 | 119.5 |
N4—C7—C8 | 122.0 (4) | C30—C31—C32 | 119.2 (6) |
N4—C7—C6 | 114.7 (5) | C30—C31—H31 | 120.4 |
C8—C7—C6 | 123.2 (5) | C32—C31—H31 | 120.4 |
C7—C8—C9 | 120.0 (5) | C33—C32—C31 | 118.1 (6) |
C7—C8—H8 | 120.0 | C33—C32—H32 | 121.0 |
C9—C8—H8 | 120.0 | C31—C32—H32 | 121.0 |
C11—C9—C8 | 117.4 (5) | C34—C33—C32 | 124.1 (5) |
C11—C9—C10 | 121.7 (5) | C34—C33—H33 | 118.0 |
C8—C9—C10 | 120.9 (5) | C32—C33—H33 | 118.0 |
C9—C10—H10A | 109.5 | C33—C34—C29 | 118.2 (5) |
C9—C10—H10B | 109.5 | C33—C34—Ir1 | 125.9 (3) |
H10A—C10—H10B | 109.5 | C29—C34—Ir1 | 115.8 (4) |
C9—C10—H10C | 109.5 | C28—N1—C24 | 117.4 (4) |
H10A—C10—H10C | 109.5 | C28—N1—Ir1 | 115.7 (4) |
H10B—C10—H10C | 109.5 | C24—N1—Ir1 | 126.7 (4) |
C12—C11—C9 | 119.9 (5) | C23—N2—C19 | 116.9 (5) |
C12—C11—H11 | 120.1 | C23—N2—Ir1 | 128.7 (4) |
C9—C11—H11 | 120.1 | C19—N2—Ir1 | 113.4 (3) |
N4—C12—C11 | 123.2 (5) | C4—N3—C6 | 118.6 (4) |
N4—C12—H12 | 118.4 | C4—N3—Ir1 | 126.3 (4) |
C11—C12—H12 | 118.4 | C6—N3—Ir1 | 115.1 (3) |
C14—C13—C18 | 119.8 (5) | C12—N4—C7 | 117.4 (4) |
C14—C13—Ir1 | 124.6 (4) | C12—N4—Ir1 | 126.6 (4) |
C18—C13—Ir1 | 115.6 (3) | C7—N4—Ir1 | 116.0 (3) |
C13—C14—C15 | 121.9 (5) | F4—P1—F3 | 89.6 (2) |
C13—C14—H14 | 119.1 | F4—P1—F5 | 90.5 (2) |
C15—C14—H14 | 119.1 | F3—P1—F5 | 90.9 (2) |
C16—C15—C14 | 118.4 (5) | F4—P1—F2 | 179.1 (2) |
C16—C15—H15 | 120.8 | F3—P1—F2 | 89.5 (2) |
C14—C15—H15 | 120.8 | F5—P1—F2 | 89.4 (2) |
C17—C16—C15 | 120.0 (6) | F4—P1—F1 | 91.0 (2) |
C17—C16—H16 | 120.0 | F3—P1—F1 | 179.0 (3) |
C15—C16—H16 | 120.0 | F5—P1—F1 | 89.86 (19) |
C16—C17—C18 | 119.1 (6) | F2—P1—F1 | 90.0 (2) |
C16—C17—H17 | 120.4 | F4—P1—F6 | 89.8 (2) |
C18—C17—H17 | 120.4 | F3—P1—F6 | 89.5 (2) |
C13—C18—C17 | 120.8 (5) | F5—P1—F6 | 179.4 (3) |
C13—C18—C19 | 115.0 (5) | F2—P1—F6 | 90.3 (2) |
C17—C18—C19 | 124.2 (5) | F1—P1—F6 | 89.7 (2) |
C20—C19—N2 | 120.7 (4) | N2—Ir1—N1 | 97.43 (19) |
C20—C19—C18 | 125.0 (5) | N2—Ir1—C34 | 95.89 (17) |
N2—C19—C18 | 114.3 (4) | N1—Ir1—C34 | 79.54 (19) |
C21—C20—C19 | 120.0 (5) | N2—Ir1—C13 | 80.55 (18) |
C21—C20—H20 | 120.0 | N1—Ir1—C13 | 95.43 (19) |
C19—C20—H20 | 120.0 | C34—Ir1—C13 | 173.47 (15) |
C22—C21—C20 | 120.5 (5) | N2—Ir1—N4 | 168.43 (17) |
C22—C21—H21 | 119.7 | N1—Ir1—N4 | 94.09 (17) |
C20—C21—H21 | 119.7 | C34—Ir1—N4 | 87.28 (16) |
C21—C22—C23 | 120.9 (5) | C13—Ir1—N4 | 97.28 (16) |
C21—C22—H22 | 119.6 | N2—Ir1—N3 | 92.06 (17) |
C23—C22—H22 | 119.6 | N1—Ir1—N3 | 169.34 (19) |
C22—C23—N2 | 120.9 (5) | C34—Ir1—N3 | 94.71 (15) |
C22—C23—H23 | 119.6 | C13—Ir1—N3 | 90.90 (15) |
N2—C23—H23 | 119.6 | N4—Ir1—N3 | 76.57 (15) |
C5—C2—C3—C4 | −5.4 (7) | C18—C19—N2—Ir1 | −12.0 (5) |
C1—C2—C3—C4 | 175.6 (5) | C3—C4—N3—C6 | 1.4 (7) |
C2—C3—C4—N3 | 4.1 (8) | C3—C4—N3—Ir1 | −174.7 (4) |
C3—C2—C5—C6 | 1.6 (7) | C5—C6—N3—C4 | −5.4 (7) |
C1—C2—C5—C6 | −179.4 (5) | C7—C6—N3—C4 | 169.9 (4) |
C2—C5—C6—N3 | 3.9 (7) | C5—C6—N3—Ir1 | 171.2 (4) |
C2—C5—C6—C7 | −171.0 (5) | C7—C6—N3—Ir1 | −13.5 (5) |
N3—C6—C7—N4 | 5.6 (6) | C11—C12—N4—C7 | 0.4 (8) |
C5—C6—C7—N4 | −179.3 (4) | C11—C12—N4—Ir1 | −179.9 (4) |
N3—C6—C7—C8 | −172.3 (5) | C8—C7—N4—C12 | 2.9 (7) |
C5—C6—C7—C8 | 2.8 (8) | C6—C7—N4—C12 | −175.1 (4) |
N4—C7—C8—C9 | −3.7 (8) | C8—C7—N4—Ir1 | −176.8 (4) |
C6—C7—C8—C9 | 174.1 (5) | C6—C7—N4—Ir1 | 5.3 (5) |
C7—C8—C9—C11 | 1.1 (8) | C23—N2—Ir1—N1 | −88.4 (5) |
C7—C8—C9—C10 | −178.2 (5) | C19—N2—Ir1—N1 | 103.5 (4) |
C8—C9—C11—C12 | 2.0 (8) | C23—N2—Ir1—C34 | −8.2 (4) |
C10—C9—C11—C12 | −178.6 (5) | C19—N2—Ir1—C34 | −176.3 (3) |
C9—C11—C12—N4 | −2.9 (8) | C23—N2—Ir1—C13 | 177.3 (5) |
C18—C13—C14—C15 | −0.9 (7) | C19—N2—Ir1—C13 | 9.2 (3) |
Ir1—C13—C14—C15 | −179.0 (4) | C23—N2—Ir1—N4 | 97.3 (10) |
C13—C14—C15—C16 | 0.1 (9) | C19—N2—Ir1—N4 | −70.9 (11) |
C14—C15—C16—C17 | 1.0 (9) | C23—N2—Ir1—N3 | 86.8 (4) |
C15—C16—C17—C18 | −1.3 (9) | C19—N2—Ir1—N3 | −81.4 (3) |
C14—C13—C18—C17 | 0.6 (7) | C28—N1—Ir1—N2 | 98.5 (4) |
Ir1—C13—C18—C17 | 178.9 (4) | C24—N1—Ir1—N2 | −86.4 (4) |
C14—C13—C18—C19 | −178.3 (4) | C28—N1—Ir1—C34 | 3.9 (4) |
Ir1—C13—C18—C19 | −0.1 (5) | C24—N1—Ir1—C34 | 179.0 (4) |
C16—C17—C18—C13 | 0.4 (8) | C28—N1—Ir1—C13 | 179.6 (4) |
C16—C17—C18—C19 | 179.3 (5) | C24—N1—Ir1—C13 | −5.2 (4) |
C13—C18—C19—C20 | −171.6 (5) | C28—N1—Ir1—N4 | −82.6 (4) |
C17—C18—C19—C20 | 9.5 (8) | C24—N1—Ir1—N4 | 92.5 (4) |
C13—C18—C19—N2 | 7.9 (6) | C28—N1—Ir1—N3 | −54.2 (11) |
C17—C18—C19—N2 | −171.0 (5) | C24—N1—Ir1—N3 | 120.9 (9) |
N2—C19—C20—C21 | −1.2 (7) | C33—C34—Ir1—N2 | 83.9 (4) |
C18—C19—C20—C21 | 178.3 (5) | C29—C34—Ir1—N2 | −99.8 (4) |
C19—C20—C21—C22 | 3.4 (8) | C33—C34—Ir1—N1 | −179.6 (4) |
C20—C21—C22—C23 | −2.2 (8) | C29—C34—Ir1—N1 | −3.4 (4) |
C21—C22—C23—N2 | −1.3 (8) | C33—C34—Ir1—N4 | −85.0 (4) |
N1—C24—C25—C26 | −2.2 (8) | C29—C34—Ir1—N4 | 91.3 (4) |
C24—C25—C26—C27 | −0.2 (9) | C33—C34—Ir1—N3 | −8.7 (4) |
C25—C26—C27—C28 | 1.2 (9) | C29—C34—Ir1—N3 | 167.6 (3) |
C26—C27—C28—N1 | 0.3 (9) | C14—C13—Ir1—N2 | 173.0 (4) |
C26—C27—C28—C29 | 176.8 (5) | C18—C13—Ir1—N2 | −5.1 (3) |
N1—C28—C29—C34 | 0.9 (7) | C14—C13—Ir1—N1 | 76.4 (4) |
C27—C28—C29—C34 | −175.7 (5) | C18—C13—Ir1—N1 | −101.8 (3) |
N1—C28—C29—C30 | 179.4 (5) | C14—C13—Ir1—N4 | −18.5 (4) |
C27—C28—C29—C30 | 2.8 (8) | C18—C13—Ir1—N4 | 163.4 (3) |
C34—C29—C30—C31 | 0.6 (8) | C14—C13—Ir1—N3 | −95.1 (4) |
C28—C29—C30—C31 | −177.8 (5) | C18—C13—Ir1—N3 | 86.8 (3) |
C29—C30—C31—C32 | −1.1 (9) | C12—N4—Ir1—N2 | 160.3 (8) |
C30—C31—C32—C33 | 0.7 (8) | C7—N4—Ir1—N2 | −20.1 (11) |
C31—C32—C33—C34 | 0.2 (9) | C12—N4—Ir1—N1 | −14.1 (5) |
C32—C33—C34—C29 | −0.7 (8) | C7—N4—Ir1—N1 | 165.5 (4) |
C32—C33—C34—Ir1 | 175.5 (4) | C12—N4—Ir1—C34 | −93.4 (4) |
C30—C29—C34—C33 | 0.3 (7) | C7—N4—Ir1—C34 | 86.2 (4) |
C28—C29—C34—C33 | 178.9 (4) | C12—N4—Ir1—C13 | 81.9 (4) |
C30—C29—C34—Ir1 | −176.3 (4) | C7—N4—Ir1—C13 | −98.5 (4) |
C28—C29—C34—Ir1 | 2.3 (5) | C12—N4—Ir1—N3 | 171.1 (4) |
C27—C28—N1—C24 | −2.7 (8) | C7—N4—Ir1—N3 | −9.3 (4) |
C29—C28—N1—C24 | −179.4 (4) | C4—N3—Ir1—N2 | 6.5 (4) |
C27—C28—N1—Ir1 | 172.9 (4) | C6—N3—Ir1—N2 | −169.8 (3) |
C29—C28—N1—Ir1 | −3.8 (6) | C4—N3—Ir1—N1 | 159.4 (9) |
C25—C24—N1—C28 | 3.6 (7) | C6—N3—Ir1—N1 | −16.9 (11) |
C25—C24—N1—Ir1 | −171.5 (4) | C4—N3—Ir1—C34 | 102.5 (4) |
C22—C23—N2—C19 | 3.4 (7) | C6—N3—Ir1—C34 | −73.7 (3) |
C22—C23—N2—Ir1 | −164.5 (4) | C4—N3—Ir1—C13 | −74.1 (4) |
C20—C19—N2—C23 | −2.1 (7) | C6—N3—Ir1—C13 | 109.6 (3) |
C18—C19—N2—C23 | 178.4 (4) | C4—N3—Ir1—N4 | −171.4 (4) |
C20—C19—N2—Ir1 | 167.5 (4) | C6—N3—Ir1—N4 | 12.3 (3) |
Experimental details
Crystal data | |
Chemical formula | [Ir(C11H8N)2(C12H12N2)]PF6 |
Mr | 829.77 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 12.5020 (9), 13.0490 (9), 19.1980 (13) |
V (Å3) | 3131.9 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.38 |
Crystal size (mm) | 0.40 × 0.30 × 0.25 |
Data collection | |
Diffractometer | Bruker APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.23, 0.33 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17622, 6124, 5760 |
Rint | 0.091 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.067, 1.00 |
No. of reflections | 6124 |
No. of parameters | 415 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.23, −0.76 |
Absolute structure | Flack (1983), 2663 Friedel pairs |
Absolute structure parameter | −0.024 (6) |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus (Sheldrick, 1990).
C13—Ir1 | 2.057 (4) | N2—Ir1 | 2.009 (5) |
C34—Ir1 | 2.049 (4) | N3—Ir1 | 2.140 (4) |
N1—Ir1 | 2.026 (5) | N4—Ir1 | 2.127 (4) |
Recently, phosphorescent materials have been extensively studied owing to their applications for organic light-emitting diodes (OLEDs) with high performances. Amongst these materials, Iridium(III) complexes containing phenylpyridine are particularly important and have been thoroughly investigated (Graces et al., 1988) because both singlet and triplet excitons can be harvested for light emission in these complexes, leading to the internal quantum efficiency of phosphorescent emitters theoretically approaching 100% (Huo et al., 2006; Wong et al., 2006). In this contribution, we present the synthesis and crystal structure of [Ir(ppy)2(dMbpy)](PF6) (ppy is 2-phenylpyridine and dMbpy is 4,4'-dimethyl-2,2'-bipyridine). The title compound reveals bright green light under excitation of UV radiation, which implies that it is a candidate for a highly efficient phosphorescent emitter in OLEDs.
The overall structural arrangement is similar to several previously reported examples, including the diketonate complex [(ppy)2Ir(acac)] (Lamansky et al.,2001), the diimine complexes such as [Ir(mppz)2(bpy-NH2)](PF6) (Lo et al., 2003). As shown in Fig.1, [Ir(ppy)2(dMbpy)](PF6) has a distorted octahedral coordination geometry with two ppy and one dMbpy around the iridium center, and one hexafluorophosphate (PF6-) anion providing for charge balance. The coordination geometry of the ppy ligands around the cation is such that the carbon atoms C(13) and C(34) are in a cis- orientation, with Ir—C bond lengths of 2.058 (4) Å and 2.055 (4) Å, respectively; on the other side, the nitrogen atoms N(1) and N(2) in ppy reside at trans- locations, with Ir—N bond lengths of 2.026 (5) Å and 2.018 (5) Å, respectively. It is to be noted that the Ir—N3 and Ir- N4 bond lengths in the dMbpy ligand are 2.141 (4)Å and 2.127 (4) Å, values which are slightly longer than those in the ppy ligand. Coordination lengths are listed in Table 1.