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The structural analysis of the title compound, C15H8ClF5O2, confirms the position of the Cl atom at C-3.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801011242/ya6042sup1.cif
Contains datablocks bchn_s, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801011242/ya6042Isup2.hkl
Contains datablock I

CCDC reference: 170906

Key indicators

  • Single-crystal X-ray study
  • T = 163 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.033
  • wR factor = 0.092
  • Data-to-parameter ratio = 13.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

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 ππ 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].

Experimental top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The structure of (I) with displacement ellipsoids drawn at the 50% probability level (Farrugia, 1999).
Pentafluorophenyl 3-chloro-3-phenylpropanoate top
Crystal data top
C15H8ClF5O2F(000) = 704
Mr = 350.66Dx = 1.646 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71069 Å
a = 15.208 (5) ÅCell parameters from 2268 reflections
b = 8.131 (5) Åθ = 2.9–26.4°
c = 12.302 (5) ŵ = 0.33 mm1
β = 111.554 (5)°T = 163 K
V = 1414.8 (11) Å3Rectangular, colourless
Z = 40.68 × 0.32 × 0.29 mm
Data collection top
CCD area detector
diffractometer
Rint = 0.032
Graphite monochromatorθmax = 26.4°, θmin = 2.9°
ϕ and ω scansh = 1818
10557 measured reflectionsk = 103
2880 independent reflectionsl = 1415
2268 reflections with I > 2σ(I)
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.033H-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 reflectionsΔρmax = 0.27 e Å3
209 parametersΔρmin = 0.31 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0040 (12)
Crystal data top
C15H8ClF5O2V = 1414.8 (11) Å3
Mr = 350.66Z = 4
Monoclinic, P21/cMo Kα radiation
a = 15.208 (5) ŵ = 0.33 mm1
b = 8.131 (5) ÅT = 163 K
c = 12.302 (5) Å0.68 × 0.32 × 0.29 mm
β = 111.554 (5)°
Data collection top
CCD area detector
diffractometer
2268 reflections with I > 2σ(I)
10557 measured reflectionsRint = 0.032
2880 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.092H-atom parameters constrained
S = 1.06Δρmax = 0.27 e Å3
2880 reflectionsΔρmin = 0.31 e Å3
209 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.43608 (11)0.05280 (16)0.70762 (13)0.0239 (3)
C20.54087 (10)0.08084 (17)0.75862 (13)0.0247 (3)
H2A0.55520.18860.73560.03*
H2B0.57230.00070.72810.03*
C30.57804 (10)0.06962 (17)0.89136 (13)0.0241 (3)
H30.5570.03570.91210.029*
C40.68378 (11)0.07951 (17)0.95381 (13)0.0256 (3)
C50.72310 (12)0.0171 (2)1.06733 (15)0.0356 (4)
H50.68370.02831.10210.043*
C60.81951 (13)0.0217 (2)1.12876 (17)0.0449 (5)
H60.84460.01951.20450.054*
C70.87902 (12)0.0880 (2)1.07737 (16)0.0417 (5)
H70.9440.09051.11850.05*
C80.84169 (12)0.1502 (2)0.96501 (16)0.0385 (4)
H80.88150.19460.93060.046*
C90.74388 (11)0.14637 (18)0.90300 (15)0.0308 (4)
H90.71890.18870.82750.037*
C100.29696 (11)0.12652 (17)0.55208 (14)0.0269 (4)
C110.23551 (12)0.18826 (18)0.60242 (14)0.0298 (4)
C120.13937 (12)0.1774 (2)0.54528 (16)0.0353 (4)
C130.10237 (12)0.1040 (2)0.43607 (16)0.0380 (4)
C140.16257 (13)0.0419 (2)0.38518 (15)0.0350 (4)
C150.25926 (12)0.05328 (19)0.44300 (14)0.0307 (4)
O10.39439 (7)0.14471 (12)0.60654 (10)0.0290 (3)
O20.39062 (7)0.03588 (12)0.74472 (9)0.0273 (3)
F110.27093 (7)0.26040 (10)0.70775 (9)0.0382 (3)
F120.08048 (8)0.23830 (13)0.59452 (10)0.0520 (3)
F130.00832 (7)0.09494 (15)0.37997 (10)0.0586 (3)
F140.12633 (8)0.02894 (14)0.27917 (9)0.0526 (3)
F150.31730 (7)0.00680 (12)0.39241 (9)0.0420 (3)
Cl10.52148 (3)0.23514 (4)0.94522 (3)0.02914 (14)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0284 (9)0.0200 (6)0.0228 (8)0.0019 (6)0.0088 (7)0.0026 (6)
C20.0244 (9)0.0234 (7)0.0270 (9)0.0011 (6)0.0104 (7)0.0031 (6)
C30.0256 (9)0.0198 (6)0.0275 (9)0.0007 (6)0.0105 (7)0.0010 (6)
C40.0249 (9)0.0236 (7)0.0269 (9)0.0000 (6)0.0078 (7)0.0031 (6)
C50.0314 (11)0.0456 (9)0.0293 (10)0.0028 (7)0.0105 (8)0.0037 (7)
C60.0368 (12)0.0616 (11)0.0286 (10)0.0030 (9)0.0031 (9)0.0063 (8)
C70.0230 (10)0.0543 (11)0.0393 (11)0.0048 (8)0.0017 (8)0.0013 (8)
C80.0265 (10)0.0458 (10)0.0433 (11)0.0072 (7)0.0129 (9)0.0016 (8)
C90.0264 (10)0.0341 (8)0.0304 (9)0.0009 (7)0.0086 (7)0.0024 (7)
C100.0238 (9)0.0275 (7)0.0275 (9)0.0008 (6)0.0074 (7)0.0050 (6)
C110.0323 (10)0.0283 (7)0.0264 (9)0.0004 (7)0.0081 (8)0.0006 (6)
C120.0274 (10)0.0417 (9)0.0376 (10)0.0068 (7)0.0130 (8)0.0039 (8)
C130.0232 (10)0.0471 (9)0.0367 (11)0.0005 (7)0.0027 (8)0.0054 (8)
C140.0360 (11)0.0377 (9)0.0242 (9)0.0005 (7)0.0024 (8)0.0010 (7)
C150.0350 (10)0.0316 (8)0.0261 (9)0.0061 (7)0.0120 (8)0.0062 (6)
O10.0235 (6)0.0320 (5)0.0294 (6)0.0021 (4)0.0072 (5)0.0069 (4)
O20.0263 (6)0.0254 (5)0.0302 (6)0.0026 (4)0.0105 (5)0.0022 (4)
F110.0401 (6)0.0397 (5)0.0325 (6)0.0018 (4)0.0108 (5)0.0074 (4)
F120.0340 (7)0.0701 (7)0.0547 (8)0.0127 (5)0.0198 (6)0.0032 (6)
F130.0253 (6)0.0824 (8)0.0547 (8)0.0007 (5)0.0013 (5)0.0021 (6)
F140.0527 (8)0.0628 (7)0.0293 (6)0.0014 (5)0.0002 (5)0.0085 (5)
F150.0441 (7)0.0522 (6)0.0312 (6)0.0125 (5)0.0156 (5)0.0020 (4)
Cl10.0319 (3)0.0284 (2)0.0294 (2)0.00291 (15)0.01393 (18)0.00220 (15)
Geometric parameters (Å, º) top
C1—O11.3884 (18)C10—C111.391 (2)
C1—O21.1992 (17)C10—C151.385 (2)
C1—C21.500 (2)C10—O11.3917 (19)
C2—C31.522 (2)C11—C121.373 (2)
C3—C41.508 (2)C11—F111.3419 (19)
C3—Cl11.8463 (16)C12—C131.387 (3)
C4—C51.397 (2)C12—F121.346 (2)
C4—C91.393 (2)C13—C141.381 (3)
C5—C61.381 (2)C13—F131.342 (2)
C6—C71.389 (2)C14—C151.381 (2)
C7—C81.383 (3)C14—F141.3448 (19)
C8—C91.401 (2)C15—F151.3448 (18)
O2—C1—O1121.81 (14)C11—C12—C13120.03 (15)
O2—C1—C2127.20 (14)C12—C11—C10120.82 (15)
O1—C1—C2110.99 (12)C13—C14—C15119.99 (16)
C1—C2—C3111.00 (12)C14—C13—C12119.75 (16)
C1—O1—C10115.41 (11)C14—C15—C10120.73 (15)
C2—C3—Cl1107.64 (10)C15—C10—C11118.68 (15)
C4—C3—C2116.72 (13)C15—C10—O1120.04 (14)
C4—C3—Cl1109.17 (10)F11—C11—C10119.39 (14)
C4—C9—C8120.31 (16)F11—C11—C12119.78 (15)
C5—C4—C3118.32 (14)F12—C12—C11120.37 (16)
C5—C6—C7119.98 (17)F12—C12—C13119.60 (16)
C6—C5—C4121.02 (16)F13—C13—C12119.89 (16)
C7—C8—C9120.01 (16)F13—C13—C14120.36 (16)
C8—C7—C6120.00 (17)F14—C14—C13119.51 (16)
C9—C4—C3123.00 (14)F14—C14—C15120.50 (15)
C9—C4—C5118.67 (15)F15—C15—C10119.74 (15)
C11—C10—O1121.20 (14)F15—C15—C14119.53 (15)

Experimental details

Crystal data
Chemical formulaC15H8ClF5O2
Mr350.66
Crystal system, space groupMonoclinic, P21/c
Temperature (K)163
a, b, c (Å)15.208 (5), 8.131 (5), 12.302 (5)
β (°) 111.554 (5)
V3)1414.8 (11)
Z4
Radiation typeMo Kα
µ (mm1)0.33
Crystal size (mm)0.68 × 0.32 × 0.29
Data collection
DiffractometerCCD area detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
10557, 2880, 2268
Rint0.032
(sin θ/λ)max1)0.626
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.092, 1.06
No. of reflections2880
No. of parameters209
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.27, 0.31

Computer programs: SHELXTL-Plus (Sheldrick, 1990), SHELXTL-Plus, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), WinGX (Farrugia, 1999), WinGX.

Selected geometric parameters (Å, º) top
C1—O11.3884 (18)C3—C41.508 (2)
C1—O21.1992 (17)C3—Cl11.8463 (16)
C1—C21.500 (2)C10—O11.3917 (19)
C2—C31.522 (2)
O2—C1—O1121.81 (14)C1—O1—C10115.41 (11)
O2—C1—C2127.20 (14)C2—C3—Cl1107.64 (10)
O1—C1—C2110.99 (12)C4—C3—C2116.72 (13)
C1—C2—C3111.00 (12)C4—C3—Cl1109.17 (10)
 

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