Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827011300663X/fa3306sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827011300663X/fa3306Isup2.hkl |
CCDC reference: 950351
For related literature, see: Baranoff et al. (2010); Colombo et al. (1994); Cooper et al. (2010); Fernández-Hernández, Yang, Beltrán, Lemaur, Polo, Fröhlich, Cornil & De Cola (2011); Görbitz (1999); Graces et al. (1988); Hirshfeld (1976); Kitaigorodskii (1973); Lamansky et al. (2001); Lyu et al. (2006); McGee & Mann (2007); Okada et al. (2005); Prince (1982); Ragni et al. (2006, 2009); Schmid et al. (1994); Sheldrick (2008); Sheldrick & Schneider (1997); Spek (2009); Sprouse et al. (1984); Ulbricht et al. (2009); Watkin (1994); Wu et al. (2007); Yang et al. (2005).
The title complex was prepared by refluxing, under a nitrogen athmosphere, 2-(4-benzylsulfonyl-2-fluorophenyl)pyridine with iridium chloride trihydrate in a mixture of water and 2-ethoxyethanol [Please give quantities or mole ratio]. The precipitate was filtered and washed with hexane and ethanol. The products were purified by column chromatography on silica gel, using first petroleum ether–ethyl acetate (1:1 v/v) as eluent to remove the residual unreacted 2-(4-benzylsulfonyl-2-fluorophenyl)pyridine, and then acetone–petroleum ether (6:4 v/v) to elute the dimers. Yellow single crystals of (I) suitable for structure analysis were obtained from a dichloromethane solution kept in a toluene atmosphere.
The relatively large ratio of minimum-to-maximum corrections applied in the multiscan process (0.653:1) reflects changes in the illuminated volume of the crystal, which it was attempting to minimize and which were taken into account (Görbitz, 1999) by the multiscan interframe scaling method (SADABS; Sheldrick, 2008). Structural refinements on both Fo and Fo2 were tested. They resulted in the same atomic positions, within 3σ. Here, the parameters derived from the refinement against Fo are reported. Reflections with I > 3σ(I) were considered observed (Watkin, 1994).
The H atoms were all located in a difference map and repositioned geometrically. They were initially refined with soft restraints on the bond lengths and angles to regularize their geometry (C—H = 0.93–0.98 Å), with Uiso(H) values in the range 1.2–1.5Ueq(parent), after which the positions were refined with riding constraints (Cooper et al., 2010).
The residual peak pattern of the difference Fourier map suggested that the solvent molecules were highly disordered, and all attempts to model the disorder were unsuccessful. In the final cycles of refinement, the contribution to electron density corresponding to disordered toluene molecules was removed from the observed data using the SQUEEZE option in PLATON (Spek, 2009). On the assumption that the two large voids in the unit cell related by a centre of inversion contain one molecule of toluene each, the contribution of one molecule of toluene has been included in the molecular formula.
Possibly owing to the influence of the solvent, the rigid-bond model (Hirshfeld, 1976) was violated for some bonds. To achieve a better correspondence for these atom pairs, default `rigid-bond restraints' (DELU) and `similar ADP restraints' (SIMU) on neighbouring atoms (Sheldrick & Schneider, 1997) were applied. In addition, some phenyl-group bond lengths were not initially consistent with the aromatic system distance, so soft restraints to the expected value were applied. Reflections with Δ(Fo - Fc)/Fo larger than 30% were manually omitted in the final cycles of refinement, because they were considered to have been poorly measured and/or affected by the structural disorder. For more details about the weighting schemes used in the refinement, see Prince (1982) and Watkin (1994).
Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003).
[Ir2(C18H13FNO2S)4Cl2]·C7H8 | Z = 2 |
Mr = 1852.97 | F(000) = 1828 |
Triclinic, P1 | Dx = 1.715 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 13.5049 (4) Å | Cell parameters from 9254 reflections |
b = 14.3144 (5) Å | θ = 2–34° |
c = 19.6770 (6) Å | µ = 3.97 mm−1 |
α = 89.772 (2)° | T = 293 K |
β = 78.954 (2)° | Plate, yellow |
γ = 74.262 (2)° | 0.75 × 0.44 × 0.08 mm |
V = 3588.8 (2) Å3 |
Bruker Kappa APEXII CCD area-detector diffractometer | 9065 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
ω/2θ scans | θmax = 26.5°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008) | h = −16→16 |
Tmin = 0.653, Tmax = 1.000 | k = −17→17 |
49952 measured reflections | l = 0→24 |
14669 independent reflections |
Refinement on F | Primary atom site location: difference Fourier map |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.043 | H-atom parameters constrained |
S = 1.14 | {Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] =
1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)], where Ai are the Chebychev coefficients listed below and x = F /Fmax. Method = robust weighting (Prince, 1982), W = [weight] * [1-(ΔF/6σF)2]2, where Ai are: 0.945 1.14 0.666 0.399 0.113} |
8337 reflections | (Δ/σ)max = 0.002 |
865 parameters | Δρmax = 2.01 e Å−3 |
440 restraints | Δρmin = −1.37 e Å−3 |
[Ir2(C18H13FNO2S)4Cl2]·C7H8 | γ = 74.262 (2)° |
Mr = 1852.97 | V = 3588.8 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 13.5049 (4) Å | Mo Kα radiation |
b = 14.3144 (5) Å | µ = 3.97 mm−1 |
c = 19.6770 (6) Å | T = 293 K |
α = 89.772 (2)° | 0.75 × 0.44 × 0.08 mm |
β = 78.954 (2)° |
Bruker Kappa APEXII CCD area-detector diffractometer | 14669 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008) | 9065 reflections with I > 2σ(I) |
Tmin = 0.653, Tmax = 1.000 | Rint = 0.048 |
49952 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 440 restraints |
wR(F2) = 0.043 | H-atom parameters constrained |
S = 1.14 | Δρmax = 2.01 e Å−3 |
8337 reflections | Δρmin = −1.37 e Å−3 |
865 parameters |
x | y | z | Uiso*/Ueq | ||
O1 | 0.7440 (5) | −0.0402 (6) | 0.1173 (3) | 0.0706 | |
O2 | 0.6208 (7) | −0.0934 (7) | 0.2073 (4) | 0.0827 | |
O3 | 1.2674 (5) | −0.1750 (6) | 0.3865 (3) | 0.0651 | |
O4 | 1.3929 (6) | −0.2892 (5) | 0.2946 (4) | 0.0777 | |
O5 | 0.6338 (6) | 0.7888 (5) | 0.3854 (4) | 0.0708 | |
O6 | 0.7521 (5) | 0.6690 (6) | 0.4461 (4) | 0.0671 | |
O7 | 1.2683 (5) | 0.5346 (6) | 0.0420 (4) | 0.0703 | |
O8 | 1.3932 (6) | 0.5857 (6) | 0.1019 (4) | 0.0787 | |
S1 | 0.6726 (2) | −0.0219 (2) | 0.18267 (13) | 0.0601 | |
S2 | 1.33590 (18) | −0.19111 (17) | 0.31941 (12) | 0.0515 | |
S3 | 0.68163 (18) | 0.69006 (18) | 0.39724 (13) | 0.0536 | |
S4 | 1.33757 (19) | 0.5166 (2) | 0.09077 (13) | 0.0571 | |
N1 | 0.9878 (5) | 0.1133 (5) | 0.3563 (3) | 0.0385 | |
C2 | 1.0540 (7) | 0.1339 (6) | 0.3924 (4) | 0.0413 | |
C3 | 1.0368 (8) | 0.1308 (7) | 0.4636 (5) | 0.0531 | |
C4 | 0.9522 (9) | 0.1157 (7) | 0.4972 (5) | 0.0549 | |
C5 | 0.8755 (7) | 0.0951 (6) | 0.4627 (4) | 0.0486 | |
C6 | 0.8977 (6) | 0.0911 (6) | 0.3896 (4) | 0.0395 | |
C7 | 0.8380 (7) | 0.0611 (7) | 0.3429 (4) | 0.0460 | |
C8 | 0.8833 (6) | 0.0600 (6) | 0.2714 (4) | 0.0357 | |
C9 | 0.8333 (6) | 0.0294 (7) | 0.2243 (5) | 0.0443 | |
C10 | 0.7389 (7) | 0.0060 (7) | 0.2453 (5) | 0.0509 | |
C11 | 0.6931 (8) | 0.0091 (9) | 0.3145 (5) | 0.0656 | |
C12 | 0.7440 (8) | 0.0371 (9) | 0.3617 (5) | 0.0664 | |
C13 | 0.5725 (8) | 0.0892 (9) | 0.1782 (6) | 0.0710 | |
C14 | 0.6130 (9) | 0.1746 (9) | 0.1587 (5) | 0.0743 | |
C15 | 0.6476 (9) | 0.1886 (11) | 0.0897 (6) | 0.0873 | |
C16 | 0.6808 (10) | 0.2677 (11) | 0.0685 (8) | 0.0985 | |
C17 | 0.6824 (10) | 0.3338 (11) | 0.1181 (8) | 0.1017 | |
C18 | 0.6494 (11) | 0.3233 (12) | 0.1877 (8) | 0.1005 | |
C19 | 0.6110 (11) | 0.2443 (10) | 0.2077 (8) | 0.0960 | |
N20 | 1.0181 (5) | 0.1038 (5) | 0.1455 (3) | 0.0312 | |
C21 | 0.9534 (6) | 0.1584 (6) | 0.1091 (4) | 0.0409 | |
C22 | 0.9725 (7) | 0.1465 (7) | 0.0346 (5) | 0.0481 | |
C23 | 1.0557 (8) | 0.0845 (7) | 0.0042 (5) | 0.0517 | |
C24 | 1.1275 (7) | 0.0231 (7) | 0.0396 (4) | 0.0477 | |
C25 | 1.1056 (6) | 0.0325 (6) | 0.1123 (4) | 0.0378 | |
C26 | 1.1623 (6) | −0.0292 (6) | 0.1604 (4) | 0.0422 | |
C27 | 1.1194 (6) | −0.0051 (7) | 0.2317 (4) | 0.0365 | |
C28 | 1.1723 (6) | −0.0608 (6) | 0.2798 (4) | 0.0385 | |
C29 | 1.2625 (7) | −0.1337 (7) | 0.2574 (5) | 0.0473 | |
C30 | 1.3044 (8) | −0.1584 (8) | 0.1878 (5) | 0.0650 | |
C31 | 1.2529 (8) | −0.1042 (8) | 0.1405 (5) | 0.0645 | |
C32 | 1.4323 (7) | −0.1269 (7) | 0.3176 (5) | 0.0561 | |
C33 | 1.3949 (7) | −0.0253 (7) | 0.3479 (5) | 0.0533 | |
C34 | 1.3984 (9) | −0.0077 (8) | 0.4174 (6) | 0.0688 | |
C35 | 1.3707 (10) | 0.0858 (9) | 0.4454 (7) | 0.0829 | |
C36 | 1.3353 (9) | 0.1641 (9) | 0.4067 (7) | 0.0763 | |
C37 | 1.3296 (8) | 0.1485 (8) | 0.3396 (6) | 0.0649 | |
C38 | 1.4367 (7) | 0.4048 (9) | 0.0661 (5) | 0.0639 | |
C39 | 1.3570 (7) | 0.0549 (7) | 0.3096 (5) | 0.0531 | |
N40 | 1.0213 (5) | 0.3824 (5) | 0.3471 (3) | 0.0362 | |
C41 | 0.9545 (6) | 0.3636 (6) | 0.4009 (4) | 0.0383 | |
C42 | 0.9714 (7) | 0.3660 (6) | 0.4709 (4) | 0.0453 | |
C43 | 1.0544 (8) | 0.3866 (7) | 0.4803 (5) | 0.0537 | |
C44 | 1.1267 (7) | 0.4080 (7) | 0.4255 (5) | 0.0493 | |
C45 | 1.1069 (6) | 0.4083 (6) | 0.3586 (4) | 0.0398 | |
C46 | 1.1683 (7) | 0.4373 (7) | 0.2958 (5) | 0.0477 | |
C47 | 1.1255 (6) | 0.4349 (7) | 0.2359 (5) | 0.0409 | |
C48 | 1.1760 (6) | 0.4650 (7) | 0.1741 (4) | 0.0432 | |
C49 | 1.2674 (7) | 0.4930 (7) | 0.1716 (5) | 0.0498 | |
C50 | 1.3085 (8) | 0.4965 (9) | 0.2307 (5) | 0.0629 | |
C51 | 1.2581 (8) | 0.4668 (9) | 0.2912 (5) | 0.0601 | |
C52 | 1.3994 (8) | 0.3197 (8) | 0.0480 (5) | 0.0602 | |
C53 | 1.3675 (8) | 0.2591 (8) | 0.0972 (6) | 0.0684 | |
C54 | 1.3388 (9) | 0.1785 (9) | 0.0771 (7) | 0.0752 | |
C55 | 1.3410 (10) | 0.1578 (10) | 0.0093 (7) | 0.0861 | |
C56 | 1.3719 (11) | 0.2183 (10) | −0.0404 (7) | 0.0897 | |
C57 | 1.4005 (10) | 0.2988 (9) | −0.0212 (6) | 0.0773 | |
N58 | 0.9932 (5) | 0.3870 (5) | 0.1451 (3) | 0.0334 | |
C59 | 1.0586 (6) | 0.3323 (6) | 0.0912 (4) | 0.0408 | |
C60 | 1.0434 (8) | 0.3419 (7) | 0.0248 (5) | 0.0504 | |
C61 | 0.9632 (8) | 0.4032 (7) | 0.0104 (4) | 0.0450 | |
C62 | 0.8846 (7) | 0.4651 (7) | 0.0664 (4) | 0.0497 | |
C63 | 0.9048 (6) | 0.4580 (6) | 0.1330 (4) | 0.0399 | |
C64 | 0.8472 (6) | 0.5184 (6) | 0.1949 (5) | 0.0425 | |
C65 | 0.8909 (6) | 0.4980 (6) | 0.2560 (4) | 0.0340 | |
C66 | 0.8405 (6) | 0.5519 (6) | 0.3153 (4) | 0.0402 | |
C67 | 0.7490 (7) | 0.6275 (7) | 0.3188 (5) | 0.0499 | |
C68 | 0.7057 (8) | 0.6491 (8) | 0.2589 (5) | 0.0732 | |
C69 | 0.7573 (9) | 0.5926 (9) | 0.1993 (5) | 0.0817 | |
C70 | 0.5787 (7) | 0.6342 (8) | 0.4242 (6) | 0.0650 | |
C71 | 0.6152 (8) | 0.5294 (9) | 0.4389 (6) | 0.0687 | |
C72 | 0.6226 (10) | 0.4603 (10) | 0.3899 (7) | 0.0883 | |
C73 | 0.6548 (11) | 0.3598 (11) | 0.4077 (8) | 0.0968 | |
C74 | 0.6757 (10) | 0.3348 (11) | 0.4700 (8) | 0.0952 | |
C75 | 0.6675 (10) | 0.4065 (11) | 0.5182 (8) | 0.0920 | |
C76 | 0.6383 (9) | 0.5032 (10) | 0.5034 (7) | 0.0771 | |
Cl1 | 0.87462 (14) | 0.28127 (15) | 0.26514 (10) | 0.0347 | |
Cl2 | 1.13626 (14) | 0.21142 (15) | 0.23118 (10) | 0.0354 | |
Ir1 | 1.00330 (2) | 0.11670 (2) | 0.250499 (16) | 0.0325 | |
Ir2 | 1.00697 (2) | 0.37639 (2) | 0.246152 (16) | 0.0326 | |
F27 | 1.3012 (6) | 0.4672 (8) | 0.3478 (3) | 0.1135 | |
F50 | 0.7135 (6) | 0.6140 (6) | 0.1427 (4) | 0.1122 | |
F69 | 1.2949 (6) | −0.1284 (7) | 0.0732 (3) | 0.1196 | |
F92 | 0.6994 (6) | 0.0421 (6) | 0.4297 (3) | 0.0944 | |
H21 | 1.1132 | 0.1508 | 0.3683 | 0.0490* | |
H31 | 1.0872 | 0.1402 | 0.4873 | 0.0672* | |
H41 | 0.9396 | 0.1186 | 0.5452 | 0.0722* | |
H51 | 0.8134 | 0.0842 | 0.4872 | 0.0570* | |
H91 | 0.8631 | 0.0250 | 0.1769 | 0.0532* | |
H111 | 0.6304 | −0.0067 | 0.3289 | 0.0842* | |
H131 | 0.5257 | 0.1039 | 0.2229 | 0.0850* | |
H132 | 0.5342 | 0.0785 | 0.1434 | 0.0852* | |
H151 | 0.6487 | 0.1428 | 0.0558 | 0.1062* | |
H161 | 0.7037 | 0.2778 | 0.0220 | 0.1441* | |
H171 | 0.7061 | 0.3879 | 0.1048 | 0.1481* | |
H181 | 0.6511 | 0.3682 | 0.2211 | 0.1511* | |
H191 | 0.5837 | 0.2373 | 0.2542 | 0.1331* | |
H211 | 0.8940 | 0.2056 | 0.1325 | 0.0501* | |
H221 | 0.9254 | 0.1836 | 0.0095 | 0.0620* | |
H231 | 1.0690 | 0.0794 | −0.0442 | 0.0652* | |
H241 | 1.1878 | −0.0221 | 0.0159 | 0.0562* | |
H281 | 1.1459 | −0.0476 | 0.3271 | 0.0464* | |
H301 | 1.3647 | −0.2092 | 0.1738 | 0.0770* | |
H321 | 1.4849 | −0.1641 | 0.3421 | 0.0670* | |
H322 | 1.4645 | −0.1236 | 0.2694 | 0.0670* | |
H341 | 1.4204 | −0.0602 | 0.4444 | 0.0853* | |
H351 | 1.3758 | 0.0968 | 0.4913 | 0.1071* | |
H361 | 1.3156 | 0.2274 | 0.4265 | 0.0962* | |
H371 | 1.3067 | 0.2011 | 0.3132 | 0.0822* | |
H381 | 1.4864 | 0.4154 | 0.0261 | 0.0742* | |
H382 | 1.4726 | 0.3880 | 0.1045 | 0.0741* | |
H391 | 1.3495 | 0.0444 | 0.2642 | 0.0623* | |
H411 | 0.8946 | 0.3482 | 0.3927 | 0.0461* | |
H421 | 0.9239 | 0.3524 | 0.5077 | 0.0533* | |
H431 | 1.0661 | 0.3880 | 0.5253 | 0.0712* | |
H441 | 1.1877 | 0.4217 | 0.4334 | 0.0601* | |
H481 | 1.1492 | 0.4647 | 0.1338 | 0.0511* | |
H501 | 1.3678 | 0.5186 | 0.2296 | 0.0811* | |
H531 | 1.3648 | 0.2730 | 0.1440 | 0.0811* | |
H541 | 1.3179 | 0.1385 | 0.1111 | 0.0922* | |
H551 | 1.3231 | 0.1027 | −0.0039 | 0.1082* | |
H561 | 1.3720 | 0.2056 | −0.0870 | 0.1191* | |
H571 | 1.4226 | 0.3393 | −0.0548 | 0.0951* | |
H591 | 1.1177 | 0.2852 | 0.0998 | 0.0500* | |
H601 | 1.0931 | 0.3023 | −0.0113 | 0.0641* | |
H611 | 0.9541 | 0.4086 | −0.0350 | 0.0583* | |
H621 | 0.8228 | 0.5079 | 0.0583 | 0.0611* | |
H661 | 0.8681 | 0.5377 | 0.3553 | 0.0482* | |
H681 | 0.6439 | 0.6990 | 0.2598 | 0.0830* | |
H701 | 0.5342 | 0.6692 | 0.4662 | 0.0781* | |
H702 | 0.5384 | 0.6392 | 0.3877 | 0.0782* | |
H721 | 0.6058 | 0.4781 | 0.3469 | 0.1172* | |
H731 | 0.6620 | 0.3115 | 0.3737 | 0.1311* | |
H741 | 0.6938 | 0.2693 | 0.4801 | 0.1242* | |
H751 | 0.6836 | 0.3893 | 0.5612 | 0.1313* | |
H761 | 0.6329 | 0.5516 | 0.5367 | 0.0943* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.057 (4) | 0.108 (6) | 0.050 (4) | −0.040 (4) | 0.007 (3) | −0.009 (4) |
O2 | 0.090 (6) | 0.103 (6) | 0.072 (5) | −0.067 (5) | 0.002 (4) | −0.002 (5) |
O3 | 0.054 (4) | 0.078 (5) | 0.052 (4) | −0.006 (3) | −0.001 (3) | 0.020 (4) |
O4 | 0.085 (5) | 0.050 (4) | 0.080 (5) | 0.015 (4) | −0.019 (4) | 0.014 (4) |
O5 | 0.068 (4) | 0.058 (4) | 0.068 (5) | 0.018 (4) | −0.021 (4) | −0.004 (4) |
O6 | 0.054 (4) | 0.085 (5) | 0.056 (4) | 0.005 (4) | −0.028 (3) | −0.010 (4) |
O7 | 0.057 (4) | 0.099 (6) | 0.059 (4) | −0.024 (4) | −0.018 (3) | 0.031 (4) |
O8 | 0.085 (5) | 0.085 (6) | 0.079 (5) | −0.053 (5) | −0.005 (4) | 0.017 (4) |
S1 | 0.0538 (14) | 0.0883 (19) | 0.0482 (13) | −0.0424 (14) | −0.0010 (11) | −0.0021 (13) |
S2 | 0.0479 (12) | 0.0481 (13) | 0.0468 (13) | 0.0031 (10) | −0.0055 (10) | 0.0143 (10) |
S3 | 0.0470 (12) | 0.0539 (14) | 0.0517 (13) | 0.0075 (10) | −0.0211 (10) | −0.0054 (11) |
S4 | 0.0529 (13) | 0.0756 (18) | 0.0545 (14) | −0.0347 (13) | −0.0141 (11) | 0.0225 (13) |
N1 | 0.042 (3) | 0.033 (3) | 0.033 (3) | −0.002 (3) | −0.002 (3) | −0.001 (3) |
C2 | 0.044 (4) | 0.038 (4) | 0.041 (4) | −0.008 (3) | −0.010 (3) | 0.003 (3) |
C3 | 0.061 (4) | 0.054 (5) | 0.042 (4) | −0.003 (4) | −0.022 (4) | 0.004 (4) |
C4 | 0.084 (5) | 0.044 (4) | 0.027 (4) | −0.005 (4) | −0.006 (4) | 0.009 (3) |
C5 | 0.060 (4) | 0.045 (4) | 0.033 (4) | −0.011 (4) | 0.005 (3) | 0.011 (3) |
C6 | 0.049 (4) | 0.031 (4) | 0.036 (4) | −0.010 (3) | −0.001 (3) | 0.007 (3) |
C7 | 0.046 (4) | 0.062 (5) | 0.032 (4) | −0.019 (4) | −0.006 (3) | 0.012 (4) |
C8 | 0.032 (3) | 0.040 (4) | 0.030 (4) | −0.009 (3) | 0.002 (3) | 0.005 (3) |
C9 | 0.043 (4) | 0.053 (4) | 0.038 (4) | −0.020 (3) | −0.001 (3) | 0.002 (3) |
C10 | 0.050 (4) | 0.069 (5) | 0.042 (4) | −0.033 (4) | −0.003 (3) | 0.000 (4) |
C11 | 0.060 (5) | 0.100 (6) | 0.046 (4) | −0.046 (4) | 0.002 (4) | 0.003 (4) |
C12 | 0.067 (4) | 0.106 (5) | 0.035 (4) | −0.048 (4) | 0.002 (3) | 0.009 (4) |
C13 | 0.043 (5) | 0.115 (10) | 0.058 (6) | −0.033 (6) | −0.001 (5) | −0.003 (6) |
C14 | 0.058 (5) | 0.095 (7) | 0.076 (6) | −0.027 (5) | −0.019 (5) | 0.014 (5) |
C15 | 0.060 (5) | 0.105 (7) | 0.089 (6) | −0.016 (5) | −0.003 (5) | 0.025 (6) |
C16 | 0.061 (5) | 0.107 (7) | 0.117 (7) | −0.012 (5) | −0.010 (6) | 0.038 (6) |
C17 | 0.064 (5) | 0.107 (7) | 0.136 (8) | −0.017 (6) | −0.034 (6) | 0.033 (6) |
C18 | 0.087 (6) | 0.107 (7) | 0.124 (7) | −0.029 (5) | −0.059 (6) | 0.008 (6) |
C19 | 0.093 (6) | 0.108 (7) | 0.099 (7) | −0.030 (6) | −0.044 (6) | 0.009 (6) |
N20 | 0.028 (3) | 0.039 (3) | 0.027 (3) | −0.011 (2) | −0.004 (2) | 0.008 (3) |
C21 | 0.044 (4) | 0.045 (4) | 0.035 (4) | −0.014 (3) | −0.010 (3) | 0.009 (3) |
C22 | 0.053 (4) | 0.055 (5) | 0.049 (4) | −0.026 (4) | −0.024 (3) | 0.016 (4) |
C23 | 0.064 (4) | 0.063 (5) | 0.033 (4) | −0.028 (4) | −0.008 (3) | 0.007 (4) |
C24 | 0.047 (4) | 0.057 (5) | 0.032 (4) | −0.008 (3) | 0.001 (3) | 0.000 (3) |
C25 | 0.032 (3) | 0.046 (4) | 0.032 (3) | −0.012 (3) | 0.002 (3) | 0.005 (3) |
C26 | 0.044 (4) | 0.043 (5) | 0.032 (4) | 0.001 (4) | −0.009 (3) | −0.001 (4) |
C27 | 0.029 (4) | 0.056 (6) | 0.023 (4) | −0.016 (4) | 0.004 (3) | 0.002 (4) |
C28 | 0.031 (4) | 0.042 (5) | 0.037 (4) | −0.002 (3) | −0.003 (3) | 0.009 (4) |
C29 | 0.042 (4) | 0.052 (5) | 0.040 (5) | −0.004 (4) | −0.004 (4) | 0.014 (4) |
C30 | 0.065 (6) | 0.067 (7) | 0.044 (6) | 0.011 (5) | −0.010 (5) | 0.005 (5) |
C31 | 0.072 (6) | 0.071 (7) | 0.028 (5) | 0.011 (5) | 0.001 (4) | 0.005 (4) |
C32 | 0.039 (5) | 0.066 (6) | 0.052 (6) | 0.001 (4) | −0.003 (4) | 0.011 (5) |
C33 | 0.048 (4) | 0.064 (5) | 0.051 (4) | −0.020 (4) | −0.010 (4) | 0.015 (4) |
C34 | 0.080 (5) | 0.065 (5) | 0.060 (5) | −0.013 (5) | −0.021 (4) | 0.017 (4) |
C35 | 0.093 (6) | 0.076 (5) | 0.077 (6) | −0.018 (5) | −0.017 (5) | 0.007 (5) |
C36 | 0.078 (5) | 0.069 (5) | 0.085 (6) | −0.020 (5) | −0.023 (5) | 0.006 (5) |
C37 | 0.060 (5) | 0.065 (5) | 0.077 (5) | −0.020 (4) | −0.028 (4) | 0.018 (4) |
C38 | 0.040 (5) | 0.103 (9) | 0.055 (6) | −0.027 (5) | −0.015 (4) | 0.023 (6) |
C39 | 0.051 (4) | 0.063 (5) | 0.057 (5) | −0.025 (4) | −0.024 (4) | 0.018 (4) |
N40 | 0.026 (3) | 0.041 (3) | 0.036 (3) | −0.001 (3) | −0.004 (2) | 0.002 (3) |
C41 | 0.036 (3) | 0.036 (4) | 0.038 (4) | −0.003 (3) | −0.006 (3) | 0.005 (3) |
C42 | 0.051 (4) | 0.034 (4) | 0.040 (4) | −0.003 (3) | 0.006 (3) | 0.007 (3) |
C43 | 0.066 (4) | 0.050 (5) | 0.038 (4) | −0.002 (4) | −0.016 (4) | 0.011 (4) |
C44 | 0.048 (4) | 0.057 (5) | 0.044 (4) | −0.012 (4) | −0.016 (3) | 0.004 (4) |
C45 | 0.035 (3) | 0.045 (4) | 0.038 (4) | −0.005 (3) | −0.014 (3) | 0.010 (3) |
C46 | 0.039 (4) | 0.061 (5) | 0.046 (4) | −0.015 (3) | −0.016 (3) | 0.012 (4) |
C47 | 0.029 (3) | 0.050 (4) | 0.049 (4) | −0.015 (3) | −0.016 (3) | 0.009 (4) |
C48 | 0.039 (4) | 0.056 (5) | 0.040 (4) | −0.016 (3) | −0.017 (3) | 0.018 (4) |
C49 | 0.043 (4) | 0.067 (5) | 0.049 (4) | −0.028 (4) | −0.014 (3) | 0.018 (4) |
C50 | 0.056 (4) | 0.092 (6) | 0.054 (5) | −0.040 (4) | −0.017 (4) | 0.013 (4) |
C51 | 0.057 (4) | 0.089 (6) | 0.049 (4) | −0.034 (4) | −0.026 (4) | 0.015 (4) |
C52 | 0.056 (5) | 0.069 (5) | 0.061 (5) | −0.020 (4) | −0.020 (4) | 0.019 (4) |
C53 | 0.063 (5) | 0.072 (5) | 0.063 (5) | −0.013 (4) | −0.004 (4) | 0.019 (4) |
C54 | 0.066 (5) | 0.066 (5) | 0.083 (6) | −0.012 (4) | 0.001 (5) | 0.021 (5) |
C55 | 0.088 (6) | 0.078 (6) | 0.093 (6) | −0.023 (5) | −0.019 (6) | 0.007 (5) |
C56 | 0.102 (6) | 0.090 (6) | 0.079 (6) | −0.022 (5) | −0.027 (5) | 0.011 (5) |
C57 | 0.088 (6) | 0.082 (6) | 0.065 (5) | −0.024 (5) | −0.021 (5) | 0.021 (5) |
N58 | 0.031 (3) | 0.029 (3) | 0.041 (3) | −0.014 (2) | −0.004 (3) | 0.010 (3) |
C59 | 0.041 (4) | 0.039 (4) | 0.042 (4) | −0.010 (3) | −0.009 (3) | 0.004 (3) |
C60 | 0.065 (5) | 0.053 (5) | 0.035 (4) | −0.022 (4) | −0.009 (4) | 0.010 (4) |
C61 | 0.079 (5) | 0.048 (4) | 0.021 (3) | −0.031 (3) | −0.021 (3) | 0.019 (3) |
C62 | 0.058 (4) | 0.053 (4) | 0.042 (4) | −0.013 (4) | −0.022 (3) | 0.019 (3) |
C63 | 0.042 (4) | 0.042 (4) | 0.041 (4) | −0.015 (3) | −0.018 (3) | 0.013 (3) |
C64 | 0.041 (4) | 0.039 (5) | 0.047 (5) | −0.009 (4) | −0.012 (4) | 0.011 (4) |
C65 | 0.030 (4) | 0.039 (5) | 0.029 (4) | −0.002 (3) | −0.008 (3) | 0.007 (3) |
C66 | 0.049 (5) | 0.035 (5) | 0.039 (5) | −0.006 (4) | −0.023 (4) | 0.008 (4) |
C67 | 0.052 (5) | 0.041 (5) | 0.052 (6) | 0.002 (4) | −0.020 (4) | 0.000 (4) |
C68 | 0.066 (7) | 0.070 (7) | 0.065 (7) | 0.024 (6) | −0.030 (6) | 0.001 (6) |
C69 | 0.089 (6) | 0.090 (7) | 0.046 (5) | 0.029 (6) | −0.041 (5) | −0.004 (5) |
C70 | 0.046 (5) | 0.074 (7) | 0.065 (7) | 0.003 (5) | −0.016 (5) | −0.003 (5) |
C71 | 0.055 (5) | 0.073 (6) | 0.071 (5) | −0.013 (4) | −0.003 (4) | 0.010 (4) |
C72 | 0.089 (6) | 0.084 (6) | 0.078 (6) | −0.018 (5) | 0.009 (5) | −0.003 (5) |
C73 | 0.087 (6) | 0.088 (6) | 0.093 (6) | −0.014 (6) | 0.022 (6) | −0.004 (6) |
C74 | 0.068 (5) | 0.088 (7) | 0.109 (7) | −0.011 (5) | 0.015 (6) | 0.023 (6) |
C75 | 0.065 (5) | 0.095 (6) | 0.108 (7) | −0.014 (5) | −0.012 (5) | 0.030 (5) |
C76 | 0.060 (5) | 0.086 (6) | 0.085 (6) | −0.020 (5) | −0.016 (5) | 0.021 (5) |
Cl1 | 0.0263 (8) | 0.0359 (12) | 0.0391 (11) | −0.0055 (8) | −0.0046 (8) | 0.0033 (9) |
Cl2 | 0.0294 (9) | 0.0378 (12) | 0.0372 (11) | −0.0069 (8) | −0.0057 (8) | 0.0061 (9) |
Ir1 | 0.03029 (16) | 0.0366 (2) | 0.02807 (19) | −0.00850 (14) | −0.00084 (13) | 0.00528 (15) |
Ir2 | 0.03050 (17) | 0.0365 (2) | 0.0312 (2) | −0.00820 (14) | −0.00887 (13) | 0.00736 (16) |
F27 | 0.100 (5) | 0.226 (10) | 0.063 (4) | −0.106 (6) | −0.045 (4) | 0.041 (5) |
F50 | 0.112 (5) | 0.124 (6) | 0.062 (4) | 0.055 (4) | −0.050 (4) | −0.009 (4) |
F69 | 0.102 (5) | 0.152 (7) | 0.040 (3) | 0.064 (5) | 0.000 (3) | −0.012 (4) |
F92 | 0.091 (4) | 0.163 (6) | 0.042 (3) | −0.073 (4) | 0.010 (3) | 0.007 (4) |
O1—S1 | 1.430 (7) | C35—H351 | 0.937 |
O2—S1 | 1.424 (8) | C36—C37 | 1.362 (15) |
O3—S2 | 1.438 (7) | C36—H361 | 0.936 |
O4—S2 | 1.442 (7) | C37—C39 | 1.390 (15) |
O5—S3 | 1.425 (7) | C37—H371 | 0.929 |
O6—S3 | 1.454 (6) | C38—C52 | 1.507 (15) |
O7—S4 | 1.439 (7) | C38—H381 | 0.972 |
O8—S4 | 1.435 (8) | C38—H382 | 0.969 |
S1—C10 | 1.760 (9) | C39—H391 | 0.936 |
S1—C13 | 1.801 (12) | N40—C41 | 1.330 (10) |
S2—C29 | 1.778 (9) | N40—C45 | 1.363 (10) |
S2—C32 | 1.780 (11) | N40—Ir2 | 2.036 (7) |
S3—C67 | 1.745 (9) | C41—C42 | 1.441 (12) |
S3—C70 | 1.780 (11) | C41—H411 | 0.937 |
S4—C38 | 1.784 (11) | C42—C43 | 1.279 (13) |
S4—C49 | 1.771 (9) | C42—H421 | 0.928 |
N1—C2 | 1.335 (11) | C43—C44 | 1.402 (13) |
N1—C6 | 1.383 (10) | C43—H431 | 0.932 |
N1—Ir1 | 2.053 (7) | C44—C45 | 1.392 (11) |
C2—C3 | 1.379 (12) | C44—H441 | 0.937 |
C2—H21 | 0.940 | C45—C46 | 1.475 (12) |
C3—C4 | 1.278 (14) | C46—C47 | 1.414 (12) |
C3—H31 | 0.932 | C46—C51 | 1.375 (13) |
C4—C5 | 1.434 (14) | C47—C48 | 1.402 (11) |
C4—H41 | 0.927 | C47—Ir2 | 1.976 (8) |
C5—C6 | 1.411 (11) | C48—C49 | 1.389 (12) |
C5—H51 | 0.936 | C48—H481 | 0.933 |
C6—C7 | 1.467 (12) | C49—C50 | 1.387 (13) |
C7—C8 | 1.421 (11) | C50—C51 | 1.380 (14) |
C7—C12 | 1.387 (12) | C50—H501 | 0.934 |
C8—C9 | 1.382 (12) | C51—F27 | 1.352 (11) |
C8—Ir1 | 1.977 (8) | C52—C53 | 1.382 (14) |
C9—C10 | 1.393 (11) | C52—C57 | 1.390 (15) |
C9—H91 | 0.938 | C53—C54 | 1.394 (17) |
C10—C11 | 1.379 (12) | C53—H531 | 0.935 |
C11—C12 | 1.376 (8) | C54—C55 | 1.361 (17) |
C11—H111 | 0.928 | C54—H541 | 0.931 |
C12—F92 | 1.352 (10) | C55—C56 | 1.384 (18) |
C13—C14 | 1.489 (16) | C55—H551 | 0.936 |
C13—H131 | 0.967 | C56—C57 | 1.386 (18) |
C13—H132 | 0.969 | C56—H561 | 0.935 |
C14—C15 | 1.381 (9) | C57—H571 | 0.937 |
C14—C19 | 1.381 (9) | N58—C59 | 1.339 (10) |
C15—C16 | 1.363 (18) | N58—C63 | 1.401 (10) |
C15—H151 | 0.933 | N58—Ir2 | 2.033 (7) |
C16—C17 | 1.369 (9) | C59—C60 | 1.362 (12) |
C16—H161 | 0.932 | C59—H591 | 0.937 |
C17—C18 | 1.376 (9) | C60—C61 | 1.274 (13) |
C17—H171 | 0.935 | C60—H601 | 0.943 |
C18—C19 | 1.392 (19) | C61—C62 | 1.474 (13) |
C18—H181 | 0.930 | C61—H611 | 0.927 |
C19—H191 | 0.935 | C62—C63 | 1.388 (11) |
N20—C21 | 1.324 (10) | C62—H621 | 0.933 |
N20—C25 | 1.385 (9) | C63—C64 | 1.455 (12) |
N20—Ir1 | 2.041 (6) | C64—C65 | 1.433 (11) |
C21—C22 | 1.443 (12) | C64—C69 | 1.367 (12) |
C21—H211 | 0.937 | C65—C66 | 1.357 (11) |
C22—C23 | 1.269 (13) | C65—Ir2 | 1.982 (7) |
C22—H221 | 0.931 | C66—C67 | 1.395 (11) |
C23—C24 | 1.411 (13) | C66—H661 | 0.933 |
C23—H231 | 0.935 | C67—C68 | 1.410 (13) |
C24—C25 | 1.403 (11) | C68—C69 | 1.379 (8) |
C24—H241 | 0.933 | C68—H681 | 0.938 |
C25—C26 | 1.471 (11) | C69—F50 | 1.355 (10) |
C26—C27 | 1.417 (11) | C70—C71 | 1.494 (15) |
C26—C31 | 1.383 (12) | C70—H701 | 0.973 |
C27—C28 | 1.409 (11) | C70—H702 | 0.971 |
C27—Ir1 | 1.984 (8) | C71—C72 | 1.355 (17) |
C28—C29 | 1.370 (11) | C71—C76 | 1.389 (16) |
C28—H281 | 0.932 | C72—C73 | 1.448 (19) |
C29—C30 | 1.384 (12) | C72—H721 | 0.934 |
C30—C31 | 1.379 (13) | C73—C74 | 1.336 (19) |
C30—H301 | 0.929 | C73—H731 | 0.936 |
C31—F69 | 1.342 (10) | C74—C75 | 1.37 (2) |
C32—C33 | 1.490 (14) | C74—H741 | 0.934 |
C32—H321 | 0.973 | C75—C76 | 1.379 (18) |
C32—H322 | 0.971 | C75—H751 | 0.931 |
C33—C34 | 1.404 (14) | C76—H761 | 0.935 |
C33—C39 | 1.403 (13) | Cl1—Ir1 | 2.4990 (19) |
C34—C35 | 1.375 (16) | Cl1—Ir2 | 2.500 (2) |
C34—H341 | 0.933 | Cl2—Ir1 | 2.502 (2) |
C35—C36 | 1.380 (16) | Cl2—Ir2 | 2.507 (2) |
O1—S1—O2 | 118.8 (5) | C33—C39—H391 | 119.1 |
O1—S1—C10 | 108.1 (4) | C37—C39—H391 | 120.8 |
O2—S1—C10 | 109.8 (5) | C41—N40—C45 | 119.1 (7) |
O1—S1—C13 | 107.8 (5) | C41—N40—Ir2 | 125.3 (6) |
O2—S1—C13 | 107.3 (5) | C45—N40—Ir2 | 115.7 (5) |
C10—S1—C13 | 104.1 (5) | N40—C41—C42 | 122.4 (8) |
O4—S2—O3 | 119.0 (5) | N40—C41—H411 | 118.5 |
O4—S2—C29 | 109.5 (5) | C42—C41—H411 | 119.2 |
O3—S2—C29 | 108.3 (4) | C41—C42—C43 | 117.6 (8) |
O4—S2—C32 | 105.9 (5) | C41—C42—H421 | 120.9 |
O3—S2—C32 | 109.4 (5) | C43—C42—H421 | 121.5 |
C29—S2—C32 | 103.7 (4) | C42—C43—C44 | 122.3 (9) |
O6—S3—O5 | 119.0 (5) | C42—C43—H431 | 118.2 |
O6—S3—C67 | 107.6 (4) | C44—C43—H431 | 119.5 |
O5—S3—C67 | 109.9 (4) | C43—C44—C45 | 119.0 (9) |
O6—S3—C70 | 108.7 (5) | C43—C44—H441 | 120.9 |
O5—S3—C70 | 107.2 (5) | C45—C44—H441 | 120.1 |
C67—S3—C70 | 103.4 (5) | C44—C45—N40 | 119.5 (8) |
O7—S4—O8 | 120.1 (5) | C44—C45—C46 | 126.7 (8) |
O7—S4—C38 | 109.4 (5) | N40—C45—C46 | 113.7 (7) |
O8—S4—C38 | 105.1 (5) | C45—C46—C47 | 113.6 (8) |
O7—S4—C49 | 108.6 (4) | C45—C46—C51 | 127.0 (8) |
O8—S4—C49 | 109.0 (5) | C47—C46—C51 | 119.3 (8) |
C38—S4—C49 | 103.3 (5) | C46—C47—C48 | 117.9 (8) |
C2—N1—C6 | 120.7 (7) | C46—C47—Ir2 | 115.6 (6) |
C2—N1—Ir1 | 125.2 (6) | C48—C47—Ir2 | 126.3 (7) |
C6—N1—Ir1 | 114.0 (6) | C47—C48—C49 | 120.9 (8) |
N1—C2—C3 | 121.4 (8) | C47—C48—H481 | 119.8 |
N1—C2—H21 | 118.5 | C49—C48—H481 | 119.3 |
C3—C2—H21 | 120.1 | S4—C49—C48 | 119.5 (7) |
C2—C3—C4 | 120.3 (10) | S4—C49—C50 | 119.2 (7) |
C2—C3—H31 | 119.7 | C48—C49—C50 | 121.1 (8) |
C4—C3—H31 | 120.0 | C49—C50—C51 | 117.5 (9) |
C3—C4—C5 | 122.0 (9) | C49—C50—H501 | 121.3 |
C3—C4—H41 | 119.2 | C51—C50—H501 | 121.2 |
C5—C4—H41 | 118.8 | C50—C51—C46 | 123.2 (9) |
C4—C5—C6 | 117.1 (8) | C50—C51—F27 | 116.9 (9) |
C4—C5—H51 | 122.1 | C46—C51—F27 | 119.9 (9) |
C6—C5—H51 | 120.8 | C38—C52—C53 | 122.6 (10) |
C5—C6—N1 | 118.2 (8) | C38—C52—C57 | 119.0 (10) |
C5—C6—C7 | 127.3 (8) | C53—C52—C57 | 118.4 (11) |
N1—C6—C7 | 114.4 (7) | C52—C53—C54 | 120.2 (11) |
C6—C7—C8 | 114.1 (7) | C52—C53—H531 | 119.4 |
C6—C7—C12 | 126.9 (8) | C54—C53—H531 | 120.4 |
C8—C7—C12 | 119.0 (8) | C53—C54—C55 | 121.2 (12) |
C7—C8—C9 | 117.4 (8) | C53—C54—H541 | 118.7 |
C7—C8—Ir1 | 115.2 (6) | C55—C54—H541 | 120.1 |
C9—C8—Ir1 | 127.1 (6) | C54—C55—C56 | 119.2 (14) |
C8—C9—C10 | 121.8 (8) | C54—C55—H551 | 120.7 |
C8—C9—H91 | 119.4 | C56—C55—H551 | 120.1 |
C10—C9—H91 | 118.9 | C55—C56—C57 | 120.2 (13) |
S1—C10—C9 | 119.8 (7) | C55—C56—H561 | 119.8 |
S1—C10—C11 | 119.0 (7) | C57—C56—H561 | 120.0 |
C9—C10—C11 | 121.1 (9) | C52—C57—C56 | 120.8 (12) |
C10—C11—C12 | 117.3 (8) | C52—C57—H571 | 118.8 |
C10—C11—H111 | 121.6 | C56—C57—H571 | 120.3 |
C12—C11—H111 | 121.0 | C59—N58—C63 | 118.7 (7) |
C7—C12—C11 | 123.2 (8) | C59—N58—Ir2 | 126.3 (5) |
C7—C12—F92 | 118.6 (8) | C63—N58—Ir2 | 115.0 (5) |
C11—C12—F92 | 118.1 (8) | N58—C59—C60 | 123.2 (8) |
S1—C13—C14 | 114.6 (7) | N58—C59—H591 | 118.0 |
S1—C13—H131 | 108.4 | C60—C59—H591 | 118.8 |
C14—C13—H131 | 108.6 | C59—C60—C61 | 121.2 (9) |
S1—C13—H132 | 107.7 | C59—C60—H601 | 119.4 |
C14—C13—H132 | 107.8 | C61—C60—H601 | 119.4 |
H131—C13—H132 | 109.7 | C60—C61—C62 | 119.9 (8) |
C13—C14—C15 | 119.8 (11) | C60—C61—H611 | 120.1 |
C13—C14—C19 | 121.7 (11) | C62—C61—H611 | 120.1 |
C15—C14—C19 | 118.4 (13) | C61—C62—C63 | 117.8 (8) |
C14—C15—C16 | 122.5 (14) | C61—C62—H621 | 122.3 |
C14—C15—H151 | 119.8 | C63—C62—H621 | 120.0 |
C16—C15—H151 | 117.8 | N58—C63—C62 | 118.9 (8) |
C15—C16—C17 | 118.1 (14) | N58—C63—C64 | 112.7 (7) |
C15—C16—H161 | 122.8 | C62—C63—C64 | 128.4 (8) |
C17—C16—H161 | 119.0 | C63—C64—C65 | 115.9 (7) |
C16—C17—C18 | 121.9 (15) | C63—C64—C69 | 126.0 (8) |
C16—C17—H171 | 119.5 | C65—C64—C69 | 118.0 (8) |
C18—C17—H171 | 118.5 | C64—C65—C66 | 118.6 (7) |
C17—C18—C19 | 118.7 (14) | C64—C65—Ir2 | 113.5 (6) |
C17—C18—H181 | 121.5 | C66—C65—Ir2 | 127.1 (6) |
C19—C18—H181 | 119.8 | C65—C66—C67 | 122.5 (8) |
C18—C19—C14 | 120.2 (14) | C65—C66—H661 | 118.6 |
C18—C19—H191 | 121.0 | C67—C66—H661 | 118.9 |
C14—C19—H191 | 118.8 | S3—C67—C66 | 121.2 (7) |
C21—N20—C25 | 120.2 (7) | S3—C67—C68 | 119.1 (7) |
C21—N20—Ir1 | 125.2 (5) | C66—C67—C68 | 119.5 (8) |
C25—N20—Ir1 | 114.6 (5) | C67—C68—C69 | 117.1 (8) |
N20—C21—C22 | 121.3 (8) | C67—C68—H681 | 121.4 |
N20—C21—H211 | 119.0 | C69—C68—H681 | 121.5 |
C22—C21—H211 | 119.7 | C68—C69—C64 | 124.2 (9) |
C21—C22—C23 | 118.1 (8) | C68—C69—F50 | 116.0 (9) |
C21—C22—H221 | 120.8 | C64—C69—F50 | 119.8 (8) |
C23—C22—H221 | 121.1 | S3—C70—C71 | 114.4 (7) |
C22—C23—C24 | 123.6 (9) | S3—C70—H701 | 107.9 |
C22—C23—H231 | 117.5 | C71—C70—H701 | 108.2 |
C24—C23—H231 | 118.9 | S3—C70—H702 | 108.5 |
C23—C24—C25 | 117.6 (8) | C71—C70—H702 | 107.9 |
C23—C24—H241 | 121.7 | H701—C70—H702 | 109.9 |
C25—C24—H241 | 120.7 | C70—C71—C72 | 119.6 (12) |
C24—C25—N20 | 119.0 (7) | C70—C71—C76 | 119.9 (11) |
C24—C25—C26 | 127.5 (7) | C72—C71—C76 | 120.4 (12) |
N20—C25—C26 | 113.4 (6) | C71—C72—C73 | 117.4 (14) |
C25—C26—C27 | 115.2 (7) | C71—C72—H721 | 120.2 |
C25—C26—C31 | 124.8 (8) | C73—C72—H721 | 122.3 |
C27—C26—C31 | 120.0 (8) | C72—C73—C74 | 122.1 (15) |
C26—C27—C28 | 117.3 (7) | C72—C73—H731 | 118.1 |
C26—C27—Ir1 | 114.3 (6) | C74—C73—H731 | 119.8 |
C28—C27—Ir1 | 127.8 (6) | C73—C74—C75 | 118.9 (15) |
C27—C28—C29 | 120.4 (7) | C73—C74—H741 | 119.7 |
C27—C28—H281 | 119.6 | C75—C74—H741 | 121.4 |
C29—C28—H281 | 119.9 | C74—C75—C76 | 121.1 (15) |
S2—C29—C28 | 118.7 (7) | C74—C75—H751 | 119.1 |
S2—C29—C30 | 118.3 (7) | C76—C75—H751 | 119.7 |
C28—C29—C30 | 122.7 (8) | C71—C76—C75 | 120.1 (14) |
C29—C30—C31 | 117.2 (9) | C71—C76—H761 | 119.6 |
C29—C30—H301 | 121.2 | C75—C76—H761 | 120.4 |
C31—C30—H301 | 121.6 | Ir1—Cl1—Ir2 | 96.58 (6) |
C26—C31—C30 | 122.4 (8) | Ir1—Cl2—Ir2 | 96.30 (6) |
C26—C31—F69 | 121.0 (9) | Cl1—Ir1—Cl2 | 83.61 (7) |
C30—C31—F69 | 116.5 (9) | Cl1—Ir1—N1 | 89.41 (18) |
S2—C32—C33 | 116.9 (6) | Cl2—Ir1—N1 | 96.6 (2) |
S2—C32—H321 | 107.7 | Cl1—Ir1—N20 | 95.43 (18) |
C33—C32—H321 | 108.3 | Cl2—Ir1—N20 | 88.40 (18) |
S2—C32—H322 | 107.7 | N1—Ir1—N20 | 173.4 (3) |
C33—C32—H322 | 106.7 | Cl1—Ir1—C27 | 172.1 (2) |
H321—C32—H322 | 109.4 | Cl2—Ir1—C27 | 89.1 (2) |
C32—C33—C34 | 119.3 (9) | N1—Ir1—C27 | 94.4 (3) |
C32—C33—C39 | 122.8 (9) | N20—Ir1—C27 | 81.4 (3) |
C34—C33—C39 | 117.9 (10) | Cl1—Ir1—C8 | 88.3 (2) |
C33—C34—C35 | 120.4 (11) | Cl2—Ir1—C8 | 171.6 (2) |
C33—C34—H341 | 119.3 | N1—Ir1—C8 | 81.0 (3) |
C35—C34—H341 | 120.2 | N20—Ir1—C8 | 94.6 (3) |
C34—C35—C36 | 121.0 (13) | C27—Ir1—C8 | 99.1 (3) |
C34—C35—H351 | 119.8 | Cl1—Ir2—Cl2 | 83.51 (7) |
C36—C35—H351 | 119.2 | Cl1—Ir2—N40 | 95.8 (2) |
C35—C36—C37 | 119.4 (12) | Cl2—Ir2—N40 | 88.87 (18) |
C35—C36—H361 | 120.3 | Cl1—Ir2—N58 | 89.35 (18) |
C37—C36—H361 | 120.3 | Cl2—Ir2—N58 | 96.11 (18) |
C36—C37—C39 | 121.1 (11) | N40—Ir2—N58 | 173.2 (3) |
C36—C37—H371 | 119.8 | Cl1—Ir2—C65 | 89.3 (2) |
C39—C37—H371 | 119.2 | Cl2—Ir2—C65 | 172.5 (3) |
S4—C38—C52 | 116.2 (7) | N40—Ir2—C65 | 94.1 (3) |
S4—C38—H381 | 108.3 | N58—Ir2—C65 | 81.5 (3) |
C52—C38—H381 | 107.9 | Cl1—Ir2—C47 | 171.6 (3) |
S4—C38—H382 | 107.3 | Cl2—Ir2—C47 | 88.9 (3) |
C52—C38—H382 | 108.3 | N40—Ir2—C47 | 80.4 (3) |
H381—C38—H382 | 108.8 | N58—Ir2—C47 | 95.1 (3) |
C33—C39—C37 | 120.1 (10) | C65—Ir2—C47 | 98.4 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C23—H231···O1i | 0.94 | 2.57 | 3.168 (15) | 122 (1) |
C32—H321···O5ii | 0.97 | 2.27 | 3.200 (15) | 161 (1) |
C32—H322···O2iii | 0.97 | 2.38 | 3.155 (15) | 137 (1) |
C43—H431···O6iv | 0.93 | 2.54 | 3.143 (15) | 123 (1) |
Symmetry codes: (i) −x+2, −y, −z; (ii) x+1, y−1, z; (iii) x+1, y, z; (iv) −x+2, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Ir2(C18H13FNO2S)4Cl2]·C7H8 |
Mr | 1852.97 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 13.5049 (4), 14.3144 (5), 19.6770 (6) |
α, β, γ (°) | 89.772 (2), 78.954 (2), 74.262 (2) |
V (Å3) | 3588.8 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 3.97 |
Crystal size (mm) | 0.75 × 0.44 × 0.08 |
Data collection | |
Diffractometer | Bruker Kappa APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2008) |
Tmin, Tmax | 0.653, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 49952, 14669, 9065 |
Rint | 0.048 |
(sin θ/λ)max (Å−1) | 0.627 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.043, 1.14 |
No. of reflections | 8337 |
No. of parameters | 865 |
No. of restraints | 440 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.01, −1.37 |
Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2009), SUPERFLIP (Palatinus & Chapuis, 2007), CRYSTALS (Betteridge et al., 2003), Mercury (Macrae et al., 2008).
N1—Ir1 | 2.053 (7) | N58—Ir2 | 2.033 (7) |
C8—Ir1 | 1.977 (8) | C65—Ir2 | 1.982 (7) |
N20—Ir1 | 2.041 (6) | Cl1—Ir1 | 2.4990 (19) |
C27—Ir1 | 1.984 (8) | Cl1—Ir2 | 2.500 (2) |
N40—Ir2 | 2.036 (7) | Cl2—Ir1 | 2.502 (2) |
C47—Ir2 | 1.976 (8) | Cl2—Ir2 | 2.507 (2) |
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Homoleptic [Ir(C^N)3] and heteroleptic [(C^N)2IrLX] organometallic complexes of iridium(III) with 2-arylpyridine (C^N) ligands have recently attracted much attention in both academic research and industry because of their use as phosphorescent emitters in highly efficient organic light-emitting diodes (Ulbricht et al., 2009). The emission colour of these complexes can be finely tuned by properly choosing the structure and functionalization of the organic ligands (C^N and LX) (Lamansky et al., 2001). Recent reports show that the stereochemistry of both homoleptic and heteroleptic phosphorescent complexes has a significant influence on their photophysical properties, as well as on device performance (Ragni et al., 2006; Baranoff et al., 2010; Fernández-Hernández et al., 2011).
A common synthetic route to homoleptic and heteroleptic iridium complexes involves the use of the dichloride-bridged dimeric precursors [(C^N)2Ir(µ-Cl)2Ir(C^N)2]. The stereochemical arrangement of the arylpyridine ligands around each iridium centre in the dimeric precursors is retained in the final phosphorescent complexes (Colombo et al., 1994; Lamansky et al., 2001).
A series of heteroleptic iridium complexes with highly tuneable emission colour, and bearing two phenylpyridine ligands functionalized with benzylsulfonyl groups and F atoms and an ancillary diketonate ligand, were recently synthesized starting from the corresponding dimeric precursors (Ragni et al., 2009). The authors postulated a mutual cis disposition of the phenylpyridine ligands around the iridium centres of these complexes on the basis of the 1H NMR spectra of their dichloride-bridged dimer precursors.
The crystal structure of one of these dimers, namely the title compound, di-µ-dichlorido-(bis{bis[2-(5-benzylsulfonyl-3-fluoro-2-(pyridin-2-yl)phenyl-κ2N,C1]}iridium(III)) toluene monosolvate, (I), enables the unambiguous assignment of its stereochemistry.
The title dichloride-bridged dimeric complex has a slightly distorted octahedral coordination for each IrIII cation (Fig. 1). Its spatial arrangement is similar to that found for the previously reported analogue [(ppy)2Ir(µ-Cl)2Ir(ppy)2], bearing nonsubstituted phenylpyridine (ppy) ligands (Graces et al., 1988), and that for the corresponding heteroleptic complex (ppy)2Ir(acac), bearing acetylacetonate (acac) as the third ancillary ligand (Lamansky et al., 2001). The present structure has the two Ir—N bonds at each IrIII cation in a unequivocal trans geometry (Fig. 1), in contrast with the hypothesis of Ragni et al. (2009). That conclusion was based on the 1H NMR spectrum recorded after dissolving the dimer complexes in deuterated dimethylsulfoxide, d6-DMSO, which was used as the NMR solvent because of the low solubility of the complexes in more common deuterated solvents, e.g. chloroform (CDCl3) or dichloromethane (CD2Cl2). In the present 1H NMR spectrum of (I), as well as in the 1H NMR spectra recorded in d6-DMSO for all the benzylsulfonyl-substituted dimer complexes reported in our previous work (Ragni et al., 2009), two different sets of protonic signals are distinguishable for the phenylpyridine ligands present in the dimer. Such spectroscopic behaviour led us to assume a cis arrangement of these ligands around each iridium centre. On the basis of the crystal structure reported here, we can infer that the recorded pattern of the 1H NMR signals was not due to the cis stereochemistry of the dimer complex, but rather to a different product generated from the reaction of the dimer complex with the coordinating DMSO solvent used to record the NMR spectrum. This hypothesis is in fact supported by previous literature reports describing reactions of dimeric complexes with coordinating molecules such as water, acetonitrile (Schmid et al., 1994; McGee & Mann, 2007), triphenylphosphine or dimethylformamide (Sprouse et al., 1984), leading to the conversion of the dimeric complexes into asymmetric mononuclear complexes. DMSO is also mentioned in one of these papers (Schmid et al., 1994). More recently, in 2011, the tendency of DMSO to cleave mono-chloro bridged iridium(III) dimer complexes to form mononuclear complexes has also been demonstrated by Fernández-Hernández et al. (2011).
The crystal structure of (I) contains cavities embedding disordered solvent molecules. The overall void volume is 474 Å3, with a total electron count per cell of 141 and a Kitaigorodskii packing index (KPI) of 61.7% (Kitaigorodskii, 1973). The largest isolated cavity has a volume of 185 Å3 (about 40% of the overall void volume and 5% of the unit-cell volume), consistent with the expected volume for a toluene molecule (100–300 Å3). The electron density in the cavities could not be modelled and was handled by means of the SQUEEZE routine of the program PLATON (Spek, 2009).
Bond lengths (Table 1) and angles are in ranges typical of comparable resonant systems (average C—C in the phenyl ring = 1.38 Å) and related compounds (Okada et al., 2005; Yang et al., 2005; Lyu et al., 2006; Wu et al., 2007). The Ir1···Ir2 distance is 3.7315 (4) Å, too long for any significant intermetallic interaction. The Ir1—N1 bond is slightly longer [2.053 (6) Å] than the other Ir—N bonds (mean Ir—N = 2.042 Å). As a consequence of the stereochemistry of the complex, this result cannot be ascribed to a trans influence, so it is believed to be caused by steric interaction of the substituted phenylpyridine ligand with a disordered solvent molecule. This interaction seems to be small, with no apparent influence on the N1—Ir1—N20 angle [173.4 (3)°].
Pairs of centrosymmetrically related molecules have slipped π–π stacking interactions between their C71–C76 phenyl rings (Fig. 2), with an interplanar distance of 3.503 Å and a centroid-to-centroid separation Cg1···Cg1i of 3.9522 (1) Å [symmetry code: (i) -x + 1, -y + 1, -z + 1].