Penta­fluoro­phenyl 3-phenyl­prop-2-enoate

In the title compound, C₁₅H₇F₅O₂, an intra­molecular C—H...O hydrogen bond induces coplanarity of the central chain and the phenyl ring. An inter­molecular C—H...O hydrogen bond leads to the formation of a dimer.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.045
• wR factor = 0.134
• Data-to-parameter ratio = 12.3

checkCIF/PLATON results

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Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    F1     -   C11     ..       7.06 su

Alert level C
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         44 Perc.
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          5

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

As part of a study of cinnamic acid reactivity towards pentafluorophenol versus pentafluorothiophenol, the title compound, (I), has been synthesized according to a literature method (Zhao et al.,1997). The regular geometry of the carbon skeleton of the phenyl ring (C4–C9) is slightly modified due to the substituent atom C3 (Fig. 1). The deformation can be attributed to hybridization and conjugation effects (Domenicano et al., 1975) and can be described in the following way: an endocyclic angle α [C5—C4—C9 118.4 (3)°] smaller than 120°, aromatic bonds adjacent to atom C4 [average of C4—C5 and C4—C9 1.386 (1) Å] longer than the neighboring ones [average of C5—C6 and C8—C9 1.380 (1) Å] and a significant shortening of the C3—C4 bond [1.459 (4) Å] compared to the reported C_aromatic—Csp² average value of 1.483 Å (Allen et al., 1987).

In the pentafluorophenyl group, the average C_aromatic —C_aromatic and C_aromatic —F bond lengths agree very well with reported values (Allen et al., 1987), although there are significant differences among the several equivalent bonds (Table 1). These are probably due to significant librational motion of the pentafluorophenyl group, as shown by the shape of the displacement ellipsoids. Within the central chain, the C1═O2 and C2═C3 distances agree well with expected values; however, the C1—C2 [1.454 (4) Å] and C10—O1 [1.376 (4) Å] bonds are significantly shorter, and the C1—O1 [1.382 (4) Å] bond is significantly larger than reported values (Allen et al., 1987). All of these observed differences can be ascribed to the resonance effects of the two terminal aryl rings and the C2═C3 double bond.

The molecule is characterized by an intramolecular C3—H3···O2 hydrogen bond (Table 2), which is responsible for the planarity of the plane C1–C10/O1/O2 including the central chain and the phenyl ring (maximum deviation 0.084 Å). The dihedral angle between this plane and theO1/C10–C15/F1–F5 plane (maximum deviation 0.0136 Å) is 62.89 (6)°. The crystal packing is stabilized by a weak intermolecular C3—H3···O2ⁱ hydrogen bond (symmetry code as Table 2), which leads to the formation of a centrosymmetric dimer.

S2. Experimental

The title compound was prepared according to the method reported by Zhao et al. (1997), treating 3-phenyl-2-propenoic acid with dicyclohexylcarbodiimide (DCC) and pentafluorophenol in anhydrous dioxane. The mixture was stirred at room temperature for 30 min and cooled. Then dicyclohexylurea was removed by filtration and the filtrate was purified by silica gel flash column chromatography (diethyl ether-petroleum ether 1:9), to provide the title compound as a crystalline product. Suitable crystals for X-ray diffraction were obtained from slow evaporation of a diethylether solution.

S3. Refinement

H atoms were refined as riding on their parent atoms, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C). The linear decay of the intensity with exposure time appears to be related to the crystal and not to the source.

Computing details

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software; data reduction: HELENA (Spek,1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson,1976); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. Molecular structure of (I). Displacement ellipsoids are drawn at the 50% probability level.

Pentafluorophenyl 3-phenylprop-2-enoate

Crystal data

C15H7F5O2	F(000) = 632
Mr = 314.21	Dx = 1.564 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 7.261 (5) Å	θ = 7.4–12.5°
b = 15.1156 (17) Å	µ = 0.15 mm^−1
c = 12.3823 (15) Å	T = 293 K
β = 101.01 (2)°	Prism, colourless
V = 1334.0 (9) Å^3	0.49 × 0.18 × 0.12 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.025
Radiation source: fine-focus sealed tube	θmax = 25.5°, θmin = 2.7°
Graphite monochromator	h = −4→8
ω–2θ scans	k = −8→18
3210 measured reflections	l = −14→14
2463 independent reflections	3 standard reflections every 200 reflections
1086 reflections with I > 2σ(I)	intensity decay: 10.6%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.045	H-atom parameters constrained
wR(F^2) = 0.134	w = 1/[σ^2(Fo^2) + (0.0424P)^2 + 0.684P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.003
2463 reflections	Δρmax = 0.24 e Å^−3
200 parameters	Δρmin = −0.23 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0144 (19)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O2	0.9933 (3)	0.92412 (16)	0.88055 (18)	0.0725 (7)
O1	0.8168 (3)	0.83009 (15)	0.76496 (18)	0.0709 (7)
C4	0.5828 (4)	0.9144 (2)	1.0904 (2)	0.0522 (8)
C3	0.7180 (4)	0.91439 (19)	1.0171 (2)	0.0522 (8)
H3	0.8260	0.9478	1.0398	0.063*
C2	0.7054 (4)	0.8726 (2)	0.9223 (2)	0.0574 (8)
H2	0.6011	0.8376	0.8958	0.069*
C1	0.8541 (5)	0.8811 (2)	0.8592 (3)	0.0567 (8)
C10	0.9514 (5)	0.8319 (2)	0.7005 (3)	0.0657 (9)
F1	1.1644 (3)	0.75371 (15)	0.83151 (19)	0.0959 (7)
C9	0.4050 (4)	0.8781 (2)	1.0607 (3)	0.0609 (9)
H9	0.3682	0.8530	0.9913	0.073*
C12	1.2545 (6)	0.7929 (3)	0.6655 (4)	0.0865 (13)
C8	0.2824 (5)	0.8788 (2)	1.1330 (3)	0.0768 (11)
H8	0.1637	0.8539	1.1124	0.092*
F3	1.3388 (4)	0.83172 (19)	0.4998 (2)	0.1425 (12)
C7	0.3344 (6)	0.9159 (3)	1.2352 (3)	0.0875 (13)
H7	0.2517	0.9157	1.2841	0.105*
F5	0.7467 (4)	0.91053 (17)	0.56455 (18)	0.1095 (8)
C11	1.1218 (6)	0.7933 (3)	0.7324 (3)	0.0741 (10)
C5	0.6327 (5)	0.9526 (2)	1.1936 (3)	0.0701 (10)
H5	0.7507	0.9780	1.2147	0.084*
C15	0.9116 (6)	0.8717 (3)	0.5989 (3)	0.0771 (11)
C13	1.2088 (7)	0.8321 (3)	0.5646 (4)	0.0942 (15)
C6	0.5088 (7)	0.9533 (3)	1.2654 (3)	0.0884 (12)
H6	0.5437	0.9791	1.3345	0.106*
F2	1.4184 (3)	0.7530 (2)	0.7001 (2)	0.1312 (11)
F4	0.9995 (4)	0.90947 (19)	0.4311 (2)	0.1363 (11)
C14	1.0410 (7)	0.8709 (3)	0.5305 (3)	0.0909 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O2	0.0621 (15)	0.0817 (17)	0.0813 (16)	−0.0234 (13)	0.0329 (12)	−0.0316 (13)
O1	0.0610 (15)	0.0868 (17)	0.0732 (15)	−0.0240 (12)	0.0336 (12)	−0.0304 (13)
C4	0.051 (2)	0.053 (2)	0.055 (2)	0.0062 (16)	0.0167 (15)	0.0080 (16)
C3	0.0457 (18)	0.0516 (19)	0.063 (2)	0.0013 (15)	0.0186 (15)	0.0018 (16)
C2	0.050 (2)	0.062 (2)	0.064 (2)	−0.0035 (16)	0.0211 (16)	−0.0037 (17)
C1	0.057 (2)	0.056 (2)	0.061 (2)	−0.0012 (18)	0.0205 (16)	−0.0116 (17)
C10	0.059 (2)	0.071 (2)	0.074 (2)	−0.0192 (19)	0.028 (2)	−0.0260 (19)
F1	0.0905 (16)	0.0959 (16)	0.0992 (17)	0.0079 (13)	0.0128 (13)	−0.0237 (14)
C9	0.056 (2)	0.063 (2)	0.067 (2)	0.0027 (17)	0.0201 (17)	0.0099 (17)
C12	0.057 (3)	0.096 (3)	0.112 (4)	−0.015 (2)	0.031 (2)	−0.054 (3)
C8	0.060 (2)	0.079 (3)	0.100 (3)	0.0058 (19)	0.037 (2)	0.023 (2)
F3	0.125 (2)	0.177 (3)	0.157 (2)	−0.0570 (19)	0.1058 (19)	−0.0681 (19)
C7	0.093 (3)	0.101 (3)	0.084 (3)	0.023 (3)	0.056 (3)	0.030 (2)
F5	0.0962 (18)	0.139 (2)	0.0952 (17)	0.0132 (16)	0.0228 (14)	−0.0032 (14)
C11	0.070 (3)	0.081 (3)	0.071 (2)	−0.014 (2)	0.015 (2)	−0.026 (2)
C5	0.070 (2)	0.085 (3)	0.059 (2)	0.003 (2)	0.0219 (18)	0.001 (2)
C15	0.070 (3)	0.088 (3)	0.080 (3)	−0.014 (2)	0.029 (2)	−0.021 (2)
C13	0.087 (3)	0.106 (4)	0.104 (4)	−0.038 (3)	0.054 (3)	−0.046 (3)
C6	0.098 (3)	0.109 (3)	0.068 (2)	0.017 (3)	0.040 (2)	0.005 (2)
F2	0.0646 (15)	0.161 (2)	0.172 (2)	0.0020 (16)	0.0328 (15)	−0.073 (2)
F4	0.176 (3)	0.158 (3)	0.0910 (18)	−0.030 (2)	0.0650 (18)	−0.0034 (17)
C14	0.106 (4)	0.101 (3)	0.076 (3)	−0.024 (3)	0.043 (3)	−0.025 (3)

Geometric parameters (Å, º)

O2—C1	1.188 (4)	C10—C11	1.356 (5)
O1—C10	1.376 (4)	C10—C15	1.375 (5)
O1—C1	1.382 (4)	C9—C8	1.379 (4)
C4—C5	1.385 (4)	C9—H9	0.9300
C4—C9	1.387 (4)	C11—C12	1.386 (5)
C4—C3	1.459 (4)	C12—C13	1.366 (6)
C3—C2	1.321 (4)	C8—C7	1.370 (5)
C3—H3	0.9300	C8—H8	0.9300
C2—C1	1.454 (4)	C7—C6	1.372 (5)
C2—H2	0.9300	C7—H7	0.9300
F1—C11	1.347 (4)	C5—C6	1.380 (5)
F2—C12	1.330 (5)	C5—H5	0.9300
F3—C13	1.351 (4)	C13—C14	1.345 (6)
F4—C14	1.344 (5)	C14—C15	1.380 (5)
F5—C15	1.329 (4)	C6—H6	0.9300
C10—O1—C1	115.6 (2)	C7—C8—H8	119.8
C5—C4—C9	118.4 (3)	C9—C8—H8	119.8
C5—C4—C3	119.1 (3)	C8—C7—C6	119.9 (3)
C9—C4—C3	122.5 (3)	C8—C7—H7	120.1
C2—C3—C4	127.8 (3)	C6—C7—H7	120.1
C2—C3—H3	116.1	F1—C11—C10	119.6 (3)
C4—C3—H3	116.1	F1—C11—C12	118.5 (4)
C3—C2—C1	120.2 (3)	C10—C11—C12	121.8 (4)
C3—C2—H2	119.9	C6—C5—C4	120.6 (4)
C1—C2—H2	119.9	C6—C5—H5	119.7
O2—C1—O1	121.0 (3)	C4—C5—H5	119.7
O2—C1—C2	128.1 (3)	F5—C15—C10	120.4 (3)
O1—C1—C2	111.0 (3)	F5—C15—C14	119.0 (4)
C11—C10—C15	118.4 (4)	C10—C15—C14	120.6 (4)
C11—C10—O1	122.2 (4)	C14—C13—F3	120.7 (5)
C15—C10—O1	119.4 (4)	C14—C13—C12	121.5 (4)
C8—C9—C4	120.6 (3)	F3—C13—C12	117.8 (5)
C8—C9—H9	119.7	C7—C6—C5	120.2 (4)
C4—C9—H9	119.7	C7—C6—H6	119.9
F2—C12—C13	122.5 (4)	C5—C6—H6	119.9
F2—C12—C11	119.4 (5)	F4—C14—C13	120.5 (4)
C13—C12—C11	118.0 (4)	F4—C14—C15	119.9 (5)
C7—C8—C9	120.3 (4)	C13—C14—C15	119.6 (4)
C5—C4—C3—C2	171.2 (3)	C9—C4—C5—C6	0.8 (5)
C9—C4—C3—C2	−9.2 (5)	C3—C4—C5—C6	−179.5 (3)
C4—C3—C2—C1	179.3 (3)	C11—C10—C15—F5	−179.7 (3)
C10—O1—C1—O2	1.1 (5)	O1—C10—C15—F5	2.1 (5)
C10—O1—C1—C2	−178.6 (3)	C11—C10—C15—C14	1.2 (5)
C3—C2—C1—O2	−1.6 (5)	O1—C10—C15—C14	−177.0 (3)
C3—C2—C1—O1	178.0 (3)	F2—C12—C13—C14	178.9 (4)
C1—O1—C10—C11	70.2 (4)	C11—C12—C13—C14	0.5 (6)
C1—O1—C10—C15	−111.6 (3)	F2—C12—C13—F3	−1.7 (6)
C5—C4—C9—C8	−1.0 (5)	C11—C12—C13—F3	179.8 (3)
C3—C4—C9—C8	179.3 (3)	C8—C7—C6—C5	−0.8 (6)
C4—C9—C8—C7	0.4 (5)	C4—C5—C6—C7	0.1 (6)
C9—C8—C7—C6	0.6 (6)	F3—C13—C14—F4	0.3 (6)
C15—C10—C11—F1	−179.9 (3)	C12—C13—C14—F4	179.7 (4)
O1—C10—C11—F1	−1.7 (5)	F3—C13—C14—C15	−179.0 (3)
C15—C10—C11—C12	−0.3 (5)	C12—C13—C14—C15	0.4 (6)
O1—C10—C11—C12	177.8 (3)	F5—C15—C14—F4	0.4 (6)
F2—C12—C11—F1	0.6 (5)	C10—C15—C14—F4	179.5 (3)
C13—C12—C11—F1	179.1 (3)	F5—C15—C14—C13	179.7 (4)
F2—C12—C11—C10	−179.0 (3)	C10—C15—C14—C13	−1.2 (6)
C13—C12—C11—C10	−0.5 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2	0.93	2.53	2.858 (4)	101
C3—H3···O2^i	0.93	2.44	3.308 (4)	156

Symmetry code: (i) −x+2, −y+2, −z+2.