Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807031145/hy2069sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807031145/hy2069Isup2.hkl |
CCDC reference: 657514
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.007 Å
- R factor = 0.031
- wR factor = 0.079
- Data-to-parameter ratio = 14.4
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT230_ALERT_2_B Hirshfeld Test Diff for C2 - C3 .. 9.74 su PLAT230_ALERT_2_B Hirshfeld Test Diff for C3 - C4 .. 7.03 su
Alert level C PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.06 PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 4 PLAT213_ALERT_2_C Atom C3 has ADP max/min Ratio ............. 3.30 prola PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.37 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.33 Ratio PLAT230_ALERT_2_C Hirshfeld Test Diff for S1 - C4 .. 6.54 su PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C2 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C3 PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C33
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 2
0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 9 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 8 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For related literature, see: DeRosa et al. (2004); Huo et al. (2006); Lamansky et al. (2001a, 2001b); Lo et al. (2003); Xu et al. (2005).
Compound (I) was obtained in two steps using standard method (Lamansky et al., 2001a). IrCl3.3H2O (0.178 g, 0.51 mmol), mpp (0.20 g, 1.26 mmol), 2-ethoxyethanol (9 ml) and water (3 ml) were heated to 393 K for 24 h under a nitrogen atmosphere. After cooling to room temperature, the precipitate was collected by filtration, washed with water and methanol, then vacuum dried. A mixture of the above-obtained chloride-bridged dimer (0.113 g, 0.10 mmol), tta (0.067 g, 0.25 mmol) and Na2CO3 (0.106 g, 1.0 mmol) in 2-ethoxyethanol (10 ml) was refluxed for 16 h under a nitrogen atmosphere. An excess of water was added after the solution was cooled to room temperature. Then the precipitate was collected by filtration and washed with methanol. The crude product was purified by column chromatography on silica gel with ethyl acetate/petroleum ether (1:10, v/v) as the eluent. Crystals suitable for X-ray diffraction were obtained by slow evaporation of the solvent.
All H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93Å (CH), 0.97 Å (CH2) and Uiso(H) = 1.2Ueq(C), and with C—H = 0.96 Å (CH3) and Uiso(H) = 1.5Ueq(C). The highest residual electron density was found 0.88 Å from atom Ir1 and the deepest hole 0.55 Å from atom S1.
In recent years, cyclometalated iridium complexes have been extensively investigated due to their promise as highly efficient phosphorescent emitters in organic light-emitting devices (OLEDs) (Lamansky et al., 2001b; Huo et al., 2006) and the other applications such as oxygen sensors (DeRosa et al., 2004) and biological labeling reagents (Lo et al., 2003). In general, heteroleptic cyclometalated iridium complexes have monoanionic derivatives of bidentate o-pyridylarene or o-pyridylheterocycle and ancillary ligands. In this paper, we utilize 3-methyl-2-phenylpyridine (mpp) as the cyclometalating ligand and thenoyltrifluoroacetone (tta) as the ancillary ligand to synthesize the title compound, (I). Compound (I) emits bright-yellow light under excitation of UV light, implying that it may find application in OLEDs as a highly efficient phosphorescent emitter.
Compound (I) shows a distorted octahedral coordination geometry around the Ir atom, formed by two mpp ligands and one tta ligand. The asymmetric unit contains one ethyl acetate solvent molecule (Fig. 1). The mpp ligands adopt a mutual eclipsed configuration with the N1 and N2 atoms residing at trans positions. The Ir—N distances are 2.041 (4)Å and 2.036 (4)Å (Table 1). The cyclometalated carbon atoms C20 and C26 are at cis positions with Ir—C distances of 1.986 (4)Å and 1.982 (4) Å. The Ir—C average bond distance (1.984 Å) is shorter than the Ir—N average bond distance (2.039 Å). This is similar to previously reported examples, including [(ppy)2Ir(acac)], [(tpy)2Ir(acac)] (Lamansky et al., 2001a) and [(dppy)2Ir(acac)] (Xu et al., 2005). The tta ligand displays an O,O'-chelating coordination mode, and the distances of Ir—O are 2.170 (3)Å and 2.171 (3) Å. All other features appear to be normal.
For related literature, see: DeRosa et al. (2004); Huo et al. (2006); Lamansky et al. (2001a, 2001b); Lo et al. (2003); Xu et al. (2005).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; 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.
Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. |
[Ir(C8H4F3O2S)(C12H10N)2]·C4H8O2 | Z = 2 |
Mr = 837.90 | F(000) = 828 |
Triclinic, P1 | Dx = 1.737 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71069 Å |
a = 11.4070 (8) Å | Cell parameters from 8940 reflections |
b = 12.889 (1) Å | θ = 1.7–26.0° |
c = 12.899 (2) Å | µ = 4.29 mm−1 |
α = 68.874 (1)° | T = 293 K |
β = 65.149 (2)° | Block, orange |
γ = 78.145 (1)° | 0.49 × 0.32 × 0.19 mm |
V = 1601.9 (3) Å3 |
Bruker APEX CCD area-detector diffractometer | 6129 independent reflections |
Radiation source: fine-focus sealed tube | 5681 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
φ and ω scans | θmax = 26.0°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −14→13 |
Tmin = 0.211, Tmax = 0.445 | k = −13→15 |
8980 measured reflections | l = −15→15 |
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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0455P)2 + 1.8469P] where P = (Fo2 + 2Fc2)/3 |
6129 reflections | (Δ/σ)max < 0.001 |
426 parameters | Δρmax = 2.03 e Å−3 |
2 restraints | Δρmin = −0.98 e Å−3 |
[Ir(C8H4F3O2S)(C12H10N)2]·C4H8O2 | γ = 78.145 (1)° |
Mr = 837.90 | V = 1601.9 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.4070 (8) Å | Mo Kα radiation |
b = 12.889 (1) Å | µ = 4.29 mm−1 |
c = 12.899 (2) Å | T = 293 K |
α = 68.874 (1)° | 0.49 × 0.32 × 0.19 mm |
β = 65.149 (2)° |
Bruker APEX CCD area-detector diffractometer | 6129 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 5681 reflections with I > 2σ(I) |
Tmin = 0.211, Tmax = 0.445 | Rint = 0.017 |
8980 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 2 restraints |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 1.05 | Δρmax = 2.03 e Å−3 |
6129 reflections | Δρmin = −0.98 e Å−3 |
426 parameters |
x | y | z | Uiso*/Ueq | ||
Ir1 | 0.179556 (14) | 0.182767 (14) | 0.202107 (14) | 0.02173 (7) | |
C1 | −0.4506 (5) | 0.1622 (6) | 0.4606 (5) | 0.0518 (15) | |
H1 | −0.5209 | 0.1660 | 0.5304 | 0.062* | |
C2 | −0.4607 (5) | 0.1454 (6) | 0.3677 (6) | 0.0580 (17) | |
H2 | −0.5402 | 0.1363 | 0.3692 | 0.070* | |
C3 | −0.3425 (3) | 0.1421 (4) | 0.2661 (3) | 0.0172 (8) | |
H3 | −0.3325 | 0.1311 | 0.1953 | 0.021* | |
C4 | −0.2386 (4) | 0.1603 (4) | 0.2993 (4) | 0.0278 (10) | |
C5 | −0.0994 (4) | 0.1644 (4) | 0.2290 (4) | 0.0252 (9) | |
C6 | −0.0528 (4) | 0.1541 (4) | 0.1117 (4) | 0.0292 (10) | |
H6 | −0.1142 | 0.1440 | 0.0869 | 0.035* | |
C7 | 0.0726 (4) | 0.1576 (4) | 0.0320 (4) | 0.0245 (9) | |
C8 | 0.1001 (5) | 0.1527 (4) | −0.0932 (4) | 0.0329 (11) | |
C9 | 0.1523 (4) | 0.4130 (4) | 0.0468 (4) | 0.0309 (10) | |
H9 | 0.1550 | 0.3765 | −0.0046 | 0.037* | |
C10 | 0.1436 (5) | 0.5277 (4) | 0.0097 (4) | 0.0339 (11) | |
H10 | 0.1412 | 0.5686 | −0.0654 | 0.041* | |
C11 | 0.1385 (4) | 0.5796 (4) | 0.0885 (4) | 0.0328 (11) | |
H11 | 0.1319 | 0.6571 | 0.0659 | 0.039* | |
C12 | 0.1431 (4) | 0.5198 (4) | 0.2002 (4) | 0.0281 (10) | |
C13 | 0.1340 (6) | 0.5842 (4) | 0.2803 (5) | 0.0425 (13) | |
H13A | 0.0700 | 0.5541 | 0.3588 | 0.064* | |
H13B | 0.1097 | 0.6611 | 0.2472 | 0.064* | |
H13C | 0.2164 | 0.5787 | 0.2860 | 0.064* | |
C14 | 0.1546 (4) | 0.4016 (4) | 0.2325 (4) | 0.0239 (9) | |
C15 | 0.1677 (4) | 0.3197 (4) | 0.3417 (4) | 0.0259 (9) | |
C16 | 0.1711 (5) | 0.3449 (4) | 0.4377 (4) | 0.0346 (11) | |
H16 | 0.1633 | 0.4190 | 0.4352 | 0.041* | |
C17 | 0.1856 (5) | 0.2623 (5) | 0.5349 (4) | 0.0378 (12) | |
H17 | 0.1881 | 0.2806 | 0.5974 | 0.045* | |
C18 | 0.1965 (5) | 0.1513 (4) | 0.5405 (4) | 0.0336 (11) | |
H18 | 0.2056 | 0.0951 | 0.6069 | 0.040* | |
C19 | 0.1939 (4) | 0.1246 (4) | 0.4467 (4) | 0.0279 (10) | |
H19 | 0.2012 | 0.0501 | 0.4512 | 0.034* | |
C20 | 0.1806 (4) | 0.2066 (4) | 0.3455 (4) | 0.0231 (9) | |
C21 | 0.4492 (4) | 0.2668 (4) | 0.0572 (4) | 0.0288 (10) | |
H21 | 0.4120 | 0.3388 | 0.0530 | 0.035* | |
C22 | 0.5807 (4) | 0.2517 (4) | −0.0065 (4) | 0.0334 (11) | |
H22 | 0.6300 | 0.3134 | −0.0523 | 0.040* | |
C23 | 0.6388 (4) | 0.1474 (4) | −0.0031 (4) | 0.0309 (10) | |
H23 | 0.7265 | 0.1385 | −0.0483 | 0.037* | |
C24 | 0.5660 (4) | 0.0538 (4) | 0.0688 (4) | 0.0274 (10) | |
H24 | 0.6058 | −0.0173 | 0.0722 | 0.033* | |
C25 | 0.4329 (4) | 0.0672 (4) | 0.1357 (4) | 0.0226 (9) | |
C26 | 0.3713 (4) | 0.1768 (4) | 0.1274 (4) | 0.0239 (9) | |
C27 | 0.3776 (4) | −0.1393 (4) | 0.2521 (4) | 0.0271 (9) | |
C28 | 0.5152 (5) | −0.1895 (4) | 0.2198 (5) | 0.0406 (12) | |
H28A | 0.5679 | −0.1444 | 0.2260 | 0.061* | |
H28B | 0.5483 | −0.1924 | 0.1390 | 0.061* | |
H28C | 0.5168 | −0.2635 | 0.2740 | 0.061* | |
C29 | 0.3453 (4) | −0.0242 (4) | 0.2139 (4) | 0.0229 (9) | |
C30 | 0.1236 (4) | −0.0567 (4) | 0.3240 (4) | 0.0321 (10) | |
H30 | 0.0379 | −0.0284 | 0.3490 | 0.039* | |
C31 | 0.2778 (5) | −0.2102 (4) | 0.3241 (4) | 0.0301 (10) | |
H31 | 0.2973 | −0.2867 | 0.3479 | 0.036* | |
C32 | 0.1501 (5) | −0.1699 (4) | 0.3613 (5) | 0.0333 (11) | |
H32 | 0.0838 | −0.2180 | 0.4102 | 0.040* | |
C33 | 0.5052 (6) | 0.4418 (5) | 0.1911 (5) | 0.0485 (14) | |
H33A | 0.5880 | 0.4156 | 0.1427 | 0.073* | |
H33B | 0.4713 | 0.5040 | 0.1409 | 0.073* | |
H33C | 0.4467 | 0.3830 | 0.2306 | 0.073* | |
C34 | 0.5199 (5) | 0.4769 (5) | 0.2825 (5) | 0.0419 (13) | |
C35 | 0.6654 (6) | 0.4854 (6) | 0.3667 (6) | 0.0528 (15) | |
H35A | 0.6182 | 0.4364 | 0.4456 | 0.063* | |
H35B | 0.6363 | 0.5618 | 0.3658 | 0.063* | |
C36 | 0.8079 (6) | 0.4676 (6) | 0.3401 (7) | 0.0622 (18) | |
H36A | 0.8254 | 0.4827 | 0.3997 | 0.093* | |
H36B | 0.8538 | 0.5168 | 0.2622 | 0.093* | |
H36C | 0.8358 | 0.3917 | 0.3414 | 0.093* | |
N1 | 0.2178 (3) | 0.0142 (3) | 0.2525 (3) | 0.0241 (8) | |
N2 | 0.1569 (3) | 0.3522 (3) | 0.1535 (3) | 0.0227 (7) | |
O1 | 0.1758 (3) | 0.1685 (3) | 0.0410 (3) | 0.0278 (7) | |
O2 | −0.0296 (3) | 0.1773 (3) | 0.2775 (3) | 0.0271 (7) | |
O3 | 0.6419 (3) | 0.4617 (3) | 0.2760 (3) | 0.0444 (9) | |
O4 | 0.4318 (4) | 0.5138 (4) | 0.3568 (4) | 0.0575 (12) | |
F1 | 0.1508 (4) | 0.2460 (3) | −0.1773 (3) | 0.0559 (9) | |
F2 | 0.1846 (3) | 0.0694 (3) | −0.1195 (3) | 0.0480 (8) | |
F3 | −0.0050 (3) | 0.1408 (3) | −0.1090 (3) | 0.0494 (8) | |
S1 | −0.29934 (14) | 0.17557 (14) | 0.43745 (14) | 0.0497 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ir1 | 0.01775 (10) | 0.02274 (10) | 0.02497 (10) | −0.00244 (6) | −0.00687 (7) | −0.00852 (7) |
C1 | 0.031 (3) | 0.065 (4) | 0.042 (3) | −0.003 (3) | −0.001 (2) | −0.014 (3) |
C2 | 0.029 (3) | 0.081 (5) | 0.061 (4) | −0.012 (3) | −0.018 (3) | −0.014 (4) |
C3 | 0.0035 (15) | 0.033 (2) | 0.0139 (18) | −0.0038 (15) | 0.0005 (14) | −0.0089 (17) |
C4 | 0.025 (2) | 0.027 (2) | 0.029 (2) | −0.0033 (18) | −0.0080 (19) | −0.0073 (19) |
C5 | 0.024 (2) | 0.018 (2) | 0.030 (2) | 0.0006 (17) | −0.0099 (19) | −0.0055 (18) |
C6 | 0.029 (2) | 0.027 (2) | 0.033 (2) | −0.0018 (19) | −0.014 (2) | −0.009 (2) |
C7 | 0.027 (2) | 0.019 (2) | 0.030 (2) | 0.0022 (17) | −0.0133 (19) | −0.0090 (18) |
C8 | 0.029 (2) | 0.039 (3) | 0.037 (3) | 0.000 (2) | −0.015 (2) | −0.016 (2) |
C9 | 0.032 (2) | 0.033 (3) | 0.030 (2) | −0.001 (2) | −0.014 (2) | −0.009 (2) |
C10 | 0.032 (2) | 0.035 (3) | 0.033 (3) | −0.001 (2) | −0.015 (2) | −0.006 (2) |
C11 | 0.025 (2) | 0.025 (2) | 0.041 (3) | 0.0006 (19) | −0.012 (2) | −0.004 (2) |
C12 | 0.019 (2) | 0.026 (2) | 0.038 (3) | −0.0028 (18) | −0.0075 (19) | −0.013 (2) |
C13 | 0.054 (3) | 0.026 (3) | 0.048 (3) | −0.001 (2) | −0.018 (3) | −0.015 (2) |
C14 | 0.0167 (19) | 0.026 (2) | 0.029 (2) | 0.0000 (17) | −0.0088 (17) | −0.0094 (19) |
C15 | 0.018 (2) | 0.030 (2) | 0.028 (2) | −0.0036 (18) | −0.0049 (17) | −0.0106 (19) |
C16 | 0.041 (3) | 0.035 (3) | 0.029 (2) | −0.007 (2) | −0.011 (2) | −0.011 (2) |
C17 | 0.041 (3) | 0.051 (3) | 0.027 (2) | −0.010 (2) | −0.012 (2) | −0.015 (2) |
C18 | 0.031 (2) | 0.040 (3) | 0.027 (2) | −0.005 (2) | −0.012 (2) | −0.004 (2) |
C19 | 0.024 (2) | 0.027 (2) | 0.031 (2) | −0.0030 (18) | −0.0099 (19) | −0.006 (2) |
C20 | 0.0122 (18) | 0.030 (2) | 0.024 (2) | −0.0023 (17) | −0.0044 (16) | −0.0076 (18) |
C21 | 0.026 (2) | 0.029 (2) | 0.034 (2) | −0.0040 (19) | −0.0127 (19) | −0.010 (2) |
C22 | 0.028 (2) | 0.043 (3) | 0.028 (2) | −0.014 (2) | −0.0089 (19) | −0.005 (2) |
C23 | 0.021 (2) | 0.047 (3) | 0.028 (2) | −0.001 (2) | −0.0089 (18) | −0.016 (2) |
C24 | 0.024 (2) | 0.034 (3) | 0.026 (2) | 0.0005 (19) | −0.0122 (18) | −0.009 (2) |
C25 | 0.020 (2) | 0.030 (2) | 0.023 (2) | −0.0020 (18) | −0.0094 (17) | −0.0124 (19) |
C26 | 0.021 (2) | 0.032 (2) | 0.025 (2) | −0.0046 (18) | −0.0116 (17) | −0.0094 (19) |
C27 | 0.032 (2) | 0.026 (2) | 0.026 (2) | 0.0008 (19) | −0.0125 (19) | −0.0099 (19) |
C28 | 0.035 (3) | 0.032 (3) | 0.050 (3) | 0.005 (2) | −0.017 (2) | −0.010 (2) |
C29 | 0.022 (2) | 0.030 (2) | 0.024 (2) | 0.0008 (18) | −0.0104 (17) | −0.0152 (19) |
C30 | 0.024 (2) | 0.033 (3) | 0.039 (3) | −0.007 (2) | −0.009 (2) | −0.011 (2) |
C31 | 0.034 (2) | 0.023 (2) | 0.033 (2) | −0.003 (2) | −0.012 (2) | −0.009 (2) |
C32 | 0.032 (2) | 0.027 (2) | 0.040 (3) | −0.010 (2) | −0.010 (2) | −0.009 (2) |
C33 | 0.044 (3) | 0.054 (4) | 0.046 (3) | −0.008 (3) | −0.018 (3) | −0.011 (3) |
C34 | 0.041 (3) | 0.032 (3) | 0.046 (3) | −0.007 (2) | −0.016 (3) | −0.003 (2) |
C35 | 0.044 (3) | 0.063 (4) | 0.059 (4) | 0.001 (3) | −0.021 (3) | −0.029 (3) |
C36 | 0.044 (3) | 0.066 (4) | 0.083 (5) | −0.006 (3) | −0.027 (3) | −0.026 (4) |
N1 | 0.0194 (17) | 0.0236 (19) | 0.030 (2) | −0.0023 (15) | −0.0071 (15) | −0.0104 (16) |
N2 | 0.0173 (17) | 0.0216 (18) | 0.0271 (19) | −0.0003 (14) | −0.0068 (14) | −0.0077 (15) |
O1 | 0.0233 (15) | 0.0345 (18) | 0.0269 (16) | −0.0026 (13) | −0.0074 (13) | −0.0130 (14) |
O2 | 0.0217 (15) | 0.0330 (18) | 0.0286 (16) | −0.0008 (13) | −0.0104 (13) | −0.0113 (14) |
O3 | 0.0309 (19) | 0.055 (2) | 0.047 (2) | 0.0013 (17) | −0.0129 (17) | −0.0194 (19) |
O4 | 0.038 (2) | 0.072 (3) | 0.072 (3) | 0.001 (2) | −0.012 (2) | −0.045 (3) |
F1 | 0.077 (2) | 0.058 (2) | 0.0277 (16) | −0.0214 (19) | −0.0157 (16) | −0.0037 (15) |
F2 | 0.0417 (17) | 0.062 (2) | 0.056 (2) | 0.0156 (16) | −0.0233 (15) | −0.0395 (18) |
F3 | 0.0341 (16) | 0.083 (3) | 0.0493 (18) | 0.0040 (16) | −0.0215 (14) | −0.0375 (18) |
S1 | 0.0400 (7) | 0.0617 (10) | 0.0450 (8) | −0.0041 (7) | −0.0121 (6) | −0.0181 (7) |
Ir1—C26 | 1.982 (4) | C17—H17 | 0.9300 |
Ir1—C20 | 1.986 (4) | C18—C19 | 1.385 (7) |
Ir1—N2 | 2.036 (4) | C18—H18 | 0.9300 |
Ir1—N1 | 2.041 (4) | C19—C20 | 1.397 (6) |
Ir1—O1 | 2.170 (3) | C19—H19 | 0.9300 |
Ir1—O2 | 2.171 (3) | C21—C22 | 1.386 (6) |
C1—C2 | 1.346 (9) | C21—C26 | 1.395 (6) |
C1—S1 | 1.657 (6) | C21—H21 | 0.9300 |
C1—H1 | 0.9300 | C22—C23 | 1.365 (7) |
C2—C3 | 1.439 (7) | C22—H22 | 0.9300 |
C2—H2 | 0.9300 | C23—C24 | 1.400 (7) |
C3—C4 | 1.501 (6) | C23—H23 | 0.9300 |
C3—H3 | 0.9300 | C24—C25 | 1.407 (6) |
C4—C5 | 1.462 (6) | C24—H24 | 0.9300 |
C4—S1 | 1.690 (5) | C25—C26 | 1.431 (6) |
C5—O2 | 1.266 (5) | C25—C29 | 1.477 (6) |
C5—C6 | 1.424 (6) | C27—C31 | 1.386 (7) |
C6—C7 | 1.365 (6) | C27—C29 | 1.407 (6) |
C6—H6 | 0.9300 | C27—C28 | 1.511 (7) |
C7—O1 | 1.271 (5) | C28—H28A | 0.9600 |
C7—C8 | 1.532 (6) | C28—H28B | 0.9600 |
C8—F2 | 1.327 (6) | C28—H28C | 0.9600 |
C8—F1 | 1.332 (6) | C29—N1 | 1.372 (5) |
C8—F3 | 1.343 (5) | C30—N1 | 1.343 (6) |
C9—N2 | 1.333 (6) | C30—C32 | 1.373 (7) |
C9—C10 | 1.375 (7) | C30—H30 | 0.9300 |
C9—H9 | 0.9300 | C31—C32 | 1.379 (7) |
C10—C11 | 1.383 (7) | C31—H31 | 0.9300 |
C10—H10 | 0.9300 | C32—H32 | 0.9300 |
C11—C12 | 1.385 (7) | C33—C34 | 1.486 (8) |
C11—H11 | 0.9300 | C33—H33A | 0.9600 |
C12—C14 | 1.421 (6) | C33—H33B | 0.9600 |
C12—C13 | 1.503 (7) | C33—H33C | 0.9600 |
C13—H13A | 0.9600 | C34—O4 | 1.215 (7) |
C13—H13B | 0.9600 | C34—O3 | 1.336 (6) |
C13—H13C | 0.9600 | C35—O3 | 1.445 (7) |
C14—N2 | 1.373 (5) | C35—C36 | 1.499 (8) |
C14—C15 | 1.470 (6) | C35—H35A | 0.9700 |
C15—C16 | 1.405 (6) | C35—H35B | 0.9700 |
C15—C20 | 1.420 (6) | C36—H36A | 0.9600 |
C16—C17 | 1.368 (7) | C36—H36B | 0.9600 |
C16—H16 | 0.9300 | C36—H36C | 0.9600 |
C17—C18 | 1.388 (7) | ||
C26—Ir1—C20 | 91.53 (16) | C18—C19—H19 | 119.1 |
C26—Ir1—N2 | 95.07 (16) | C20—C19—H19 | 119.1 |
C20—Ir1—N2 | 80.34 (16) | C19—C20—C15 | 117.9 (4) |
C26—Ir1—N1 | 80.47 (16) | C19—C20—Ir1 | 126.9 (3) |
C20—Ir1—N1 | 96.68 (17) | C15—C20—Ir1 | 115.3 (3) |
N2—Ir1—N1 | 174.61 (13) | C22—C21—C26 | 121.7 (5) |
C26—Ir1—O1 | 89.07 (14) | C22—C21—H21 | 119.2 |
C20—Ir1—O1 | 176.21 (15) | C26—C21—H21 | 119.2 |
N2—Ir1—O1 | 95.88 (13) | C23—C22—C21 | 120.9 (5) |
N1—Ir1—O1 | 87.11 (13) | C23—C22—H22 | 119.5 |
C26—Ir1—O2 | 174.81 (14) | C21—C22—H22 | 119.5 |
C20—Ir1—O2 | 92.52 (14) | C22—C23—C24 | 119.8 (4) |
N2—Ir1—O2 | 88.82 (13) | C22—C23—H23 | 120.1 |
N1—Ir1—O2 | 95.81 (13) | C24—C23—H23 | 120.1 |
O1—Ir1—O2 | 87.11 (11) | C23—C24—C25 | 120.2 (4) |
C2—C1—S1 | 112.8 (4) | C23—C24—H24 | 119.9 |
C2—C1—H1 | 123.6 | C25—C24—H24 | 119.9 |
S1—C1—H1 | 123.6 | C24—C25—C26 | 119.8 (4) |
C1—C2—C3 | 116.7 (5) | C24—C25—C29 | 125.5 (4) |
C1—C2—H2 | 121.6 | C26—C25—C29 | 114.7 (4) |
C3—C2—H2 | 121.6 | C21—C26—C25 | 117.5 (4) |
C2—C3—C4 | 104.9 (4) | C21—C26—Ir1 | 127.0 (4) |
C2—C3—H3 | 127.6 | C25—C26—Ir1 | 115.0 (3) |
C4—C3—H3 | 127.6 | C31—C27—C29 | 118.2 (4) |
C5—C4—C3 | 128.3 (4) | C31—C27—C28 | 118.3 (4) |
C5—C4—S1 | 119.7 (3) | C29—C27—C28 | 123.5 (4) |
C3—C4—S1 | 111.9 (3) | C27—C28—H28A | 109.5 |
O2—C5—C6 | 125.1 (4) | C27—C28—H28B | 109.5 |
O2—C5—C4 | 117.0 (4) | H28A—C28—H28B | 109.5 |
C6—C5—C4 | 117.8 (4) | C27—C28—H28C | 109.5 |
C7—C6—C5 | 126.7 (4) | H28A—C28—H28C | 109.5 |
C7—C6—H6 | 116.7 | H28B—C28—H28C | 109.5 |
C5—C6—H6 | 116.7 | N1—C29—C27 | 119.3 (4) |
O1—C7—C6 | 130.8 (4) | N1—C29—C25 | 112.2 (4) |
O1—C7—C8 | 111.1 (4) | C27—C29—C25 | 128.5 (4) |
C6—C7—C8 | 118.0 (4) | N1—C30—C32 | 121.8 (4) |
F2—C8—F1 | 106.6 (4) | N1—C30—H30 | 119.1 |
F2—C8—F3 | 106.3 (4) | C32—C30—H30 | 119.1 |
F1—C8—F3 | 106.3 (4) | C32—C31—C27 | 121.4 (5) |
F2—C8—C7 | 112.2 (4) | C32—C31—H31 | 119.3 |
F1—C8—C7 | 110.6 (4) | C27—C31—H31 | 119.3 |
F3—C8—C7 | 114.3 (4) | C30—C32—C31 | 118.2 (4) |
N2—C9—C10 | 122.7 (4) | C30—C32—H32 | 120.9 |
N2—C9—H9 | 118.6 | C31—C32—H32 | 120.9 |
C10—C9—H9 | 118.6 | C34—C33—H33A | 109.5 |
C9—C10—C11 | 117.3 (4) | C34—C33—H33B | 109.5 |
C9—C10—H10 | 121.4 | H33A—C33—H33B | 109.5 |
C11—C10—H10 | 121.4 | C34—C33—H33C | 109.5 |
C10—C11—C12 | 122.0 (5) | H33A—C33—H33C | 109.5 |
C10—C11—H11 | 119.0 | H33B—C33—H33C | 109.5 |
C12—C11—H11 | 119.0 | O4—C34—O3 | 122.9 (5) |
C11—C12—C14 | 118.1 (4) | O4—C34—C33 | 124.7 (5) |
C11—C12—C13 | 117.8 (4) | O3—C34—C33 | 112.4 (5) |
C14—C12—C13 | 124.1 (4) | O3—C35—C36 | 108.3 (5) |
C12—C13—H13A | 109.5 | O3—C35—H35A | 110.0 |
C12—C13—H13B | 109.5 | C36—C35—H35A | 110.0 |
H13A—C13—H13B | 109.5 | O3—C35—H35B | 110.0 |
C12—C13—H13C | 109.5 | C36—C35—H35B | 110.0 |
H13A—C13—H13C | 109.5 | H35A—C35—H35B | 108.4 |
H13B—C13—H13C | 109.5 | C35—C36—H36A | 109.5 |
N2—C14—C12 | 118.7 (4) | C35—C36—H36B | 109.5 |
N2—C14—C15 | 112.5 (4) | H36A—C36—H36B | 109.5 |
C12—C14—C15 | 128.9 (4) | C35—C36—H36C | 109.5 |
C16—C15—C20 | 119.3 (4) | H36A—C36—H36C | 109.5 |
C16—C15—C14 | 125.7 (4) | H36B—C36—H36C | 109.5 |
C20—C15—C14 | 115.0 (4) | C30—N1—C29 | 120.9 (4) |
C17—C16—C15 | 121.1 (5) | C30—N1—Ir1 | 122.0 (3) |
C17—C16—H16 | 119.5 | C29—N1—Ir1 | 117.0 (3) |
C15—C16—H16 | 119.5 | C9—N2—C14 | 121.2 (4) |
C16—C17—C18 | 120.2 (5) | C9—N2—Ir1 | 121.8 (3) |
C16—C17—H17 | 119.9 | C14—N2—Ir1 | 116.9 (3) |
C18—C17—H17 | 119.9 | C7—O1—Ir1 | 123.1 (3) |
C19—C18—C17 | 119.6 (5) | C5—O2—Ir1 | 127.0 (3) |
C19—C18—H18 | 120.2 | C34—O3—C35 | 116.9 (4) |
C17—C18—H18 | 120.2 | C1—S1—C4 | 93.7 (3) |
C18—C19—C20 | 121.9 (5) | ||
S1—C1—C2—C3 | −0.2 (8) | O1—Ir1—C26—C21 | 90.3 (4) |
C1—C2—C3—C4 | −0.2 (7) | C20—Ir1—C26—C25 | 102.1 (3) |
C2—C3—C4—C5 | 179.7 (5) | N2—Ir1—C26—C25 | −177.5 (3) |
C2—C3—C4—S1 | 0.5 (5) | N1—Ir1—C26—C25 | 5.5 (3) |
C3—C4—C5—O2 | −177.8 (4) | O1—Ir1—C26—C25 | −81.7 (3) |
S1—C4—C5—O2 | 1.4 (6) | C31—C27—C29—N1 | 2.5 (6) |
C3—C4—C5—C6 | 2.5 (7) | C28—C27—C29—N1 | −176.8 (4) |
S1—C4—C5—C6 | −178.3 (3) | C31—C27—C29—C25 | −178.7 (4) |
O2—C5—C6—C7 | −0.8 (8) | C28—C27—C29—C25 | 2.0 (7) |
C4—C5—C6—C7 | 178.9 (4) | C24—C25—C29—N1 | −170.4 (4) |
C5—C6—C7—O1 | 1.2 (8) | C26—C25—C29—N1 | 7.3 (5) |
C5—C6—C7—C8 | −175.9 (4) | C24—C25—C29—C27 | 10.8 (7) |
O1—C7—C8—F2 | 58.6 (5) | C26—C25—C29—C27 | −171.5 (4) |
C6—C7—C8—F2 | −123.8 (5) | C29—C27—C31—C32 | −2.1 (7) |
O1—C7—C8—F1 | −60.3 (5) | C28—C27—C31—C32 | 177.2 (4) |
C6—C7—C8—F1 | 117.3 (5) | N1—C30—C32—C31 | 0.5 (7) |
O1—C7—C8—F3 | 179.8 (4) | C27—C31—C32—C30 | 0.6 (7) |
C6—C7—C8—F3 | −2.6 (6) | C32—C30—N1—C29 | −0.1 (7) |
N2—C9—C10—C11 | −0.5 (7) | C32—C30—N1—Ir1 | −177.6 (4) |
C9—C10—C11—C12 | 0.5 (7) | C27—C29—N1—C30 | −1.4 (6) |
C10—C11—C12—C14 | 0.7 (7) | C25—C29—N1—C30 | 179.6 (4) |
C10—C11—C12—C13 | −178.7 (4) | C27—C29—N1—Ir1 | 176.2 (3) |
C11—C12—C14—N2 | −1.9 (6) | C25—C29—N1—Ir1 | −2.8 (4) |
C13—C12—C14—N2 | 177.4 (4) | C26—Ir1—N1—C30 | 176.1 (4) |
C11—C12—C14—C15 | 176.7 (4) | C20—Ir1—N1—C30 | 85.7 (4) |
C13—C12—C14—C15 | −4.0 (7) | O1—Ir1—N1—C30 | −94.3 (4) |
N2—C14—C15—C16 | 178.8 (4) | O2—Ir1—N1—C30 | −7.5 (4) |
C12—C14—C15—C16 | 0.1 (7) | C26—Ir1—N1—C29 | −1.5 (3) |
N2—C14—C15—C20 | 0.2 (5) | C20—Ir1—N1—C29 | −91.9 (3) |
C12—C14—C15—C20 | −178.5 (4) | O1—Ir1—N1—C29 | 88.1 (3) |
C20—C15—C16—C17 | −0.5 (7) | O2—Ir1—N1—C29 | 174.9 (3) |
C14—C15—C16—C17 | −179.0 (4) | C10—C9—N2—C14 | −0.7 (7) |
C15—C16—C17—C18 | −0.4 (8) | C10—C9—N2—Ir1 | −176.6 (3) |
C16—C17—C18—C19 | 0.6 (8) | C12—C14—N2—C9 | 1.9 (6) |
C17—C18—C19—C20 | 0.1 (7) | C15—C14—N2—C9 | −176.9 (4) |
C18—C19—C20—C15 | −0.9 (6) | C12—C14—N2—Ir1 | 178.0 (3) |
C18—C19—C20—Ir1 | 178.3 (3) | C15—C14—N2—Ir1 | −0.8 (4) |
C16—C15—C20—C19 | 1.1 (6) | C26—Ir1—N2—C9 | 86.2 (4) |
C14—C15—C20—C19 | 179.8 (4) | C20—Ir1—N2—C9 | 176.9 (4) |
C16—C15—C20—Ir1 | −178.2 (3) | O1—Ir1—N2—C9 | −3.4 (3) |
C14—C15—C20—Ir1 | 0.5 (5) | O2—Ir1—N2—C9 | −90.4 (3) |
C26—Ir1—C20—C19 | −85.0 (4) | C26—Ir1—N2—C14 | −89.9 (3) |
N2—Ir1—C20—C19 | −179.9 (4) | C20—Ir1—N2—C14 | 0.8 (3) |
N1—Ir1—C20—C19 | −4.4 (4) | O1—Ir1—N2—C14 | −179.5 (3) |
O2—Ir1—C20—C19 | 91.7 (4) | O2—Ir1—N2—C14 | 93.6 (3) |
C26—Ir1—C20—C15 | 94.2 (3) | C6—C7—O1—Ir1 | 1.3 (7) |
N2—Ir1—C20—C15 | −0.7 (3) | C8—C7—O1—Ir1 | 178.5 (3) |
N1—Ir1—C20—C15 | 174.8 (3) | C26—Ir1—O1—C7 | 173.9 (4) |
O2—Ir1—C20—C15 | −89.1 (3) | N2—Ir1—O1—C7 | −91.1 (4) |
C26—C21—C22—C23 | 0.2 (7) | N1—Ir1—O1—C7 | 93.4 (4) |
C21—C22—C23—C24 | −2.1 (7) | O2—Ir1—O1—C7 | −2.6 (3) |
C22—C23—C24—C25 | 1.0 (7) | C6—C5—O2—Ir1 | −2.0 (6) |
C23—C24—C25—C26 | 1.9 (6) | C4—C5—O2—Ir1 | 178.3 (3) |
C23—C24—C25—C29 | 179.5 (4) | C20—Ir1—O2—C5 | 179.3 (4) |
C22—C21—C26—C25 | 2.6 (6) | N2—Ir1—O2—C5 | 99.0 (4) |
C22—C21—C26—Ir1 | −169.2 (3) | N1—Ir1—O2—C5 | −83.7 (4) |
C24—C25—C26—C21 | −3.6 (6) | O1—Ir1—O2—C5 | 3.1 (4) |
C29—C25—C26—C21 | 178.5 (4) | O4—C34—O3—C35 | 3.4 (8) |
C24—C25—C26—Ir1 | 169.1 (3) | C33—C34—O3—C35 | −175.5 (5) |
C29—C25—C26—Ir1 | −8.7 (5) | C36—C35—O3—C34 | −177.7 (5) |
C20—Ir1—C26—C21 | −86.0 (4) | C2—C1—S1—C4 | 0.5 (6) |
N2—Ir1—C26—C21 | −5.6 (4) | C5—C4—S1—C1 | −179.8 (4) |
N1—Ir1—C26—C21 | 177.5 (4) | C3—C4—S1—C1 | −0.5 (4) |
Experimental details
Crystal data | |
Chemical formula | [Ir(C8H4F3O2S)(C12H10N)2]·C4H8O2 |
Mr | 837.90 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 11.4070 (8), 12.889 (1), 12.899 (2) |
α, β, γ (°) | 68.874 (1), 65.149 (2), 78.145 (1) |
V (Å3) | 1601.9 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 4.29 |
Crystal size (mm) | 0.49 × 0.32 × 0.19 |
Data collection | |
Diffractometer | Bruker APEX CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.211, 0.445 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8980, 6129, 5681 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.079, 1.05 |
No. of reflections | 6129 |
No. of parameters | 426 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.03, −0.98 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus (Sheldrick, 1990), SHELXL97.
Ir1—C26 | 1.982 (4) | Ir1—N1 | 2.041 (4) |
Ir1—C20 | 1.986 (4) | Ir1—O1 | 2.170 (3) |
Ir1—N2 | 2.036 (4) | Ir1—O2 | 2.171 (3) |
C26—Ir1—C20 | 91.53 (16) | N2—Ir1—O1 | 95.88 (13) |
C26—Ir1—N2 | 95.07 (16) | N1—Ir1—O1 | 87.11 (13) |
C20—Ir1—N2 | 80.34 (16) | C26—Ir1—O2 | 174.81 (14) |
C26—Ir1—N1 | 80.47 (16) | C20—Ir1—O2 | 92.52 (14) |
C20—Ir1—N1 | 96.68 (17) | N2—Ir1—O2 | 88.82 (13) |
N2—Ir1—N1 | 174.61 (13) | N1—Ir1—O2 | 95.81 (13) |
C26—Ir1—O1 | 89.07 (14) | O1—Ir1—O2 | 87.11 (11) |
C20—Ir1—O1 | 176.21 (15) |
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In recent years, cyclometalated iridium complexes have been extensively investigated due to their promise as highly efficient phosphorescent emitters in organic light-emitting devices (OLEDs) (Lamansky et al., 2001b; Huo et al., 2006) and the other applications such as oxygen sensors (DeRosa et al., 2004) and biological labeling reagents (Lo et al., 2003). In general, heteroleptic cyclometalated iridium complexes have monoanionic derivatives of bidentate o-pyridylarene or o-pyridylheterocycle and ancillary ligands. In this paper, we utilize 3-methyl-2-phenylpyridine (mpp) as the cyclometalating ligand and thenoyltrifluoroacetone (tta) as the ancillary ligand to synthesize the title compound, (I). Compound (I) emits bright-yellow light under excitation of UV light, implying that it may find application in OLEDs as a highly efficient phosphorescent emitter.
Compound (I) shows a distorted octahedral coordination geometry around the Ir atom, formed by two mpp ligands and one tta ligand. The asymmetric unit contains one ethyl acetate solvent molecule (Fig. 1). The mpp ligands adopt a mutual eclipsed configuration with the N1 and N2 atoms residing at trans positions. The Ir—N distances are 2.041 (4)Å and 2.036 (4)Å (Table 1). The cyclometalated carbon atoms C20 and C26 are at cis positions with Ir—C distances of 1.986 (4)Å and 1.982 (4) Å. The Ir—C average bond distance (1.984 Å) is shorter than the Ir—N average bond distance (2.039 Å). This is similar to previously reported examples, including [(ppy)2Ir(acac)], [(tpy)2Ir(acac)] (Lamansky et al., 2001a) and [(dppy)2Ir(acac)] (Xu et al., 2005). The tta ligand displays an O,O'-chelating coordination mode, and the distances of Ir—O are 2.170 (3)Å and 2.171 (3) Å. All other features appear to be normal.