Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106039527/gd3050sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106039527/gd3050IIsup2.hkl |
CCDC reference: 628503
For the synthesis of (I), a mixture of pentafluorobenzyl bromide (2.10 g, 7.96 mmol) and 1-benzylbenzimidazole (1.652 g; 7.94 mmol) was refluxed in toluene (15 ml) for 2 h. The volume of the solution was reduced to ca 3–4 ml under vacuum. Diethyl ether was added and the solution was filtered. The remaining white precipitate was dissolved in methanol (4 ml) and diethyl ether was added (15 ml). The resutling white crystals were filtered off and dried under vacuum (yield 3.4 g, 91%; m.p. 418 K). Analysis calculated for C21H14BrF5N2; C 53.73, H 2.99, N 5.97%; found: C 53.53, H 2.94, N 5.89%. 1H NMR (CDCl3): δ 5.89 (s, 2H, CH2C6H5), 6.19 (s, 2H, CH2C6F5), 7.34–7.63 (m, 9H, Ar—H), 11.71 (s, 1H, CH). 13C NMR (CDCl3): δ 39.58 (CH2C6H5), 52.01 (CH2C6F5), 107.01, 114.58, 127.86, 128.56, 129.48, 131.25, 112.75, 132.63, 136.85, 139.31, 141.30, 143.74, 144.51 (Ar—C), 147.08 (CH). 19F NMR (CDCl3): δ −140.75 (2 F, Fo), −149.76 (1 F, Fp), −159.22 (2 F, Fm). For the synthesis of (2), a 50 ml Schlenk tube was charged with (I) (187.60 mg, 0.4 mmol), Pd(OAc)2 (44.88 mg, 0.2 mmol) and THF (5 ml). The solution was heated under reflux for 24 h. The color of the solution was changed from orange to yellow. Upon cooling to room temperature, hexane (10 ml) was added to the mixture. The solid was filtered off and then was recrystallized in CH2Cl2/MeOH (yield 160 mg, 77%; m.p. 541–542 K). Analysis calculated for C42H26Br2F10N4Pd; C 48.35, H 2.49, N 5.37%; found C 47.60, H 1.96, N 5.36%. 1H NMR (CDCl3): δ 5.91 (s, 4H, CH2C6H5), 6.07 (d, 4H, J = 10 Hz, CH2C6F5), 6.99–7.42 (m, 18H, Ar—H). 13C NMR (CDCl3): δ 53.00 (CH2C6H5), 41.30 (CH2C6F5), 110.33 (d, J = 15.3 Hz), 111.96 (d, J = 10.7 Hz), 123.68, 127.40, 127.65, 128.88, 128.81, 134.56, 134.63, 134.76, 134.89, 135.11, 135.49 (Ar—C), 183.06 (Ccarb—Pd). 19F NMR (CDCl3): δ −140.82 (2 F, Fo), −150.57 (1 F, Fp), −159.44 (2 F, Fm).
All H atoms were treated as riding atoms, with C—H distances in the range 0.93–0.97 Å and with Uiso(H) values of 1.2Ueq(C).
Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999).
[PdBr2(C21H13F5N2)2] | Z = 2 |
Mr = 1042.89 | F(000) = 1024 |
Triclinic, P1 | Dx = 1.811 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 11.6122 (8) Å | Cell parameters from 22882 reflections |
b = 12.1401 (9) Å | θ = 2.2–28.1° |
c = 13.6590 (11) Å | µ = 2.66 mm−1 |
α = 92.589 (6)° | T = 293 K |
β = 95.610 (6)° | Prism, colorless |
γ = 92.520 (6)° | 0.18 × 0.16 × 0.09 mm |
V = 1912.1 (2) Å3 |
Stoe IPDS-II diffractometer | 7493 independent reflections |
Radiation source: fine-focus sealed tube | 3911 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.121 |
Detector resolution: 6.67 pixels mm-1 | θmax = 26.0°, θmin = 2.2° |
ω scans | h = −14→14 |
Absorption correction: integration ? | k = −14→13 |
Tmin = 0.646, Tmax = 0.796 | l = −16→16 |
23746 measured reflections |
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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 0.95 | w = 1/[σ2(Fo2) + (0.035P)2] where P = (Fo2 + 2Fc2)/3 |
7493 reflections | (Δ/σ)max = 0.002 |
535 parameters | Δρmax = 0.68 e Å−3 |
1 restraint | Δρmin = −0.55 e Å−3 |
[PdBr2(C21H13F5N2)2] | γ = 92.520 (6)° |
Mr = 1042.89 | V = 1912.1 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.6122 (8) Å | Mo Kα radiation |
b = 12.1401 (9) Å | µ = 2.66 mm−1 |
c = 13.6590 (11) Å | T = 293 K |
α = 92.589 (6)° | 0.18 × 0.16 × 0.09 mm |
β = 95.610 (6)° |
Stoe IPDS-II diffractometer | 7493 independent reflections |
Absorption correction: integration ? | 3911 reflections with I > 2σ(I) |
Tmin = 0.646, Tmax = 0.796 | Rint = 0.121 |
23746 measured reflections |
R[F2 > 2σ(F2)] = 0.059 | 1 restraint |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 0.95 | Δρmax = 0.68 e Å−3 |
7493 reflections | Δρmin = −0.55 e Å−3 |
535 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
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 | ||
Pd1A | 0.5000 | 0.5000 | 0.5000 | 0.0390 (2) | |
Pd1B | 1.0000 | 0.0000 | 0.0000 | 0.0522 (3) | |
Br1A | 0.68688 (7) | 0.43920 (9) | 0.56497 (9) | 0.0748 (3) | |
Br1B | 0.84040 (8) | −0.13100 (10) | 0.02265 (8) | 0.0749 (3) | |
F1A | 0.6118 (4) | 0.3252 (5) | 0.2509 (4) | 0.0777 (16) | |
F2A | 0.5235 (6) | 0.4242 (6) | 0.0911 (5) | 0.106 (2) | |
F3A | 0.2915 (6) | 0.4317 (6) | 0.0506 (5) | 0.109 (2) | |
F4A | 0.1487 (5) | 0.3474 (6) | 0.1782 (5) | 0.101 (2) | |
F5A | 0.2366 (4) | 0.2533 (5) | 0.3394 (4) | 0.0862 (18) | |
F1B | 0.8375 (4) | 0.3596 (5) | −0.0761 (4) | 0.0865 (18) | |
F2B | 0.6224 (5) | 0.3594 (6) | −0.1673 (5) | 0.0960 (19) | |
F3B | 0.4505 (5) | 0.2324 (7) | −0.1020 (5) | 0.112 (2) | |
F4B | 0.4963 (5) | 0.1100 (7) | 0.0540 (5) | 0.119 (3) | |
F5B | 0.7084 (4) | 0.1107 (5) | 0.1475 (4) | 0.0890 (18) | |
N1A | 0.4238 (5) | 0.2565 (5) | 0.4813 (5) | 0.0444 (15) | |
N2A | 0.3633 (4) | 0.3349 (5) | 0.6103 (5) | 0.0434 (15) | |
N1B | 0.9413 (5) | 0.1680 (6) | 0.1571 (5) | 0.0505 (17) | |
N2B | 1.0168 (5) | 0.0260 (6) | 0.2225 (5) | 0.0519 (17) | |
C1A | 0.4238 (5) | 0.3543 (6) | 0.5328 (6) | 0.0429 (19) | |
C2A | 0.3635 (6) | 0.1746 (7) | 0.5274 (6) | 0.048 (2) | |
C3A | 0.3414 (7) | 0.0620 (8) | 0.5055 (7) | 0.062 (2) | |
H3A | 0.3647 | 0.0278 | 0.4489 | 0.074* | |
C4A | 0.2840 (8) | 0.0042 (9) | 0.5707 (10) | 0.079 (3) | |
H4A | 0.2680 | −0.0711 | 0.5581 | 0.095* | |
C5A | 0.2489 (7) | 0.0544 (10) | 0.6553 (10) | 0.078 (3) | |
H5A | 0.2114 | 0.0115 | 0.6984 | 0.093* | |
C6A | 0.2679 (6) | 0.1666 (8) | 0.6775 (7) | 0.061 (2) | |
H6A | 0.2434 | 0.2006 | 0.7336 | 0.074* | |
C7A | 0.3261 (5) | 0.2254 (7) | 0.6102 (6) | 0.047 (2) | |
C21A | 0.3459 (6) | 0.4187 (7) | 0.6870 (6) | 0.048 (2) | |
H21A | 0.3719 | 0.4902 | 0.6665 | 0.058* | |
H22A | 0.3934 | 0.4033 | 0.7468 | 0.058* | |
C22A | 0.2210 (6) | 0.4239 (7) | 0.7094 (6) | 0.048 (2) | |
C23A | 0.1337 (6) | 0.4276 (7) | 0.6351 (7) | 0.057 (2) | |
H23A | 0.1504 | 0.4269 | 0.5699 | 0.069* | |
C24A | 0.0203 (7) | 0.4326 (9) | 0.6573 (7) | 0.067 (3) | |
H24A | −0.0390 | 0.4367 | 0.6068 | 0.081* | |
C25A | −0.0049 (8) | 0.4314 (10) | 0.7515 (9) | 0.079 (3) | |
H25A | −0.0818 | 0.4322 | 0.7652 | 0.095* | |
C26A | 0.0796 (9) | 0.4292 (10) | 0.8260 (8) | 0.089 (3) | |
H26A | 0.0614 | 0.4304 | 0.8908 | 0.106* | |
C27A | 0.1953 (8) | 0.4249 (9) | 0.8055 (7) | 0.075 (3) | |
H27A | 0.2542 | 0.4229 | 0.8566 | 0.090* | |
C11A | 0.4816 (7) | 0.2367 (8) | 0.3934 (6) | 0.057 (2) | |
H11A | 0.4826 | 0.1576 | 0.3801 | 0.069* | |
H12A | 0.5613 | 0.2648 | 0.4063 | 0.069* | |
C12A | 0.4280 (6) | 0.2877 (7) | 0.3024 (6) | 0.049 (2) | |
C13A | 0.4954 (7) | 0.3313 (8) | 0.2357 (7) | 0.057 (2) | |
C14A | 0.4517 (9) | 0.3799 (9) | 0.1513 (7) | 0.070 (3) | |
C15A | 0.3334 (9) | 0.3840 (9) | 0.1340 (8) | 0.075 (3) | |
C16A | 0.2633 (8) | 0.3418 (9) | 0.1953 (8) | 0.069 (3) | |
C17A | 0.3098 (7) | 0.2945 (8) | 0.2803 (7) | 0.062 (2) | |
C1B | 0.9845 (6) | 0.0689 (7) | 0.1351 (6) | 0.052 (2) | |
C2B | 0.9470 (6) | 0.1897 (7) | 0.2584 (6) | 0.049 (2) | |
C3B | 0.9115 (8) | 0.2746 (9) | 0.3142 (8) | 0.076 (3) | |
H3B | 0.8737 | 0.3331 | 0.2858 | 0.091* | |
C4B | 0.9341 (9) | 0.2702 (10) | 0.4150 (8) | 0.080 (3) | |
H4B | 0.9118 | 0.3273 | 0.4556 | 0.097* | |
C5B | 0.9900 (9) | 0.1816 (11) | 0.4573 (8) | 0.081 (3) | |
H5B | 1.0051 | 0.1813 | 0.5254 | 0.097* | |
C6B | 1.0226 (7) | 0.0957 (9) | 0.4004 (7) | 0.064 (3) | |
H6B | 1.0603 | 0.0370 | 0.4282 | 0.076* | |
C7B | 0.9974 (6) | 0.0992 (8) | 0.3000 (6) | 0.051 (2) | |
C21B | 1.0625 (7) | −0.0834 (7) | 0.2335 (7) | 0.060 (2) | |
H21B | 1.0396 | −0.1281 | 0.1735 | 0.072* | |
H22B | 1.0277 | −0.1182 | 0.2868 | 0.072* | |
C22B | 1.1924 (6) | −0.0821 (7) | 0.2544 (6) | 0.052 (2) | |
C23B | 1.2424 (7) | −0.1631 (8) | 0.3096 (7) | 0.065 (2) | |
H23B | 1.1960 | −0.2148 | 0.3378 | 0.077* | |
C24B | 1.3616 (8) | −0.1670 (9) | 0.3228 (8) | 0.073 (3) | |
H24B | 1.3956 | −0.2214 | 0.3601 | 0.088* | |
C25B | 1.4303 (8) | −0.0903 (9) | 0.2809 (8) | 0.076 (3) | |
H25B | 1.5105 | −0.0934 | 0.2895 | 0.091* | |
C26B | 1.3809 (7) | −0.0103 (8) | 0.2270 (7) | 0.063 (2) | |
H26B | 1.4274 | 0.0413 | 0.1988 | 0.076* | |
C27B | 1.2622 (7) | −0.0053 (8) | 0.2141 (7) | 0.063 (2) | |
H27B | 1.2290 | 0.0503 | 0.1779 | 0.076* | |
C11B | 0.9074 (6) | 0.2468 (8) | 0.0840 (7) | 0.061 (2) | |
H11B | 0.9575 | 0.2406 | 0.0314 | 0.073* | |
H12B | 0.9204 | 0.3207 | 0.1143 | 0.073* | |
C12B | 0.7833 (6) | 0.2333 (7) | 0.0394 (6) | 0.053 (2) | |
C13B | 0.7549 (7) | 0.2956 (8) | −0.0429 (7) | 0.063 (2) | |
C14B | 0.6443 (8) | 0.2966 (9) | −0.0902 (7) | 0.069 (3) | |
C15B | 0.5589 (8) | 0.2336 (11) | −0.0594 (8) | 0.083 (3) | |
C16B | 0.5815 (7) | 0.1711 (9) | 0.0206 (8) | 0.073 (3) | |
C17B | 0.6924 (7) | 0.1694 (8) | 0.0671 (7) | 0.061 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1A | 0.0329 (4) | 0.0381 (6) | 0.0473 (6) | 0.0008 (3) | 0.0059 (4) | 0.0120 (4) |
Pd1B | 0.0522 (5) | 0.0550 (7) | 0.0488 (6) | 0.0014 (4) | 0.0007 (4) | 0.0067 (5) |
Br1A | 0.0458 (4) | 0.0747 (7) | 0.1049 (9) | 0.0047 (4) | −0.0021 (5) | 0.0361 (6) |
Br1B | 0.0697 (6) | 0.0823 (8) | 0.0709 (7) | −0.0145 (5) | 0.0038 (5) | 0.0092 (6) |
F1A | 0.069 (3) | 0.091 (4) | 0.078 (4) | 0.003 (3) | 0.029 (3) | 0.007 (3) |
F2A | 0.142 (5) | 0.110 (6) | 0.072 (4) | −0.001 (4) | 0.040 (4) | 0.023 (4) |
F3A | 0.157 (6) | 0.100 (5) | 0.065 (4) | 0.010 (4) | −0.027 (4) | 0.015 (4) |
F4A | 0.079 (4) | 0.128 (6) | 0.089 (5) | 0.012 (3) | −0.027 (3) | 0.012 (4) |
F5A | 0.052 (3) | 0.119 (5) | 0.086 (4) | −0.011 (3) | −0.002 (3) | 0.029 (4) |
F1B | 0.085 (3) | 0.094 (5) | 0.085 (4) | 0.002 (3) | 0.017 (3) | 0.043 (4) |
F2B | 0.112 (4) | 0.100 (5) | 0.073 (4) | 0.014 (4) | −0.022 (3) | 0.031 (4) |
F3B | 0.070 (4) | 0.164 (7) | 0.097 (5) | 0.005 (4) | −0.020 (3) | 0.014 (5) |
F4B | 0.071 (4) | 0.158 (7) | 0.125 (6) | −0.038 (4) | 0.003 (4) | 0.027 (5) |
F5B | 0.085 (3) | 0.103 (5) | 0.081 (4) | −0.014 (3) | 0.004 (3) | 0.046 (4) |
N1A | 0.042 (3) | 0.043 (4) | 0.049 (4) | −0.002 (3) | 0.004 (3) | 0.011 (3) |
N2A | 0.038 (3) | 0.047 (4) | 0.046 (4) | −0.003 (3) | 0.005 (3) | 0.012 (3) |
N1B | 0.050 (3) | 0.052 (5) | 0.049 (5) | 0.007 (3) | −0.002 (3) | 0.008 (4) |
N2B | 0.052 (3) | 0.053 (5) | 0.051 (5) | 0.007 (3) | 0.002 (3) | 0.013 (4) |
C1A | 0.033 (3) | 0.040 (5) | 0.055 (5) | 0.003 (3) | 0.000 (3) | 0.006 (4) |
C2A | 0.040 (4) | 0.037 (5) | 0.065 (6) | 0.000 (3) | −0.003 (4) | 0.010 (4) |
C3A | 0.063 (5) | 0.047 (6) | 0.071 (7) | 0.002 (4) | −0.008 (4) | −0.001 (5) |
C4A | 0.065 (6) | 0.050 (7) | 0.117 (10) | −0.020 (5) | −0.017 (6) | 0.028 (7) |
C5A | 0.048 (5) | 0.075 (8) | 0.109 (10) | −0.011 (5) | −0.007 (5) | 0.047 (7) |
C6A | 0.045 (4) | 0.070 (7) | 0.070 (6) | −0.005 (4) | 0.002 (4) | 0.023 (5) |
C7A | 0.031 (3) | 0.049 (5) | 0.062 (6) | −0.002 (3) | 0.001 (3) | 0.017 (4) |
C21A | 0.048 (4) | 0.059 (6) | 0.038 (5) | 0.000 (4) | 0.007 (3) | 0.001 (4) |
C22A | 0.049 (4) | 0.051 (5) | 0.044 (5) | 0.002 (4) | 0.003 (4) | 0.007 (4) |
C23A | 0.050 (4) | 0.066 (6) | 0.057 (6) | 0.005 (4) | 0.006 (4) | 0.005 (5) |
C24A | 0.056 (5) | 0.081 (8) | 0.064 (7) | 0.003 (5) | 0.001 (4) | −0.003 (6) |
C25A | 0.052 (5) | 0.098 (9) | 0.089 (9) | 0.000 (5) | 0.019 (5) | 0.004 (7) |
C26A | 0.101 (8) | 0.111 (10) | 0.061 (7) | 0.006 (7) | 0.039 (6) | 0.004 (7) |
C27A | 0.070 (6) | 0.104 (9) | 0.055 (6) | 0.006 (5) | 0.017 (5) | 0.013 (6) |
C11A | 0.055 (4) | 0.060 (6) | 0.058 (6) | 0.004 (4) | 0.010 (4) | 0.002 (5) |
C12A | 0.056 (4) | 0.047 (5) | 0.045 (5) | 0.000 (4) | 0.009 (4) | 0.000 (4) |
C13A | 0.064 (5) | 0.057 (6) | 0.051 (6) | 0.003 (4) | 0.013 (4) | −0.009 (5) |
C14A | 0.106 (8) | 0.062 (7) | 0.044 (6) | −0.004 (5) | 0.025 (5) | 0.002 (5) |
C15A | 0.100 (8) | 0.074 (8) | 0.045 (6) | 0.009 (6) | −0.014 (5) | −0.009 (5) |
C16A | 0.075 (6) | 0.065 (7) | 0.062 (7) | −0.002 (5) | −0.009 (5) | 0.000 (6) |
C17A | 0.062 (5) | 0.065 (7) | 0.055 (6) | −0.008 (4) | −0.002 (4) | 0.015 (5) |
C1B | 0.050 (4) | 0.055 (6) | 0.050 (5) | 0.002 (4) | 0.001 (4) | 0.012 (4) |
C2B | 0.047 (4) | 0.048 (5) | 0.050 (6) | −0.002 (4) | −0.002 (4) | 0.000 (4) |
C3B | 0.075 (6) | 0.071 (7) | 0.083 (8) | 0.011 (5) | 0.012 (5) | −0.001 (6) |
C4B | 0.104 (7) | 0.079 (8) | 0.057 (7) | −0.007 (6) | 0.015 (6) | −0.017 (6) |
C5B | 0.095 (7) | 0.102 (10) | 0.045 (6) | −0.006 (6) | 0.007 (5) | 0.007 (6) |
C6B | 0.056 (5) | 0.080 (8) | 0.055 (6) | −0.006 (5) | 0.004 (4) | 0.017 (6) |
C7B | 0.046 (4) | 0.066 (6) | 0.040 (5) | −0.003 (4) | 0.001 (3) | 0.012 (5) |
C21B | 0.063 (5) | 0.049 (6) | 0.068 (6) | 0.009 (4) | 0.003 (4) | 0.014 (5) |
C22B | 0.051 (4) | 0.051 (6) | 0.051 (5) | 0.005 (4) | −0.002 (4) | −0.001 (4) |
C23B | 0.070 (5) | 0.051 (6) | 0.070 (7) | 0.007 (4) | −0.008 (4) | 0.015 (5) |
C24B | 0.070 (6) | 0.062 (7) | 0.084 (8) | 0.011 (5) | −0.018 (5) | 0.014 (6) |
C25B | 0.056 (5) | 0.077 (8) | 0.092 (8) | 0.013 (5) | −0.009 (5) | −0.006 (6) |
C26B | 0.054 (5) | 0.081 (7) | 0.055 (6) | −0.001 (4) | 0.010 (4) | 0.009 (5) |
C27B | 0.064 (5) | 0.065 (7) | 0.060 (6) | 0.010 (5) | −0.004 (4) | 0.015 (5) |
C11B | 0.055 (4) | 0.057 (6) | 0.070 (6) | 0.004 (4) | −0.002 (4) | 0.018 (5) |
C12B | 0.056 (4) | 0.052 (6) | 0.051 (5) | 0.007 (4) | 0.004 (4) | 0.010 (4) |
C13B | 0.064 (5) | 0.073 (7) | 0.055 (6) | 0.007 (5) | 0.011 (4) | 0.017 (5) |
C14B | 0.072 (6) | 0.075 (7) | 0.059 (6) | 0.013 (5) | −0.008 (5) | 0.016 (6) |
C15B | 0.061 (6) | 0.107 (10) | 0.077 (8) | 0.016 (6) | −0.013 (5) | 0.001 (7) |
C16B | 0.056 (5) | 0.084 (8) | 0.079 (8) | −0.017 (5) | 0.006 (5) | 0.009 (6) |
C17B | 0.068 (5) | 0.072 (7) | 0.046 (5) | 0.003 (5) | 0.012 (4) | 0.018 (5) |
Pd1A—C1Ai | 2.030 (8) | C24A—H24A | 0.9300 |
Pd1A—C1A | 2.030 (8) | C25A—C26A | 1.346 (14) |
Pd1A—Br1Ai | 2.4218 (8) | C25A—H25A | 0.9300 |
Pd1A—Br1A | 2.4218 (8) | C26A—C27A | 1.401 (12) |
Pd1B—C1Bii | 2.018 (9) | C26A—H26A | 0.9300 |
Pd1B—C1B | 2.018 (9) | C27A—H27A | 0.9300 |
Pd1B—Br1B | 2.4407 (10) | C11A—C12A | 1.506 (11) |
Pd1B—Br1Bii | 2.4407 (10) | C11A—H11A | 0.9700 |
F1A—C13A | 1.353 (9) | C11A—H12A | 0.9700 |
F2A—C14A | 1.340 (10) | C12A—C13A | 1.367 (11) |
F3A—C15A | 1.359 (11) | C12A—C17A | 1.384 (11) |
F4A—C16A | 1.333 (10) | C13A—C14A | 1.381 (13) |
F5A—C17A | 1.326 (10) | C14A—C15A | 1.374 (13) |
F1B—C13B | 1.334 (10) | C15A—C16A | 1.328 (14) |
F2B—C14B | 1.338 (10) | C16A—C17A | 1.390 (13) |
F3B—C15B | 1.333 (10) | C2B—C3B | 1.356 (13) |
F4B—C16B | 1.337 (11) | C2B—C7B | 1.385 (11) |
F5B—C17B | 1.338 (9) | C3B—C4B | 1.381 (14) |
N1A—C1A | 1.352 (10) | C3B—H3B | 0.9300 |
N1A—C2A | 1.399 (9) | C4B—C5B | 1.399 (15) |
N1A—C11A | 1.448 (10) | C4B—H4B | 0.9300 |
N2A—C1A | 1.351 (9) | C5B—C6B | 1.361 (14) |
N2A—C7A | 1.380 (10) | C5B—H5B | 0.9300 |
N2A—C21A | 1.461 (10) | C6B—C7B | 1.377 (12) |
C2A—C7A | 1.379 (11) | C6B—H6B | 0.9300 |
N1B—C1B | 1.357 (10) | C21B—C22B | 1.507 (10) |
N1B—C2B | 1.392 (10) | C21B—H21B | 0.9700 |
N1B—C11B | 1.453 (10) | C21B—H22B | 0.9700 |
N2B—C1B | 1.350 (10) | C22B—C27B | 1.378 (12) |
N2B—C7B | 1.392 (11) | C22B—C23B | 1.380 (11) |
N2B—C21B | 1.460 (10) | C23B—C24B | 1.382 (11) |
C2A—C3A | 1.393 (12) | C23B—H23B | 0.9300 |
C3A—C4A | 1.365 (13) | C24B—C25B | 1.380 (14) |
C3A—H3A | 0.9300 | C24B—H24B | 0.9300 |
C4A—C5A | 1.386 (15) | C25B—C26B | 1.359 (13) |
C4A—H4A | 0.9300 | C25B—H25B | 0.9300 |
C5A—C6A | 1.385 (14) | C26B—C27B | 1.376 (11) |
C5A—H5A | 0.9300 | C26B—H26B | 0.9300 |
C6A—C7A | 1.396 (11) | C27B—H27B | 0.9300 |
C6A—H6A | 0.9300 | C11B—C12B | 1.507 (11) |
C21A—C22A | 1.514 (9) | C11B—H11B | 0.9700 |
C21A—H21A | 0.9700 | C11B—H12B | 0.9700 |
C21A—H22A | 0.9700 | C12B—C17B | 1.376 (11) |
C22A—C23A | 1.367 (11) | C12B—C13B | 1.404 (12) |
C22A—C27A | 1.374 (12) | C13B—C14B | 1.380 (12) |
C23A—C24A | 1.383 (10) | C14B—C15B | 1.338 (14) |
C23A—H23A | 0.9300 | C15B—C16B | 1.370 (14) |
C24A—C25A | 1.348 (14) | C16B—C17B | 1.381 (12) |
C1Ai—Pd1A—C1A | 180.000 (1) | F2A—C14A—C15A | 122.1 (10) |
C1Ai—Pd1A—Br1Ai | 90.13 (17) | F2A—C14A—C13A | 120.4 (9) |
C1A—Pd1A—Br1Ai | 89.87 (18) | C15A—C14A—C13A | 117.5 (9) |
C1Ai—Pd1A—Br1A | 89.87 (17) | C16A—C15A—F3A | 121.5 (10) |
C1A—Pd1A—Br1A | 90.13 (18) | C16A—C15A—C14A | 121.5 (10) |
Br1Ai—Pd1A—Br1A | 180.000 (1) | F3A—C15A—C14A | 117.0 (10) |
C1Bii—Pd1B—C1B | 180.0 (4) | C15A—C16A—F4A | 120.8 (10) |
C1Bii—Pd1B—Br1B | 91.1 (2) | C15A—C16A—C17A | 119.7 (9) |
C1Bii—Pd1B—Br1Bii | 88.9 (2) | F4A—C16A—C17A | 119.4 (9) |
C1B—Pd1B—Br1Bii | 91.1 (2) | F5A—C17A—C12A | 120.4 (8) |
C1B—Pd1B—Br1B | 88.9 (2) | F5A—C17A—C16A | 117.7 (8) |
Br1B—Pd1B—Br1Bii | 180.00 (5) | C12A—C17A—C16A | 121.9 (9) |
C1A—N1A—C2A | 110.3 (6) | N2B—C1B—N1B | 105.7 (7) |
C1A—N1A—C11A | 125.6 (7) | N2B—C1B—Pd1B | 126.9 (6) |
C2A—N1A—C11A | 124.1 (7) | N1B—C1B—Pd1B | 127.4 (6) |
C1A—N2A—C7A | 111.3 (7) | C3B—C2B—C7B | 122.1 (9) |
C1A—N2A—C21A | 123.8 (7) | C3B—C2B—N1B | 132.6 (8) |
C7A—N2A—C21A | 124.9 (6) | C7B—C2B—N1B | 105.3 (7) |
C1B—N1B—C2B | 111.5 (7) | C2B—C3B—C4B | 116.9 (10) |
C1B—N1B—C11B | 123.7 (7) | C2B—C3B—H3B | 121.6 |
C2B—N1B—C11B | 124.4 (7) | C4B—C3B—H3B | 121.6 |
C1B—N2B—C7B | 110.6 (7) | C3B—C4B—C5B | 121.3 (10) |
C1B—N2B—C21B | 124.3 (8) | C3B—C4B—H4B | 119.4 |
C7B—N2B—C21B | 125.1 (7) | C5B—C4B—H4B | 119.4 |
N2A—C1A—N1A | 105.9 (6) | C6B—C5B—C4B | 121.1 (10) |
N2A—C1A—Pd1A | 127.3 (6) | C6B—C5B—H5B | 119.4 |
N1A—C1A—Pd1A | 126.8 (5) | C4B—C5B—H5B | 119.4 |
C7A—C2A—C3A | 121.2 (8) | C5B—C6B—C7B | 117.4 (9) |
C7A—C2A—N1A | 106.2 (7) | C5B—C6B—H6B | 121.3 |
C3A—C2A—N1A | 132.5 (8) | C7B—C6B—H6B | 121.3 |
C4A—C3A—C2A | 117.1 (9) | C6B—C7B—C2B | 121.1 (9) |
C4A—C3A—H3A | 121.5 | C6B—C7B—N2B | 132.0 (8) |
C2A—C3A—H3A | 121.5 | C2B—C7B—N2B | 106.9 (7) |
C3A—C4A—C5A | 121.9 (10) | N2B—C21B—C22B | 113.9 (7) |
C3A—C4A—H4A | 119.0 | N2B—C21B—H21B | 108.8 |
C5A—C4A—H4A | 119.0 | C22B—C21B—H21B | 108.8 |
C6A—C5A—C4A | 121.9 (10) | N2B—C21B—H22B | 108.8 |
C6A—C5A—H5A | 119.0 | C22B—C21B—H22B | 108.8 |
C4A—C5A—H5A | 119.0 | H21B—C21B—H22B | 107.7 |
C5A—C6A—C7A | 115.8 (10) | C27B—C22B—C23B | 119.5 (7) |
C5A—C6A—H6A | 122.1 | C27B—C22B—C21B | 120.9 (7) |
C7A—C6A—H6A | 122.1 | C23B—C22B—C21B | 119.5 (8) |
C2A—C7A—N2A | 106.3 (7) | C22B—C23B—C24B | 119.7 (9) |
C2A—C7A—C6A | 122.0 (9) | C22B—C23B—H23B | 120.1 |
N2A—C7A—C6A | 131.6 (9) | C24B—C23B—H23B | 120.1 |
N2A—C21A—C22A | 113.5 (6) | C25B—C24B—C23B | 120.1 (9) |
N2A—C21A—H21A | 108.9 | C25B—C24B—H24B | 119.9 |
C22A—C21A—H21A | 108.9 | C23B—C24B—H24B | 119.9 |
N2A—C21A—H22A | 108.9 | C26B—C25B—C24B | 120.1 (8) |
C22A—C21A—H22A | 108.9 | C26B—C25B—H25B | 120.0 |
H21A—C21A—H22A | 107.7 | C24B—C25B—H25B | 120.0 |
C23A—C22A—C27A | 119.6 (7) | C25B—C26B—C27B | 120.2 (9) |
C23A—C22A—C21A | 120.7 (7) | C25B—C26B—H26B | 119.9 |
C27A—C22A—C21A | 119.6 (7) | C27B—C26B—H26B | 119.9 |
C22A—C23A—C24A | 119.8 (8) | C26B—C27B—C22B | 120.4 (8) |
C22A—C23A—H23A | 120.1 | C26B—C27B—H27B | 119.8 |
C24A—C23A—H23A | 120.1 | C22B—C27B—H27B | 119.8 |
C25A—C24A—C23A | 120.5 (9) | N1B—C11B—C12B | 115.2 (7) |
C25A—C24A—H24A | 119.8 | N1B—C11B—H11B | 108.5 |
C23A—C24A—H24A | 119.8 | C12B—C11B—H11B | 108.5 |
C26A—C25A—C24A | 120.9 (9) | N1B—C11B—H12B | 108.5 |
C26A—C25A—H25A | 119.6 | C12B—C11B—H12B | 108.5 |
C24A—C25A—H25A | 119.6 | H11B—C11B—H12B | 107.5 |
C25A—C26A—C27A | 119.7 (9) | C17B—C12B—C13B | 114.3 (7) |
C25A—C26A—H26A | 120.1 | C17B—C12B—C11B | 130.0 (8) |
C27A—C26A—H26A | 120.1 | C13B—C12B—C11B | 115.7 (8) |
C22A—C27A—C26A | 119.5 (9) | F1B—C13B—C14B | 117.8 (9) |
C22A—C27A—H27A | 120.2 | F1B—C13B—C12B | 118.9 (8) |
C26A—C27A—H27A | 120.2 | C14B—C13B—C12B | 123.3 (9) |
N1A—C11A—C12A | 115.3 (6) | C15B—C14B—F2B | 119.9 (8) |
N1A—C11A—H11A | 108.5 | C15B—C14B—C13B | 119.7 (9) |
C12A—C11A—H11A | 108.5 | F2B—C14B—C13B | 120.4 (9) |
N1A—C11A—H12A | 108.5 | F3B—C15B—C14B | 122.1 (11) |
C12A—C11A—H12A | 108.5 | F3B—C15B—C16B | 118.3 (11) |
H11A—C11A—H12A | 107.5 | C14B—C15B—C16B | 119.6 (8) |
C13A—C12A—C17A | 115.5 (8) | F4B—C16B—C15B | 120.3 (9) |
C13A—C12A—C11A | 121.1 (7) | F4B—C16B—C17B | 119.3 (10) |
C17A—C12A—C11A | 123.4 (7) | C15B—C16B—C17B | 120.4 (9) |
F1A—C13A—C12A | 119.0 (8) | F5B—C17B—C12B | 119.4 (8) |
F1A—C13A—C14A | 117.1 (8) | F5B—C17B—C16B | 117.8 (8) |
C12A—C13A—C14A | 123.8 (8) | C12B—C17B—C16B | 122.5 (9) |
C7A—N2A—C1A—N1A | 1.0 (8) | C7B—N2B—C1B—N1B | −1.8 (8) |
C21A—N2A—C1A—N1A | 177.7 (6) | C21B—N2B—C1B—N1B | 176.6 (7) |
C7A—N2A—C1A—Pd1A | −178.7 (5) | C7B—N2B—C1B—Pd1B | 177.3 (5) |
C21A—N2A—C1A—Pd1A | −1.9 (9) | C21B—N2B—C1B—Pd1B | −4.3 (11) |
C2A—N1A—C1A—N2A | −0.4 (7) | C2B—N1B—C1B—N2B | 0.8 (9) |
C11A—N1A—C1A—N2A | −178.0 (6) | C11B—N1B—C1B—N2B | 173.5 (7) |
C2A—N1A—C1A—Pd1A | 179.2 (5) | C2B—N1B—C1B—Pd1B | −178.4 (5) |
C11A—N1A—C1A—Pd1A | 1.7 (10) | C11B—N1B—C1B—Pd1B | −5.7 (11) |
Br1Ai—Pd1A—C1A—N2A | −78.4 (6) | Br1B—Pd1B—C1B—N2B | 73.5 (7) |
Br1A—Pd1A—C1A—N2A | 101.6 (6) | Br1Bii—Pd1B—C1B—N2B | −106.5 (7) |
Br1Ai—Pd1A—C1A—N1A | 102.0 (6) | Br1B—Pd1B—C1B—N1B | −107.5 (7) |
Br1A—Pd1A—C1A—N1A | −78.0 (6) | Br1Bii—Pd1B—C1B—N1B | 72.5 (7) |
C1A—N1A—C2A—C7A | −0.3 (8) | C1B—N1B—C2B—C3B | −177.5 (9) |
C11A—N1A—C2A—C7A | 177.4 (6) | C11B—N1B—C2B—C3B | 9.9 (14) |
C1A—N1A—C2A—C3A | −178.4 (8) | C1B—N1B—C2B—C7B | 0.6 (9) |
C11A—N1A—C2A—C3A | −0.7 (12) | C11B—N1B—C2B—C7B | −172.1 (7) |
C7A—C2A—C3A—C4A | −1.6 (11) | C7B—C2B—C3B—C4B | 3.7 (14) |
N1A—C2A—C3A—C4A | 176.3 (8) | N1B—C2B—C3B—C4B | −178.5 (9) |
C2A—C3A—C4A—C5A | 0.0 (13) | C2B—C3B—C4B—C5B | −0.6 (16) |
C3A—C4A—C5A—C6A | 1.3 (14) | C3B—C4B—C5B—C6B | −1.0 (17) |
C4A—C5A—C6A—C7A | −1.0 (12) | C4B—C5B—C6B—C7B | −0.6 (15) |
C3A—C2A—C7A—N2A | 179.2 (6) | C5B—C6B—C7B—C2B | 3.6 (13) |
N1A—C2A—C7A—N2A | 0.8 (7) | C5B—C6B—C7B—N2B | −179.0 (9) |
C3A—C2A—C7A—C6A | 2.0 (11) | C3B—C2B—C7B—C6B | −5.4 (13) |
N1A—C2A—C7A—C6A | −176.3 (6) | N1B—C2B—C7B—C6B | 176.3 (7) |
C1A—N2A—C7A—C2A | −1.2 (8) | C3B—C2B—C7B—N2B | 176.7 (8) |
C21A—N2A—C7A—C2A | −177.9 (6) | N1B—C2B—C7B—N2B | −1.6 (8) |
C1A—N2A—C7A—C6A | 175.6 (7) | C1B—N2B—C7B—C6B | −175.4 (8) |
C21A—N2A—C7A—C6A | −1.1 (12) | C21B—N2B—C7B—C6B | 6.2 (13) |
C5A—C6A—C7A—C2A | −0.7 (11) | C1B—N2B—C7B—C2B | 2.2 (9) |
C5A—C6A—C7A—N2A | −177.1 (7) | C21B—N2B—C7B—C2B | −176.2 (7) |
C1A—N2A—C21A—C22A | 131.5 (7) | C1B—N2B—C21B—C22B | 100.8 (9) |
C7A—N2A—C21A—C22A | −52.2 (9) | C7B—N2B—C21B—C22B | −81.0 (10) |
N2A—C21A—C22A—C23A | −48.5 (11) | N2B—C21B—C22B—C27B | −34.3 (12) |
N2A—C21A—C22A—C27A | 131.6 (9) | N2B—C21B—C22B—C23B | 149.8 (8) |
C27A—C22A—C23A—C24A | 0.0 (14) | C27B—C22B—C23B—C24B | −0.7 (14) |
C21A—C22A—C23A—C24A | −179.9 (8) | C21B—C22B—C23B—C24B | 175.2 (9) |
C22A—C23A—C24A—C25A | −1.4 (15) | C22B—C23B—C24B—C25B | −0.1 (15) |
C23A—C24A—C25A—C26A | 2.2 (17) | C23B—C24B—C25B—C26B | 0.5 (16) |
C24A—C25A—C26A—C27A | −1.7 (18) | C24B—C25B—C26B—C27B | 0.0 (16) |
C23A—C22A—C27A—C26A | 0.4 (15) | C25B—C26B—C27B—C22B | −0.9 (14) |
C21A—C22A—C27A—C26A | −179.7 (9) | C23B—C22B—C27B—C26B | 1.2 (14) |
C25A—C26A—C27A—C22A | 0.4 (17) | C21B—C22B—C27B—C26B | −174.7 (9) |
C1A—N1A—C11A—C12A | −70.9 (10) | C1B—N1B—C11B—C12B | 89.3 (9) |
C2A—N1A—C11A—C12A | 111.9 (8) | C2B—N1B—C11B—C12B | −98.9 (10) |
N1A—C11A—C12A—C13A | 142.7 (8) | N1B—C11B—C12B—C17B | 11.1 (14) |
N1A—C11A—C12A—C17A | −37.1 (12) | N1B—C11B—C12B—C13B | −169.3 (8) |
C17A—C12A—C13A—F1A | −178.3 (7) | C17B—C12B—C13B—F1B | −179.5 (8) |
C11A—C12A—C13A—F1A | 1.9 (13) | C11B—C12B—C13B—F1B | 0.9 (13) |
C17A—C12A—C13A—C14A | 0.3 (14) | C17B—C12B—C13B—C14B | 2.4 (14) |
C11A—C12A—C13A—C14A | −179.5 (9) | C11B—C12B—C13B—C14B | −177.3 (9) |
F1A—C13A—C14A—F2A | −3.6 (13) | F1B—C13B—C14B—C15B | 180.0 (10) |
C12A—C13A—C14A—F2A | 177.7 (9) | C12B—C13B—C14B—C15B | −1.9 (16) |
F1A—C13A—C14A—C15A | 178.4 (8) | F1B—C13B—C14B—F2B | 0.7 (14) |
C12A—C13A—C14A—C15A | −0.2 (15) | C12B—C13B—C14B—F2B | 178.8 (9) |
F2A—C14A—C15A—C16A | −178.6 (10) | F2B—C14B—C15B—F3B | −1.3 (17) |
C13A—C14A—C15A—C16A | −0.8 (15) | C13B—C14B—C15B—F3B | 179.4 (9) |
F2A—C14A—C15A—F3A | 2.4 (15) | F2B—C14B—C15B—C16B | −178.9 (9) |
C13A—C14A—C15A—F3A | −179.7 (9) | C13B—C14B—C15B—C16B | 1.8 (17) |
F3A—C15A—C16A—F4A | −1.8 (16) | F3B—C15B—C16B—F4B | 0.5 (16) |
C14A—C15A—C16A—F4A | 179.3 (9) | C14B—C15B—C16B—F4B | 178.2 (10) |
F3A—C15A—C16A—C17A | −179.6 (9) | F3B—C15B—C16B—C17B | 179.8 (9) |
C14A—C15A—C16A—C17A | 1.6 (16) | C14B—C15B—C16B—C17B | −2.5 (17) |
C13A—C12A—C17A—F5A | 179.0 (9) | C13B—C12B—C17B—F5B | −176.8 (8) |
C11A—C12A—C17A—F5A | −1.2 (14) | C11B—C12B—C17B—F5B | 2.8 (15) |
C13A—C12A—C17A—C16A | 0.5 (14) | C13B—C12B—C17B—C16B | −3.1 (14) |
C11A—C12A—C17A—C16A | −179.7 (9) | C11B—C12B—C17B—C16B | 176.5 (10) |
C15A—C16A—C17A—F5A | 180.0 (10) | F4B—C16B—C17B—F5B | −3.6 (15) |
F4A—C16A—C17A—F5A | 2.2 (14) | C15B—C16B—C17B—F5B | 177.1 (10) |
C15A—C16A—C17A—C12A | −1.4 (16) | F4B—C16B—C17B—C12B | −177.4 (10) |
F4A—C16A—C17A—C12A | −179.2 (9) | C15B—C16B—C17B—C12B | 3.3 (16) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [PdBr2(C21H13F5N2)2] |
Mr | 1042.89 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 11.6122 (8), 12.1401 (9), 13.6590 (11) |
α, β, γ (°) | 92.589 (6), 95.610 (6), 92.520 (6) |
V (Å3) | 1912.1 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.66 |
Crystal size (mm) | 0.18 × 0.16 × 0.09 |
Data collection | |
Diffractometer | Stoe IPDS-II diffractometer |
Absorption correction | Integration |
Tmin, Tmax | 0.646, 0.796 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23746, 7493, 3911 |
Rint | 0.121 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.119, 0.95 |
No. of reflections | 7493 |
No. of parameters | 535 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.68, −0.55 |
Computer programs: X-AREA (Stoe & Cie, 2002), X-AREA, X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2003), WinGX (Farrugia, 1999).
N1A—C1A | 1.352 (10) | N1B—C1B | 1.357 (10) |
N1A—C2A | 1.399 (9) | N1B—C2B | 1.392 (10) |
N1A—C11A | 1.448 (10) | N1B—C11B | 1.453 (10) |
N2A—C1A | 1.351 (9) | N2B—C1B | 1.350 (10) |
N2A—C7A | 1.380 (10) | N2B—C7B | 1.392 (11) |
N2A—C21A | 1.461 (10) | N2B—C21B | 1.460 (10) |
C2A—C7A | 1.379 (11) | C2B—C7B | 1.385 (11) |
C1A—Pd1A—Br1Ai | 89.87 (18) | C1B—Pd1B—Br1Bii | 91.1 (2) |
C1A—Pd1A—Br1A | 90.13 (18) | C1B—Pd1B—Br1B | 88.9 (2) |
N2A—C21A—C22A—C27A | 131.6 (9) | N2B—C21B—C22B—C27B | −34.3 (12) |
N1A—C11A—C12A—C13A | 142.7 (8) | N1B—C11B—C12B—C13B | −169.3 (8) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C21A—H21A··· F1Ai | 0.97 | 2.45 | 3.19 (1) | 132 |
C11A—H12A···F1A | 0.97 | 2.39 | 2.80 (1) | 105 |
C11B—H11B···Br1Bii | 0.97 | 2.89 | 3.70 (1) | 142 |
C26B—H26B···F4Biii | 0.93 | 2.38 | 3.21 (1) | 148 |
C25B—H25B···Cg1iv | 0.93 | 2.59 | 3.41 (1) | 148 |
C3A—H3A···Cg2v | 0.93 | 2.78 | 3.62 (1) | 150 |
Cg1 and Cg2 are the centroids of the C2A–C7A and C22B–C27B rings, respectively. Symmetry codes: (iii) x + 1, y, z; (iv) −x + 2, −y, −z + 1; (v) x − 1, y, z. |
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N-heterocyclic carbenes (NHC) have been the subject of intense research in the field of organometallic chemistry (Herrmann et al., 2001; Crudden & Allen, 2004; Scott & Nolan, 2005). NHCs and their metal complexes continue to attract interest as components in homogeneous catalysis (Herrmann, 2002). NHCs are becoming substantial structure unit [being increasingly used as structural units?] for many organometallic compounds and homogeneous catalysts, but little attention has been paid to the synthesis of NHC derivatives with fluorophilic properties. NHC complexes with fluorinated substituents are rare (Xu et al., 2000; McGrandle & Saunders, 2005; Dinçer et al., 2006; Burling et al., 2006). Prompted by the novel properties of these carbene ligands, we decided to prepare some supercritical carbon dioxide (scCO2) soluble derivatives in the hope that the resulting carbene complexes can be adapted for catalysis in scCO2, which is an attractive alternative to conventional organic liquids for clean synthesis. One of the major limitations of scCO2 as a reaction medium for homogeneous catalysis is its rather low solvent strength towards catalysts derived from common organometallic complexes (Smart et al., 1997; Kainz et al.,1997; Jessop et al., 1999). In order to accomplish this goal, we required a ligand that has electronic properties similar to those of an NHC ligand but allows solubility in scCO2 . To solve this problem, we have synthesized ligands with different numbers of fluorine-containing groups. We report here the synthesis of (I) and (II), and the crystal structure of the title compound, [PdBr2(C21H13F5N2)2], (II) (Fig. 1).
Compound (II) crystallizes with two independent centrosymmetric conformational isomers, molecules A and B. While one-half of each molecule is crystallographically independent, the other half is generated by an inversion centre located at the metal centre of the molecule. The conformational isomers differ by orientations of their benzyl and pentafluorobenzyl rings. The benzyl and pentafluorobenzyl rings of molecule A are located on same side of the benzimidazole ring plane, while these rings in molecule B are located on opposite sides of the benzimidazole ring plane.
The coordination geometries around the Pd atoms are slightly distorted square planar, formed by the two coordinating C atoms of the benzimidazole rings and two Br atoms in a trans arrangement. The cis angles deviate by up to 1.1° from the ideal value of 90°. The planes of the benzimidazole rings make dihedral angles of 79.1 (2) and 75.2 (1)° with the coordination planes for molecule A and B, respectively.
The Pd—Br bond lengths are 2.4218 (8) and 2.4407 (10) Å for molecules A and B. The Pd—C bond distances between the NHC ligand and the metal atom are 2.030 (8) and 2.018 (9) Å, comparable to those in other palladium(II)–NHC complexes (Magill et al., 2001; Liu et al., 2003; Gökçe et al., 2004). Although both C—N bonds in the NHC rings are single bonds, their distances are different, as found in related complexes (Gökçe et al., 2004, 2006; Karabıyık et al., 2006a,b PLEASE CHECK CITATIONS). The bond distances between the carbene C atom bonded to Pd and N atoms in the NHC ring are shorter than the other C—N bond distances (Table 1). This is possibly indicative of a greater partial double-bond character due to partial electron donation by N to the carbene C-atom donor (Fröhlich et al., 1997; Herrmann et al., 2001). Theoretical study also indicates that the stability of these carbenes is due to electron donation from the nitrogen lone pairs into the formally vacant p(π) orbital of the carbene C atom (herein C1A and C1B) (Karabıyık et al., 2005).
There are three short intramolecular contacts in the crystal structure (Table 2), two of C—H···F type for molecule A and one of C—H···Br type for molecule B. As shown in Figs. 2 and 3, atoms C25B and C3A in the molecule at (x, y, z) act as hydrogen-bond donors to the C2A–C7A ring in the molecule at (2 − x, −y, 1 − z) and the C22B–C27B ring in the molecule at (−1 + x, y, z), respectively.