Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801011242/ya6042sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801011242/ya6042Isup2.hkl |
CCDC reference: 170906
A mixture of pentafluorophenyl (2R*,3S*)-3-bromo-2-chloro-3-phenylpropanoate (3.0 g, 8.0 mmol) and tri-n-butyltin hydride (4.1 g, 13.8 mmol) in benzene (5 ml) was stirred at room temperature with irradiation from a 160 W mercury gas discharge lamp for 2 h. The reaction mixture was treated with small amounts of iodine until the brown colour of iodine persisted. Aqueous KF (1 M, 10 ml) was added to the mixture and the resulting mixture stirred for 2 h. The precipitate formed was removed by filtration and the mixture evaporated under reduced pressure. The residue was purified by column chromatography on silica gel (Sorbsil, particle size 32–63 mm) eluting with CH2Cl2. The crude product was recrystallized from hexane to give compound (I) as white crystals, in 53% yield.
Data collection: SHELXTL-Plus (Sheldrick, 1990); cell refinement: SHELXTL-Plus; data reduction: SHELXTL-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: WinGX (Farrugia, 1999); software used to prepare material for publication: WinGX.
Fig. 1. The structure of (I) with displacement ellipsoids drawn at the 50% probability level (Farrugia, 1999). |
C15H8ClF5O2 | F(000) = 704 |
Mr = 350.66 | Dx = 1.646 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
a = 15.208 (5) Å | Cell parameters from 2268 reflections |
b = 8.131 (5) Å | θ = 2.9–26.4° |
c = 12.302 (5) Å | µ = 0.33 mm−1 |
β = 111.554 (5)° | T = 163 K |
V = 1414.8 (11) Å3 | Rectangular, colourless |
Z = 4 | 0.68 × 0.32 × 0.29 mm |
CCD area detector diffractometer | Rint = 0.032 |
Graphite monochromator | θmax = 26.4°, θmin = 2.9° |
ϕ and ω scans | h = −18→18 |
10557 measured reflections | k = −10→3 |
2880 independent reflections | l = −14→15 |
2268 reflections with I > 2σ(I) |
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)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.092 | w = 1/[σ2(Fo2) + (0.0563P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
2880 reflections | Δρmax = 0.27 e Å−3 |
209 parameters | Δρmin = −0.31 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: 0.0040 (12) |
C15H8ClF5O2 | V = 1414.8 (11) Å3 |
Mr = 350.66 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.208 (5) Å | µ = 0.33 mm−1 |
b = 8.131 (5) Å | T = 163 K |
c = 12.302 (5) Å | 0.68 × 0.32 × 0.29 mm |
β = 111.554 (5)° |
CCD area detector diffractometer | 2268 reflections with I > 2σ(I) |
10557 measured reflections | Rint = 0.032 |
2880 independent reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.092 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.27 e Å−3 |
2880 reflections | Δρmin = −0.31 e Å−3 |
209 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 | ||
C1 | 0.43608 (11) | 0.05280 (16) | 0.70762 (13) | 0.0239 (3) | |
C2 | 0.54087 (10) | 0.08084 (17) | 0.75862 (13) | 0.0247 (3) | |
H2A | 0.5552 | 0.1886 | 0.7356 | 0.03* | |
H2B | 0.5723 | −0.0007 | 0.7281 | 0.03* | |
C3 | 0.57804 (10) | 0.06962 (17) | 0.89136 (13) | 0.0241 (3) | |
H3 | 0.557 | −0.0357 | 0.9121 | 0.029* | |
C4 | 0.68378 (11) | 0.07951 (17) | 0.95381 (13) | 0.0256 (3) | |
C5 | 0.72310 (12) | 0.0171 (2) | 1.06733 (15) | 0.0356 (4) | |
H5 | 0.6837 | −0.0283 | 1.1021 | 0.043* | |
C6 | 0.81951 (13) | 0.0217 (2) | 1.12876 (17) | 0.0449 (5) | |
H6 | 0.8446 | −0.0195 | 1.2045 | 0.054* | |
C7 | 0.87902 (12) | 0.0880 (2) | 1.07737 (16) | 0.0417 (5) | |
H7 | 0.944 | 0.0905 | 1.1185 | 0.05* | |
C8 | 0.84169 (12) | 0.1502 (2) | 0.96501 (16) | 0.0385 (4) | |
H8 | 0.8815 | 0.1946 | 0.9306 | 0.046* | |
C9 | 0.74388 (11) | 0.14637 (18) | 0.90300 (15) | 0.0308 (4) | |
H9 | 0.7189 | 0.1887 | 0.8275 | 0.037* | |
C10 | 0.29696 (11) | 0.12652 (17) | 0.55208 (14) | 0.0269 (4) | |
C11 | 0.23551 (12) | 0.18826 (18) | 0.60242 (14) | 0.0298 (4) | |
C12 | 0.13937 (12) | 0.1774 (2) | 0.54528 (16) | 0.0353 (4) | |
C13 | 0.10237 (12) | 0.1040 (2) | 0.43607 (16) | 0.0380 (4) | |
C14 | 0.16257 (13) | 0.0419 (2) | 0.38518 (15) | 0.0350 (4) | |
C15 | 0.25926 (12) | 0.05328 (19) | 0.44300 (14) | 0.0307 (4) | |
O1 | 0.39439 (7) | 0.14471 (12) | 0.60654 (10) | 0.0290 (3) | |
O2 | 0.39062 (7) | −0.03588 (12) | 0.74472 (9) | 0.0273 (3) | |
F11 | 0.27093 (7) | 0.26040 (10) | 0.70775 (9) | 0.0382 (3) | |
F12 | 0.08048 (8) | 0.23830 (13) | 0.59452 (10) | 0.0520 (3) | |
F13 | 0.00832 (7) | 0.09494 (15) | 0.37997 (10) | 0.0586 (3) | |
F14 | 0.12633 (8) | −0.02894 (14) | 0.27917 (9) | 0.0526 (3) | |
F15 | 0.31730 (7) | −0.00680 (12) | 0.39241 (9) | 0.0420 (3) | |
Cl1 | 0.52148 (3) | 0.23514 (4) | 0.94522 (3) | 0.02914 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0284 (9) | 0.0200 (6) | 0.0228 (8) | 0.0019 (6) | 0.0088 (7) | −0.0026 (6) |
C2 | 0.0244 (9) | 0.0234 (7) | 0.0270 (9) | −0.0011 (6) | 0.0104 (7) | −0.0031 (6) |
C3 | 0.0256 (9) | 0.0198 (6) | 0.0275 (9) | 0.0007 (6) | 0.0105 (7) | −0.0010 (6) |
C4 | 0.0249 (9) | 0.0236 (7) | 0.0269 (9) | 0.0000 (6) | 0.0078 (7) | −0.0031 (6) |
C5 | 0.0314 (11) | 0.0456 (9) | 0.0293 (10) | −0.0028 (7) | 0.0105 (8) | 0.0037 (7) |
C6 | 0.0368 (12) | 0.0616 (11) | 0.0286 (10) | −0.0030 (9) | 0.0031 (9) | 0.0063 (8) |
C7 | 0.0230 (10) | 0.0543 (11) | 0.0393 (11) | −0.0048 (8) | 0.0017 (8) | −0.0013 (8) |
C8 | 0.0265 (10) | 0.0458 (10) | 0.0433 (11) | −0.0072 (7) | 0.0129 (9) | −0.0016 (8) |
C9 | 0.0264 (10) | 0.0341 (8) | 0.0304 (9) | −0.0009 (7) | 0.0086 (7) | 0.0024 (7) |
C10 | 0.0238 (9) | 0.0275 (7) | 0.0275 (9) | 0.0008 (6) | 0.0074 (7) | 0.0050 (6) |
C11 | 0.0323 (10) | 0.0283 (7) | 0.0264 (9) | 0.0004 (7) | 0.0081 (8) | 0.0006 (6) |
C12 | 0.0274 (10) | 0.0417 (9) | 0.0376 (10) | 0.0068 (7) | 0.0130 (8) | 0.0039 (8) |
C13 | 0.0232 (10) | 0.0471 (9) | 0.0367 (11) | 0.0005 (7) | 0.0027 (8) | 0.0054 (8) |
C14 | 0.0360 (11) | 0.0377 (9) | 0.0242 (9) | 0.0005 (7) | 0.0024 (8) | 0.0010 (7) |
C15 | 0.0350 (10) | 0.0316 (8) | 0.0261 (9) | 0.0061 (7) | 0.0120 (8) | 0.0062 (6) |
O1 | 0.0235 (6) | 0.0320 (5) | 0.0294 (6) | −0.0021 (4) | 0.0072 (5) | 0.0069 (4) |
O2 | 0.0263 (6) | 0.0254 (5) | 0.0302 (6) | −0.0026 (4) | 0.0105 (5) | 0.0022 (4) |
F11 | 0.0401 (6) | 0.0397 (5) | 0.0325 (6) | 0.0018 (4) | 0.0108 (5) | −0.0074 (4) |
F12 | 0.0340 (7) | 0.0701 (7) | 0.0547 (8) | 0.0127 (5) | 0.0198 (6) | −0.0032 (6) |
F13 | 0.0253 (6) | 0.0824 (8) | 0.0547 (8) | 0.0007 (5) | −0.0013 (5) | −0.0021 (6) |
F14 | 0.0527 (8) | 0.0628 (7) | 0.0293 (6) | 0.0014 (5) | −0.0002 (5) | −0.0085 (5) |
F15 | 0.0441 (7) | 0.0522 (6) | 0.0312 (6) | 0.0125 (5) | 0.0156 (5) | 0.0020 (4) |
Cl1 | 0.0319 (3) | 0.0284 (2) | 0.0294 (2) | 0.00291 (15) | 0.01393 (18) | −0.00220 (15) |
C1—O1 | 1.3884 (18) | C10—C11 | 1.391 (2) |
C1—O2 | 1.1992 (17) | C10—C15 | 1.385 (2) |
C1—C2 | 1.500 (2) | C10—O1 | 1.3917 (19) |
C2—C3 | 1.522 (2) | C11—C12 | 1.373 (2) |
C3—C4 | 1.508 (2) | C11—F11 | 1.3419 (19) |
C3—Cl1 | 1.8463 (16) | C12—C13 | 1.387 (3) |
C4—C5 | 1.397 (2) | C12—F12 | 1.346 (2) |
C4—C9 | 1.393 (2) | C13—C14 | 1.381 (3) |
C5—C6 | 1.381 (2) | C13—F13 | 1.342 (2) |
C6—C7 | 1.389 (2) | C14—C15 | 1.381 (2) |
C7—C8 | 1.383 (3) | C14—F14 | 1.3448 (19) |
C8—C9 | 1.401 (2) | C15—F15 | 1.3448 (18) |
O2—C1—O1 | 121.81 (14) | C11—C12—C13 | 120.03 (15) |
O2—C1—C2 | 127.20 (14) | C12—C11—C10 | 120.82 (15) |
O1—C1—C2 | 110.99 (12) | C13—C14—C15 | 119.99 (16) |
C1—C2—C3 | 111.00 (12) | C14—C13—C12 | 119.75 (16) |
C1—O1—C10 | 115.41 (11) | C14—C15—C10 | 120.73 (15) |
C2—C3—Cl1 | 107.64 (10) | C15—C10—C11 | 118.68 (15) |
C4—C3—C2 | 116.72 (13) | C15—C10—O1 | 120.04 (14) |
C4—C3—Cl1 | 109.17 (10) | F11—C11—C10 | 119.39 (14) |
C4—C9—C8 | 120.31 (16) | F11—C11—C12 | 119.78 (15) |
C5—C4—C3 | 118.32 (14) | F12—C12—C11 | 120.37 (16) |
C5—C6—C7 | 119.98 (17) | F12—C12—C13 | 119.60 (16) |
C6—C5—C4 | 121.02 (16) | F13—C13—C12 | 119.89 (16) |
C7—C8—C9 | 120.01 (16) | F13—C13—C14 | 120.36 (16) |
C8—C7—C6 | 120.00 (17) | F14—C14—C13 | 119.51 (16) |
C9—C4—C3 | 123.00 (14) | F14—C14—C15 | 120.50 (15) |
C9—C4—C5 | 118.67 (15) | F15—C15—C10 | 119.74 (15) |
C11—C10—O1 | 121.20 (14) | F15—C15—C14 | 119.53 (15) |
Experimental details
Crystal data | |
Chemical formula | C15H8ClF5O2 |
Mr | 350.66 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 163 |
a, b, c (Å) | 15.208 (5), 8.131 (5), 12.302 (5) |
β (°) | 111.554 (5) |
V (Å3) | 1414.8 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.33 |
Crystal size (mm) | 0.68 × 0.32 × 0.29 |
Data collection | |
Diffractometer | CCD area detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10557, 2880, 2268 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.626 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.092, 1.06 |
No. of reflections | 2880 |
No. of parameters | 209 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.31 |
Computer programs: SHELXTL-Plus (Sheldrick, 1990), SHELXTL-Plus, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), WinGX (Farrugia, 1999), WinGX.
C1—O1 | 1.3884 (18) | C3—C4 | 1.508 (2) |
C1—O2 | 1.1992 (17) | C3—Cl1 | 1.8463 (16) |
C1—C2 | 1.500 (2) | C10—O1 | 1.3917 (19) |
C2—C3 | 1.522 (2) | ||
O2—C1—O1 | 121.81 (14) | C1—O1—C10 | 115.41 (11) |
O2—C1—C2 | 127.20 (14) | C2—C3—Cl1 | 107.64 (10) |
O1—C1—C2 | 110.99 (12) | C4—C3—C2 | 116.72 (13) |
C1—C2—C3 | 111.00 (12) | C4—C3—Cl1 | 109.17 (10) |
The title compound, (I), was investigated as part of a study into an unusual 1,2-chlorine migration that occurs in 2-chlorohydrocinnamate derivatives (Tan et al., 2001). Compound (I) is only the second example of a crystallographically characterized pentafluorophenyl ester, the first being the related compound N-tert-butyloxycarbonylphenylalanine pentafluorophenyl ester, (II) (Czugler et al., 1976).
The structure confirms the identity of (I) (Fig. 1) and shows that the Cl atom has migrated from C-2 in the reactant to C-3 in the product. In contrast to (II), where the phenyl and pentafluorophenyl rings are essentially coplanar, the angle between the planes in (I) defined by the phenyl [maximum deviation from its mean plane is 0.0027 (19) Å] and pentafluorophenyl [maximum deviation 0.0008 (15) Å] rings is 53.3 (1)°. The molecules pack as dimers in a `head-to-tail' fashion, such that there are significant π–π interactions between the phenyl and pentafluorophenyl rings within each dimer, the distances between the ring centroids being 3.826 (3) Å. There is also a short intermolecular distance of 2.368 (2) Å between O2 and the H2Ai atom of an adjacent molecule [symmetry code: (i) 1 - x, y - 0.5, 1.5 - z].