Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107015417/av3078sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107015417/av3078IIsup2.hkl |
CCDC reference: 649079
All manipulations were carried out under an atmosphere of dry Ar using standard Schlenk techniques. Solvent and reagents were obtained from Aldrich, Fluka and Merck. [Rh(µ-OMe)(1,5-COD)]2 (Uson et al., 1985) was synthesized according to literature procedures. A 50 ml Schlenk tube was charged with (I) (Gülcemal, 2005) (111.80 mg, 0.2 mmol), [Rh(OMe)(η4-COD)]2 (48.40 mg, 0.1 mmol) and 5 ml of dichloromethane. The solution was stirred for 24 h at room temperature and heated under reflux for 2 h. Upon cooling to room temperature, hexane (10 ml) was added to the mixture. The resulting solid was filtered off and recrystallized from CH2Cl2/MeOH (1:5 v/v, 18 ml) (yield 115 mg, 78%; m.p. 509–511 K). Analysis calculated for C29H20BrF10N2Rh: C 46.97, H 2.70, N 3.78%; found: C 46.27, H 2.94, N 3.71%. 1H NMR (CDCl3): δ 1.94 (q, J = 9.5 Hz, 4H, COD-CH2), 2.37 (br, 4H, COD-CH2), 3.52 (s, 2H, COD-CH), 5.22 (s, 2H, COD-CH), 5.92 (d, 2H, J = 16 Hz, CH2—C6F5), 6.39 (d, 2H, J = 16 Hz, CH2—C6F5), 7.09 (q, J = 2.8 Hz, 2H, Ar—H), 7.21 (q, J = 3.1 Hz, 2H, Ar—H); 13C NMR (CDCl3): δ 27.42 (d, J = 21.4 Hz, COD-CH2), 31.88 (d, J = 22.2 Hz, COD-CH2), 40.78 (CH2—C6F5), 69.04 (d, J = 13.8 Hz, COD-CH), 100.28 (d, J = 6.9 Hz, COD-CH), 108.42, 108.85, 122.13, 133.79, 135.70, 138.16, 139.16, 141.64, 143.37, 145.83 (Ar—C), 199.03 (d, J = 50.6 Hz, Ccarb—Rh); 19F NMR (CDCl3): δ -140.98 (2 F, Fo), -153.83 (1 F, Fp), -161.51 (2 F, Fm).
H atoms were positioned geometrically and treated using a riding model, fixing the C—H bond lengths at 0.97, 0.98 and 0.93 Å for CH2, CH and aromatic CH groups, respectively. The Uiso(H) values were set at 1.2Ueq of the pivot atom.
Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).
[RhBr(C8H12)(C21H8N2F10)] | F(000) = 1512 |
Mr = 769.29 | Dx = 1.828 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 31719 reflections |
a = 10.3441 (5) Å | θ = 1.6–27.2° |
b = 21.4937 (10) Å | µ = 2.13 mm−1 |
c = 15.4717 (7) Å | T = 296 K |
β = 125.629 (3)° | Prism, yellow |
V = 2795.9 (2) Å3 | 0.52 × 0.42 × 0.36 mm |
Z = 4 |
Stoe IPDS-II diffractometer | 6179 independent reflections |
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus | 4843 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.056 |
Detector resolution: 6.67 pixels mm-1 | θmax = 27.2°, θmin = 1.9° |
ω scans | h = −13→13 |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | k = −27→27 |
Tmin = 0.288, Tmax = 0.545 | l = −19→19 |
36192 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.101 | w = 1/[σ2(Fo2) + (0.0488P)2 + 1.2219P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
6179 reflections | Δρmax = 0.41 e Å−3 |
389 parameters | Δρmin = −0.79 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0027 (3) |
[RhBr(C8H12)(C21H8N2F10)] | V = 2795.9 (2) Å3 |
Mr = 769.29 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.3441 (5) Å | µ = 2.13 mm−1 |
b = 21.4937 (10) Å | T = 296 K |
c = 15.4717 (7) Å | 0.52 × 0.42 × 0.36 mm |
β = 125.629 (3)° |
Stoe IPDS-II diffractometer | 6179 independent reflections |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | 4843 reflections with I > 2σ(I) |
Tmin = 0.288, Tmax = 0.545 | Rint = 0.056 |
36192 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.41 e Å−3 |
6179 reflections | Δρmin = −0.79 e Å−3 |
389 parameters |
Experimental. 1H, 13C and 19F NMR spectra were recorded using a Varian 400 MHz s pectrometer with chemical shifts referenced to residual solvent CDCl3. Elemental analysis was carried out by the analytical service of TÜBİTAK (the Scientific & Technical Research Council of Turkey) with a CHNS-932 (LECO) apparatus. Melting points were determined using an electro thermal melting point detection apparatus. |
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 | ||
Rh1 | 1.06906 (3) | 0.160433 (12) | 0.76436 (2) | 0.05361 (10) | |
Br1 | 0.81298 (5) | 0.210453 (19) | 0.61874 (3) | 0.07439 (14) | |
F1 | 0.6657 (3) | 0.20549 (13) | 0.8181 (3) | 0.1033 (9) | |
F2 | 0.4795 (4) | 0.29422 (16) | 0.6782 (3) | 0.1159 (10) | |
F3 | 0.6130 (5) | 0.39550 (13) | 0.6564 (3) | 0.1201 (11) | |
F4 | 0.9343 (5) | 0.40495 (14) | 0.7727 (3) | 0.1442 (14) | |
F5 | 1.1180 (4) | 0.31665 (14) | 0.9127 (3) | 0.1126 (10) | |
F6 | 0.9339 (4) | 0.01534 (15) | 0.5720 (2) | 0.1082 (9) | |
F7 | 0.7248 (6) | 0.05384 (18) | 0.3723 (3) | 0.1621 (18) | |
F8 | 0.4412 (5) | 0.10236 (15) | 0.3120 (2) | 0.1635 (19) | |
F9 | 0.3674 (3) | 0.10778 (16) | 0.4532 (3) | 0.1405 (14) | |
F10 | 0.5754 (3) | 0.06782 (14) | 0.6525 (2) | 0.0938 (7) | |
N1 | 0.9050 (3) | 0.06318 (12) | 0.8118 (2) | 0.0507 (6) | |
N2 | 0.9578 (3) | 0.14510 (12) | 0.9066 (2) | 0.0554 (6) | |
C1 | 0.9690 (4) | 0.12105 (14) | 0.8300 (2) | 0.0513 (7) | |
C2 | 0.8530 (4) | 0.05093 (15) | 0.8752 (2) | 0.0536 (7) | |
C3 | 0.7801 (4) | −0.00053 (17) | 0.8832 (3) | 0.0643 (9) | |
H3 | 0.7589 | −0.0361 | 0.8428 | 0.077* | |
C4 | 0.7403 (5) | 0.0036 (2) | 0.9541 (3) | 0.0744 (11) | |
H4 | 0.6891 | −0.0296 | 0.9607 | 0.089* | |
C5 | 0.7747 (5) | 0.0558 (2) | 1.0151 (3) | 0.0771 (11) | |
H5 | 0.7482 | 0.0565 | 1.0632 | 0.092* | |
C6 | 0.8474 (5) | 0.1075 (2) | 1.0076 (3) | 0.0696 (9) | |
H6 | 0.8689 | 0.1430 | 1.0483 | 0.083* | |
C7 | 0.8862 (4) | 0.10316 (15) | 0.9360 (3) | 0.0554 (7) | |
C8 | 1.0064 (5) | 0.20827 (17) | 0.9490 (3) | 0.0686 (9) | |
H8A | 1.1136 | 0.2154 | 0.9698 | 0.082* | |
H8B | 1.0083 | 0.2118 | 1.0122 | 0.082* | |
C9 | 0.8986 (5) | 0.25774 (16) | 0.8710 (3) | 0.0636 (9) | |
C10 | 0.7349 (5) | 0.25522 (18) | 0.8094 (4) | 0.0718 (10) | |
C11 | 0.6373 (6) | 0.3000 (2) | 0.7371 (4) | 0.0817 (12) | |
C12 | 0.7048 (7) | 0.3505 (2) | 0.7252 (4) | 0.0845 (13) | |
C13 | 0.8651 (7) | 0.35587 (19) | 0.7844 (4) | 0.0879 (14) | |
C14 | 0.9612 (5) | 0.31027 (19) | 0.8565 (4) | 0.0770 (11) | |
C15 | 0.8845 (4) | 0.02064 (16) | 0.7314 (3) | 0.0593 (8) | |
H15A | 0.8532 | −0.0198 | 0.7413 | 0.071* | |
H15B | 0.9859 | 0.0157 | 0.7417 | 0.071* | |
C16 | 0.7627 (4) | 0.04194 (15) | 0.6192 (3) | 0.0585 (8) | |
C17 | 0.7954 (6) | 0.03886 (18) | 0.5447 (3) | 0.0783 (11) | |
C18 | 0.6868 (9) | 0.0585 (2) | 0.4418 (4) | 0.1026 (18) | |
C19 | 0.5465 (8) | 0.0824 (2) | 0.4121 (4) | 0.1034 (19) | |
C20 | 0.5076 (6) | 0.0855 (2) | 0.4826 (4) | 0.0920 (15) | |
C21 | 0.6168 (5) | 0.06489 (17) | 0.5857 (3) | 0.0701 (10) | |
C22 | 1.2604 (4) | 0.0965 (2) | 0.8417 (3) | 0.0718 (10) | |
H22 | 1.2377 | 0.0587 | 0.8660 | 0.086* | |
C23 | 1.2981 (4) | 0.1476 (2) | 0.9077 (3) | 0.0740 (11) | |
H23 | 1.2961 | 0.1385 | 0.9690 | 0.089* | |
C24 | 1.4091 (6) | 0.1997 (3) | 0.9273 (5) | 0.126 (2) | |
H24A | 1.4226 | 0.2260 | 0.9830 | 0.151* | |
H24B | 1.5121 | 0.1818 | 0.9541 | 0.151* | |
C25 | 1.3626 (6) | 0.2389 (3) | 0.8376 (5) | 0.1008 (15) | |
H25A | 1.4425 | 0.2347 | 0.8239 | 0.121* | |
H25B | 1.3652 | 0.2817 | 0.8582 | 0.121* | |
C26 | 1.2046 (5) | 0.2274 (2) | 0.7363 (4) | 0.0781 (11) | |
H26 | 1.1457 | 0.2654 | 0.6993 | 0.094* | |
C27 | 1.1652 (6) | 0.1770 (2) | 0.6699 (4) | 0.0798 (12) | |
H27 | 1.0839 | 0.1858 | 0.5945 | 0.096* | |
C28 | 1.2764 (7) | 0.1257 (3) | 0.6897 (5) | 0.1087 (18) | |
H28A | 1.2261 | 0.1007 | 0.6257 | 0.130* | |
H28B | 1.3708 | 0.1441 | 0.7011 | 0.130* | |
C29 | 1.3272 (7) | 0.0840 (3) | 0.7788 (5) | 0.123 (2) | |
H29A | 1.4422 | 0.0858 | 0.8273 | 0.147* | |
H29B | 1.2987 | 0.0419 | 0.7515 | 0.147* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Rh1 | 0.05673 (16) | 0.05533 (16) | 0.05389 (16) | 0.00292 (11) | 0.03513 (13) | 0.00857 (11) |
Br1 | 0.0737 (2) | 0.0689 (2) | 0.0642 (2) | 0.01353 (18) | 0.0309 (2) | 0.00471 (17) |
F1 | 0.0771 (15) | 0.0925 (18) | 0.151 (3) | −0.0002 (13) | 0.0724 (17) | 0.0390 (17) |
F2 | 0.0910 (19) | 0.134 (3) | 0.133 (3) | 0.0276 (17) | 0.0714 (19) | 0.042 (2) |
F3 | 0.184 (3) | 0.0799 (17) | 0.106 (2) | 0.0204 (19) | 0.090 (2) | 0.0233 (16) |
F4 | 0.202 (4) | 0.090 (2) | 0.131 (3) | −0.065 (2) | 0.092 (3) | 0.0055 (18) |
F5 | 0.110 (2) | 0.104 (2) | 0.118 (2) | −0.0535 (17) | 0.0630 (19) | −0.0161 (17) |
F6 | 0.139 (3) | 0.119 (2) | 0.112 (2) | 0.0158 (19) | 0.099 (2) | −0.0010 (17) |
F7 | 0.302 (6) | 0.123 (3) | 0.106 (2) | −0.003 (3) | 0.144 (3) | 0.002 (2) |
F8 | 0.227 (4) | 0.091 (2) | 0.0549 (16) | −0.010 (2) | 0.015 (2) | 0.0060 (14) |
F9 | 0.0806 (18) | 0.115 (2) | 0.129 (3) | 0.0228 (17) | 0.0065 (17) | 0.011 (2) |
F10 | 0.0687 (14) | 0.117 (2) | 0.0950 (19) | 0.0156 (13) | 0.0475 (14) | 0.0049 (15) |
N1 | 0.0551 (14) | 0.0502 (14) | 0.0478 (14) | −0.0012 (11) | 0.0305 (12) | 0.0019 (11) |
N2 | 0.0643 (16) | 0.0522 (14) | 0.0577 (16) | −0.0078 (12) | 0.0400 (14) | −0.0056 (11) |
C1 | 0.0508 (16) | 0.0520 (17) | 0.0496 (16) | 0.0014 (13) | 0.0284 (14) | 0.0020 (13) |
C2 | 0.0555 (17) | 0.0539 (17) | 0.0497 (17) | 0.0002 (13) | 0.0296 (15) | 0.0055 (13) |
C3 | 0.067 (2) | 0.0578 (19) | 0.063 (2) | −0.0060 (16) | 0.0345 (18) | 0.0076 (15) |
C4 | 0.072 (2) | 0.079 (3) | 0.073 (3) | −0.0060 (19) | 0.043 (2) | 0.019 (2) |
C5 | 0.084 (3) | 0.094 (3) | 0.070 (2) | 0.003 (2) | 0.055 (2) | 0.015 (2) |
C6 | 0.079 (2) | 0.079 (2) | 0.061 (2) | −0.0037 (19) | 0.0463 (19) | −0.0038 (18) |
C7 | 0.0590 (17) | 0.0569 (18) | 0.0512 (17) | −0.0020 (14) | 0.0325 (15) | 0.0026 (14) |
C8 | 0.073 (2) | 0.062 (2) | 0.070 (2) | −0.0172 (17) | 0.041 (2) | −0.0185 (17) |
C9 | 0.089 (2) | 0.0500 (18) | 0.074 (2) | −0.0086 (17) | 0.060 (2) | −0.0099 (16) |
C10 | 0.085 (3) | 0.061 (2) | 0.097 (3) | −0.0028 (18) | 0.069 (2) | 0.0049 (19) |
C11 | 0.099 (3) | 0.078 (3) | 0.092 (3) | 0.007 (2) | 0.070 (3) | 0.010 (2) |
C12 | 0.127 (4) | 0.063 (2) | 0.082 (3) | 0.005 (2) | 0.071 (3) | 0.003 (2) |
C13 | 0.143 (4) | 0.056 (2) | 0.081 (3) | −0.026 (3) | 0.074 (3) | −0.008 (2) |
C14 | 0.096 (3) | 0.067 (2) | 0.085 (3) | −0.034 (2) | 0.062 (3) | −0.024 (2) |
C15 | 0.0632 (18) | 0.0551 (18) | 0.062 (2) | 0.0058 (15) | 0.0379 (17) | −0.0038 (15) |
C16 | 0.069 (2) | 0.0516 (17) | 0.0520 (18) | −0.0034 (15) | 0.0339 (16) | −0.0059 (14) |
C17 | 0.114 (3) | 0.057 (2) | 0.071 (3) | −0.004 (2) | 0.058 (3) | −0.0076 (18) |
C18 | 0.181 (6) | 0.066 (3) | 0.068 (3) | −0.014 (3) | 0.076 (4) | −0.007 (2) |
C19 | 0.142 (5) | 0.054 (2) | 0.054 (3) | −0.011 (3) | 0.023 (3) | −0.0034 (19) |
C20 | 0.082 (3) | 0.059 (2) | 0.079 (3) | −0.003 (2) | 0.015 (2) | −0.003 (2) |
C21 | 0.070 (2) | 0.058 (2) | 0.063 (2) | −0.0024 (17) | 0.0281 (19) | −0.0047 (16) |
C22 | 0.062 (2) | 0.077 (2) | 0.074 (2) | 0.0161 (18) | 0.0387 (19) | 0.020 (2) |
C23 | 0.0529 (19) | 0.092 (3) | 0.062 (2) | −0.0034 (18) | 0.0247 (17) | 0.020 (2) |
C24 | 0.086 (3) | 0.145 (5) | 0.098 (4) | −0.054 (3) | 0.026 (3) | 0.023 (3) |
C25 | 0.093 (3) | 0.094 (3) | 0.123 (4) | −0.027 (3) | 0.067 (3) | 0.004 (3) |
C26 | 0.093 (3) | 0.075 (3) | 0.090 (3) | −0.003 (2) | 0.066 (3) | 0.022 (2) |
C27 | 0.106 (3) | 0.085 (3) | 0.086 (3) | 0.008 (2) | 0.077 (3) | 0.019 (2) |
C28 | 0.146 (5) | 0.104 (4) | 0.141 (5) | 0.015 (3) | 0.120 (4) | 0.011 (3) |
C29 | 0.121 (4) | 0.154 (5) | 0.125 (5) | 0.070 (4) | 0.090 (4) | 0.042 (4) |
Rh1—C1 | 2.010 (3) | C9—C10 | 1.378 (6) |
Rh1—C22 | 2.116 (4) | C9—C14 | 1.384 (5) |
Rh1—C23 | 2.118 (4) | C10—C11 | 1.371 (6) |
Rh1—C26 | 2.222 (4) | C11—C12 | 1.361 (6) |
Rh1—C27 | 2.224 (4) | C12—C13 | 1.353 (7) |
Rh1—Br1 | 2.5090 (5) | C13—C14 | 1.379 (7) |
F1—C10 | 1.336 (4) | C15—C16 | 1.504 (5) |
F2—C11 | 1.333 (5) | C15—H15A | 0.9700 |
F3—C12 | 1.339 (5) | C15—H15B | 0.9700 |
F4—C13 | 1.345 (5) | C16—C21 | 1.370 (5) |
F5—C14 | 1.327 (5) | C16—C17 | 1.379 (5) |
F6—C17 | 1.334 (5) | C17—C18 | 1.375 (7) |
F7—C18 | 1.347 (6) | C18—C19 | 1.342 (8) |
F8—C19 | 1.343 (5) | C19—C20 | 1.367 (8) |
F9—C20 | 1.331 (6) | C20—C21 | 1.384 (6) |
F10—C21 | 1.331 (5) | C22—C23 | 1.392 (6) |
N1—C1 | 1.359 (4) | C22—C29 | 1.510 (6) |
N1—C2 | 1.392 (4) | C22—H22 | 0.9800 |
N1—C15 | 1.456 (4) | C23—C24 | 1.503 (6) |
N2—C1 | 1.359 (4) | C23—H23 | 0.9800 |
N2—C7 | 1.400 (4) | C24—C25 | 1.444 (7) |
N2—C8 | 1.464 (4) | C24—H24A | 0.9700 |
C2—C7 | 1.373 (5) | C24—H24B | 0.9700 |
C2—C3 | 1.385 (5) | C25—C26 | 1.484 (7) |
C3—C4 | 1.381 (5) | C25—H25A | 0.9700 |
C3—H3 | 0.9300 | C25—H25B | 0.9700 |
C4—C5 | 1.373 (6) | C26—C27 | 1.381 (6) |
C4—H4 | 0.9300 | C26—H26 | 0.9800 |
C5—C6 | 1.383 (6) | C27—C28 | 1.492 (7) |
C5—H5 | 0.9300 | C27—H27 | 0.9800 |
C6—C7 | 1.384 (5) | C28—C29 | 1.460 (7) |
C6—H6 | 0.9300 | C28—H28A | 0.9700 |
C8—C9 | 1.504 (6) | C28—H28B | 0.9700 |
C8—H8A | 0.9700 | C29—H29A | 0.9700 |
C8—H8B | 0.9700 | C29—H29B | 0.9700 |
C1—Rh1—C22 | 91.62 (14) | N1—C15—H15B | 108.8 |
C1—Rh1—C23 | 90.43 (14) | C16—C15—H15B | 108.8 |
C22—Rh1—C23 | 38.38 (17) | H15A—C15—H15B | 107.7 |
C1—Rh1—C26 | 160.15 (16) | C21—C16—C17 | 117.0 (4) |
C22—Rh1—C26 | 92.39 (16) | C21—C16—C15 | 123.0 (3) |
C23—Rh1—C26 | 80.80 (16) | C17—C16—C15 | 120.1 (4) |
C1—Rh1—C27 | 163.35 (16) | F6—C17—C18 | 119.1 (4) |
C22—Rh1—C27 | 81.17 (16) | F6—C17—C16 | 119.6 (4) |
C23—Rh1—C27 | 93.05 (18) | C18—C17—C16 | 121.3 (5) |
C26—Rh1—C27 | 36.19 (17) | C19—C18—F7 | 121.0 (5) |
C1—Rh1—Br1 | 92.82 (9) | C19—C18—C17 | 120.4 (5) |
C22—Rh1—Br1 | 159.47 (12) | F7—C18—C17 | 118.6 (6) |
C23—Rh1—Br1 | 161.40 (13) | C18—C19—F8 | 120.4 (6) |
C26—Rh1—Br1 | 90.20 (12) | C18—C19—C20 | 120.4 (4) |
C27—Rh1—Br1 | 89.06 (13) | F8—C19—C20 | 119.1 (6) |
C1—N1—C2 | 111.6 (3) | F9—C20—C19 | 120.9 (5) |
C1—N1—C15 | 124.2 (3) | F9—C20—C21 | 120.3 (5) |
C2—N1—C15 | 124.0 (3) | C19—C20—C21 | 118.8 (5) |
C1—N2—C7 | 111.6 (3) | F10—C21—C16 | 120.3 (3) |
C1—N2—C8 | 124.2 (3) | F10—C21—C20 | 117.6 (4) |
C7—N2—C8 | 124.1 (3) | C16—C21—C20 | 122.1 (4) |
N2—C1—N1 | 104.5 (3) | C23—C22—C29 | 125.2 (5) |
N2—C1—Rh1 | 127.7 (2) | C23—C22—Rh1 | 70.9 (2) |
N1—C1—Rh1 | 127.8 (2) | C29—C22—Rh1 | 112.3 (3) |
C7—C2—C3 | 121.6 (3) | C23—C22—H22 | 113.6 |
C7—C2—N1 | 106.5 (3) | C29—C22—H22 | 113.6 |
C3—C2—N1 | 132.0 (3) | Rh1—C22—H22 | 113.6 |
C4—C3—C2 | 116.7 (4) | C22—C23—C24 | 126.2 (5) |
C4—C3—H3 | 121.6 | C22—C23—Rh1 | 70.7 (2) |
C2—C3—H3 | 121.6 | C24—C23—Rh1 | 111.8 (3) |
C5—C4—C3 | 121.4 (4) | C22—C23—H23 | 113.4 |
C5—C4—H4 | 119.3 | C24—C23—H23 | 113.4 |
C3—C4—H4 | 119.3 | Rh1—C23—H23 | 113.4 |
C4—C5—C6 | 122.3 (4) | C25—C24—C23 | 116.9 (4) |
C4—C5—H5 | 118.9 | C25—C24—H24A | 108.1 |
C6—C5—H5 | 118.9 | C23—C24—H24A | 108.1 |
C5—C6—C7 | 116.0 (4) | C25—C24—H24B | 108.1 |
C5—C6—H6 | 122.0 | C23—C24—H24B | 108.1 |
C7—C6—H6 | 122.0 | H24A—C24—H24B | 107.3 |
C2—C7—C6 | 122.0 (3) | C24—C25—C26 | 117.6 (4) |
C2—C7—N2 | 105.8 (3) | C24—C25—H25A | 107.9 |
C6—C7—N2 | 132.2 (3) | C26—C25—H25A | 107.9 |
N2—C8—C9 | 113.3 (3) | C24—C25—H25B | 107.9 |
N2—C8—H8A | 108.9 | C26—C25—H25B | 107.9 |
C9—C8—H8A | 108.9 | H25A—C25—H25B | 107.2 |
N2—C8—H8B | 108.9 | C27—C26—C25 | 125.6 (5) |
C9—C8—H8B | 108.9 | C27—C26—Rh1 | 72.0 (2) |
H8A—C8—H8B | 107.7 | C25—C26—Rh1 | 109.5 (3) |
C10—C9—C14 | 115.0 (4) | C27—C26—H26 | 113.9 |
C10—C9—C8 | 124.4 (3) | C25—C26—H26 | 113.9 |
C14—C9—C8 | 120.6 (4) | Rh1—C26—H26 | 113.9 |
F1—C10—C11 | 117.4 (4) | C26—C27—C28 | 124.7 (5) |
F1—C10—C9 | 118.4 (4) | C26—C27—Rh1 | 71.8 (2) |
C11—C10—C9 | 124.1 (4) | C28—C27—Rh1 | 109.4 (3) |
F2—C11—C12 | 120.2 (4) | C26—C27—H27 | 114.3 |
F2—C11—C10 | 121.3 (4) | C28—C27—H27 | 114.3 |
C12—C11—C10 | 118.6 (5) | Rh1—C27—H27 | 114.3 |
F3—C12—C13 | 119.9 (4) | C29—C28—C27 | 117.2 (4) |
F3—C12—C11 | 120.1 (5) | C29—C28—H28A | 108.0 |
C13—C12—C11 | 120.0 (4) | C27—C28—H28A | 108.0 |
F4—C13—C12 | 120.9 (5) | C29—C28—H28B | 108.0 |
F4—C13—C14 | 118.5 (5) | C27—C28—H28B | 108.0 |
C12—C13—C14 | 120.6 (4) | H28A—C28—H28B | 107.2 |
F5—C14—C13 | 119.1 (4) | C28—C29—C22 | 116.8 (4) |
F5—C14—C9 | 119.1 (4) | C28—C29—H29A | 108.1 |
C13—C14—C9 | 121.8 (4) | C22—C29—H29A | 108.1 |
N1—C15—C16 | 113.7 (3) | C28—C29—H29B | 108.1 |
N1—C15—H15A | 108.8 | C22—C29—H29B | 108.1 |
C16—C15—H15A | 108.8 | H29A—C29—H29B | 107.3 |
C7—N2—C1—N1 | −0.5 (4) | F6—C17—C18—C19 | 180.0 (4) |
C8—N2—C1—N1 | −177.4 (3) | C16—C17—C18—C19 | 1.2 (7) |
C7—N2—C1—Rh1 | −177.4 (2) | F6—C17—C18—F7 | −0.6 (7) |
C8—N2—C1—Rh1 | 5.7 (5) | C16—C17—C18—F7 | −179.4 (4) |
C2—N1—C1—N2 | 0.4 (3) | F7—C18—C19—F8 | −0.3 (7) |
C15—N1—C1—N2 | 177.0 (3) | C17—C18—C19—F8 | 179.1 (4) |
C2—N1—C1—Rh1 | 177.4 (2) | F7—C18—C19—C20 | 178.4 (4) |
C15—N1—C1—Rh1 | −6.1 (4) | C17—C18—C19—C20 | −2.2 (7) |
C22—Rh1—C1—N2 | 109.5 (3) | C18—C19—C20—F9 | −178.5 (4) |
C23—Rh1—C1—N2 | 71.1 (3) | F8—C19—C20—F9 | 0.2 (7) |
C26—Rh1—C1—N2 | 7.9 (6) | C18—C19—C20—C21 | 1.4 (7) |
C27—Rh1—C1—N2 | 173.3 (5) | F8—C19—C20—C21 | −179.9 (4) |
Br1—Rh1—C1—N2 | −90.6 (3) | C17—C16—C21—F10 | 178.4 (3) |
C22—Rh1—C1—N1 | −66.8 (3) | C15—C16—C21—F10 | −1.6 (5) |
C23—Rh1—C1—N1 | −105.2 (3) | C17—C16—C21—C20 | −1.4 (6) |
C26—Rh1—C1—N1 | −168.4 (4) | C15—C16—C21—C20 | 178.6 (3) |
C27—Rh1—C1—N1 | −3.0 (7) | F9—C20—C21—F10 | 0.6 (6) |
Br1—Rh1—C1—N1 | 93.2 (3) | C19—C20—C21—F10 | −179.3 (4) |
C1—N1—C2—C7 | −0.2 (4) | F9—C20—C21—C16 | −179.7 (4) |
C15—N1—C2—C7 | −176.8 (3) | C19—C20—C21—C16 | 0.4 (6) |
C1—N1—C2—C3 | 179.3 (3) | C1—Rh1—C22—C23 | −88.6 (2) |
C15—N1—C2—C3 | 2.7 (5) | C26—Rh1—C22—C23 | 71.9 (3) |
C7—C2—C3—C4 | 0.9 (5) | C27—Rh1—C22—C23 | 106.4 (3) |
N1—C2—C3—C4 | −178.4 (3) | Br1—Rh1—C22—C23 | 168.9 (2) |
C2—C3—C4—C5 | −1.3 (6) | C1—Rh1—C22—C29 | 150.2 (4) |
C3—C4—C5—C6 | 1.5 (6) | C23—Rh1—C22—C29 | −121.1 (5) |
C4—C5—C6—C7 | −1.0 (6) | C26—Rh1—C22—C29 | −49.2 (4) |
C3—C2—C7—C6 | −0.6 (5) | C27—Rh1—C22—C29 | −14.7 (4) |
N1—C2—C7—C6 | 178.9 (3) | Br1—Rh1—C22—C29 | 47.8 (6) |
C3—C2—C7—N2 | −179.6 (3) | C29—C22—C23—C24 | 0.9 (7) |
N1—C2—C7—N2 | −0.1 (4) | Rh1—C22—C23—C24 | −103.4 (4) |
C5—C6—C7—C2 | 0.6 (5) | C29—C22—C23—Rh1 | 104.3 (4) |
C5—C6—C7—N2 | 179.3 (4) | C1—Rh1—C23—C22 | 92.1 (2) |
C1—N2—C7—C2 | 0.4 (4) | C26—Rh1—C23—C22 | −105.8 (3) |
C8—N2—C7—C2 | 177.3 (3) | C27—Rh1—C23—C22 | −71.6 (3) |
C1—N2—C7—C6 | −178.5 (4) | Br1—Rh1—C23—C22 | −167.8 (3) |
C8—N2—C7—C6 | −1.6 (6) | C1—Rh1—C23—C24 | −145.7 (4) |
C1—N2—C8—C9 | 70.6 (4) | C22—Rh1—C23—C24 | 122.3 (5) |
C7—N2—C8—C9 | −105.9 (4) | C26—Rh1—C23—C24 | 16.5 (4) |
N2—C8—C9—C10 | 45.3 (5) | C27—Rh1—C23—C24 | 50.6 (4) |
N2—C8—C9—C14 | −134.5 (4) | Br1—Rh1—C23—C24 | −45.5 (6) |
C14—C9—C10—F1 | 179.2 (4) | C22—C23—C24—C25 | 64.8 (8) |
C8—C9—C10—F1 | −0.6 (6) | Rh1—C23—C24—C25 | −16.7 (8) |
C14—C9—C10—C11 | 0.9 (6) | C23—C24—C25—C26 | 4.4 (9) |
C8—C9—C10—C11 | −178.8 (4) | C24—C25—C26—C27 | −72.0 (7) |
F1—C10—C11—F2 | 0.4 (7) | C24—C25—C26—Rh1 | 9.4 (7) |
C9—C10—C11—F2 | 178.6 (4) | C1—Rh1—C26—C27 | 173.0 (4) |
F1—C10—C11—C12 | −178.7 (4) | C22—Rh1—C26—C27 | 71.5 (3) |
C9—C10—C11—C12 | −0.4 (7) | C23—Rh1—C26—C27 | 108.2 (3) |
F2—C11—C12—F3 | 1.9 (7) | Br1—Rh1—C26—C27 | −88.1 (3) |
C10—C11—C12—F3 | −179.1 (4) | C1—Rh1—C26—C25 | 50.7 (6) |
F2—C11—C12—C13 | −179.4 (4) | C22—Rh1—C26—C25 | −50.8 (4) |
C10—C11—C12—C13 | −0.3 (7) | C23—Rh1—C26—C25 | −14.1 (4) |
F3—C12—C13—F4 | −2.2 (7) | C27—Rh1—C26—C25 | −122.3 (5) |
C11—C12—C13—F4 | 179.0 (4) | Br1—Rh1—C26—C25 | 149.5 (3) |
F3—C12—C13—C14 | 179.2 (4) | C25—C26—C27—C28 | 0.0 (6) |
C11—C12—C13—C14 | 0.4 (7) | Rh1—C26—C27—C28 | −101.5 (4) |
F4—C13—C14—F5 | 0.8 (6) | C25—C26—C27—Rh1 | 101.4 (4) |
C12—C13—C14—F5 | 179.4 (4) | C1—Rh1—C27—C26 | −171.7 (4) |
F4—C13—C14—C9 | −178.5 (4) | C22—Rh1—C27—C26 | −106.5 (3) |
C12—C13—C14—C9 | 0.1 (7) | C23—Rh1—C27—C26 | −69.9 (3) |
C10—C9—C14—F5 | 180.0 (4) | Br1—Rh1—C27—C26 | 91.6 (3) |
C8—C9—C14—F5 | −0.3 (6) | C1—Rh1—C27—C28 | −50.4 (8) |
C10—C9—C14—C13 | −0.8 (6) | C22—Rh1—C27—C28 | 14.8 (4) |
C8—C9—C14—C13 | 179.0 (4) | C23—Rh1—C27—C28 | 51.4 (4) |
C1—N1—C15—C16 | −67.9 (4) | C26—Rh1—C27—C28 | 121.3 (5) |
C2—N1—C15—C16 | 108.3 (4) | Br1—Rh1—C27—C28 | −147.1 (4) |
N1—C15—C16—C21 | −45.2 (5) | C26—C27—C28—C29 | 68.3 (7) |
N1—C15—C16—C17 | 134.8 (3) | Rh1—C27—C28—C29 | −12.6 (7) |
C21—C16—C17—F6 | −178.2 (4) | C27—C28—C29—C22 | 0.7 (9) |
C15—C16—C17—F6 | 1.8 (5) | C23—C22—C29—C28 | −69.3 (7) |
C21—C16—C17—C18 | 0.6 (6) | Rh1—C22—C29—C28 | 12.5 (7) |
C15—C16—C17—C18 | −179.4 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C25—H25A···F1i | 0.97 | 2.44 | 3.397 (6) | 167 |
C3—H3···F8ii | 0.93 | 2.50 | 3.331 (5) | 148 |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [RhBr(C8H12)(C21H8N2F10)] |
Mr | 769.29 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 10.3441 (5), 21.4937 (10), 15.4717 (7) |
β (°) | 125.629 (3) |
V (Å3) | 2795.9 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.13 |
Crystal size (mm) | 0.52 × 0.42 × 0.36 |
Data collection | |
Diffractometer | Stoe IPDS-II diffractometer |
Absorption correction | Integration (X-RED32; Stoe & Cie, 2002) |
Tmin, Tmax | 0.288, 0.545 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 36192, 6179, 4843 |
Rint | 0.056 |
(sin θ/λ)max (Å−1) | 0.643 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.101, 1.05 |
No. of reflections | 6179 |
No. of parameters | 389 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.79 |
Computer programs: X-AREA (Stoe & Cie, 2002), X-AREA, X-RED32 (Stoe & Cie, 2002), SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and PLATON (Spek, 2003).
Rh1—C1 | 2.010 (3) | N1—C1 | 1.359 (4) |
Rh1—C22 | 2.116 (4) | N1—C2 | 1.392 (4) |
Rh1—C23 | 2.118 (4) | N1—C15 | 1.456 (4) |
Rh1—C26 | 2.222 (4) | N2—C1 | 1.359 (4) |
Rh1—C27 | 2.224 (4) | N2—C7 | 1.400 (4) |
Rh1—Br1 | 2.5090 (5) | N2—C8 | 1.464 (4) |
C1—Rh1—C22 | 91.62 (14) | C1—N2—C7 | 111.6 (3) |
C1—Rh1—C23 | 90.43 (14) | C1—N2—C8 | 124.2 (3) |
C22—Rh1—C23 | 38.38 (17) | C7—N2—C8 | 124.1 (3) |
C1—Rh1—C26 | 160.15 (16) | N2—C1—N1 | 104.5 (3) |
C1—Rh1—C27 | 163.35 (16) | N2—C1—Rh1 | 127.7 (2) |
C26—Rh1—C27 | 36.19 (17) | N1—C1—Rh1 | 127.8 (2) |
C1—N1—C2 | 111.6 (3) | N2—C8—C9 | 113.3 (3) |
C1—N1—C15 | 124.2 (3) | N1—C15—C16 | 113.7 (3) |
C2—N1—C15 | 124.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C25—H25A···F1i | 0.97 | 2.44 | 3.397 (6) | 167 |
C3—H3···F8ii | 0.93 | 2.50 | 3.331 (5) | 148 |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y, −z+1. |
N-Heterocyclic carbenes (NHCs) based on the imidazole ring system are a novel class of ligands in organometallic chemistry (Weskamp et al., 2000) which tend to coordinate very strongly to the metal centre. NHCs and their metal complexes continue to attract interest as components in homogeneous catalysis (Herrmann, 2002a). The isolation of the stable imidazolin-2-ylidene and the saturated imidazolidin-2-ylidene derivative sparked renewed interest in the chemistry of N-heterocyclic carbenes and their metal complexes (Hahn, 2006). Recently, transition metal complexes of NHCs have been the focus of considerable attention since they can act as catalysts or catalyst precursors in Rh-catalyzed hydroformylation (Chen et al., 2000), Ru-catalyzed olefin metathesis (Fürstner, 2000), cyclopropanation (Çetinkaya et al., 1997), furan synthesis (Küçükbay et al., 1996; Çetinkaya et al., 2002) and Pd-catalyzed Heck or Suzuki coupling (McGuinnes & Cavell, 2000; Weskamp et al., 1999). However, NHC complexes with fluorinated substituents are rare (Xu et al., 2000). We report here the preparation and characterization of a novel RhI complex, (II), bearing the fluorinated NHC ligand (Saunders & McGrandle, 2005).
Complex (II) has a slightly distorted pseudo-square-planar geometry (Fig. 1 and Table 1), if the mid-points of the two double bonds of the cycloocta-1,5-diene (COD) ligand are considered as coordination sites. The metal centre is coordinated to two alkene bonds of the COD ligand, to a non-substituted C atom of the benzimidazole ring and to the Br atom. The whole molecule has an approximate twofold symmetry on the mid-points of the C22═C23 and C26═ C27 bonds; when these mid-points are considered, it can be said that the complex has a cis arrangement. The angle between the carbene heterocycle and the coordination plane (Br1/mid-point C22═C23/mid-point C26═C27) is 88.29 (14)°. This value is somewhat lower than that reported by Herrmann (2002a) but significantly higher than that reported by Dinçer et al. (2006). The COD ring exhibits a boat conformation with the Rh—C(COD) distances ranging from 2.116 (4) to 2.224 (4) Å. The Rh1—C22 and Rh1—C23 bond distances are shorter than Rh1—C26 and Rh1—C27; this is not unexpected and is due to the trans influence of the chelating ligand. These results agree with the values in the literature (Ingleson et al., 2001; Vicente et al., 2001).
Comparing the average Rh—C(COD) bond length of 2.17 (2) Å and the Rh—C(benzimidazole) bond length of 2.010 (3) Å with literature values, it is observed that Rh—C(COD) increases with decreasing Rh—C(benzimidazole) distance [2.167 (4) and 2.016 (4) Å (Baker et al., 2004); 2.161 (2) and 2.018 (2) Å (Hahn et al., 2004); 2.143 (3) and 2.059 (3) Å (Duan et al., 2003)]. The C═C bond lengths of the cyclooctadiene ligand differ in that the double bond trans to the carbene ligand [C26═C27 = 1.381 (6) Å] is shorter than the C═C bond trans to the bromo ligand [C22═C23 = 1.392 (6) Å]. However, these distances fall in the expected range for coordinated olefins (Cambridge Structural Database, Version 5.28; CONQUEST, Version 1.9; Allen, 2002).
The benzimidazole ring is planar, with a maximum deviation from the plane of -0.012 (2) Å for atom C1, and makes dihedral angles of 88.69 (9) and 88.98 (12)° with the C9–C14 and C16–C21 pentafluorophenyl ring planes, respectively, indicating that two pentafluorophenyl rings are almost perpendicular with respect to the benzimidazole ring. The metal–carbon bond distance between the Rh atom and the NHC ligand is in good agreement with those of other rhodium NHC complexes (Günay et al., 2006; Dinçer et al., 2005, 2006). The N1—C1 and N2—C1 bond distances are both 1.359 (4) Å. These are significantly shorter than the other N—C(carbene) bond distances in (II) (Table 1). The shorter N—C(carbene) bonds are indicative of a greater multiple-bond character due to partial electron donation by the N atom to the carbene C-atom donor (Herrmann, 2002b; Fröhlich et al., 1997). Theoretical studies also indicate that the stability of these carbenes is due to electron donation from the N-atom lone pairs into the formally empty p(π) orbital on the carbene C atom (Heinemann et al., 1996; Böhme & Frenking, 1996). For this reason, the N1—C1 and N2—C1 bonds are shortened. It is observed that the steric effect of the pentafluorophenyl rings on the Br—Rh—C(carbene) angle and Rh—Br bond results in increased angle [92.82 (9)°] and shortened bond [2.5090 (5) Å] values relative to those in similar compounds (Günay et al., 2006; Dinçer et al., 2005; Herrmann, 2002b; Danopoulos et al., 2002).
In the crystal structure (Fig. 2), molecules of the title compound are packed in columns running along the a axis. The molecules in each column are linked to one another in a zigzag arrangement via C25—H25A···F1i hydrogen bonds (geometric parameters and symmetry codes for hydrogen bonds are given in Table 2), resulting in the formation of molecular chains along the a axis. In addition, there are π–π stacking and C3—H3···F8ii interactions between the molecules in inversion-related columns. In these weak π–π interactions, the C16–C21 pentafluorophenyl ring in the molecule at (x, y, z) stacks above the ring at (1 - x, -y, 1 - z), with a distance of 3.956 (8) Å between the ring centroids, and a perpendicular distance of 3.402 (8) Å between the rings. Inversion-related columns are connected to similar neighboring columns by means of another weak π–π interaction. In these π–π interactions, the C2–C7 benzimidazole ring in the molecule at (x, y, z) stacks above the ring at (2 - x, -y, 2 - z), with a distance of 3.924 (8) Å between the ring centroids, and a perpendicular distance of 3.537 (8) Å between the rings. There are no other significant intermolecular interactions, such as C—H···π interactions, in the crystal structure of (II).