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Acta Crystallogr Sect E Struct Rep Online. 2008 June 1; 64(Pt 6): o1013.
Published online 2008 May 7. doi:  10.1107/S1600536808012920
PMCID: PMC2961507

(E)-4-(4-Fluoro­styr­yl)benzoic acid

Abstract

The title compound, C15H11FO2, is an important inter­mediate in the synthesis of side-chain ligands for polymeric liquid crystals. The vinyl group is almost coplanar with both the aromatic rings. The crystal structure is stabilized by inter­molecular O—H(...)O hydrogen bonding.

Related literature

For related literature, see: Ahmad et al. (2003 [triangle]); Collings & Hird (1997 [triangle]); Frazee & Foraker (2008 [triangle]); Hameed & Rama (2004 [triangle]); Hussain et al. (2005 [triangle]); Nazir et al. (2008 [triangle]); Ribeiro et al. (2008 [triangle]); Wang et al. (2008 [triangle]); Higashi (1999 [triangle]); Yasuda et al. (2000 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o1013-scheme1.jpg

Experimental

Crystal data

  • C15H11FO2
  • M r = 242.24
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1013-efi1.jpg
  • a = 6.261 (4) Å
  • b = 23.096 (15) Å
  • c = 8.269 (5) Å
  • β = 107.072 (8)°
  • V = 1143.1 (13) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 123 (2) K
  • 0.45 × 0.30 × 0.18 mm

Data collection

  • Rigaku/MSC Mercury CCD diffractometer
  • Absorption correction: none
  • 9111 measured reflections
  • 2589 independent reflections
  • 2399 reflections with I > 2σ(I)
  • R int = 0.036

Refinement

  • R[F 2 > 2σ(F 2)] = 0.065
  • wR(F 2) = 0.155
  • S = 1.16
  • 2589 reflections
  • 167 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.55 e Å−3
  • Δρmin = −0.28 e Å−3

Data collection: CrystalClear (MSC/Rigaku, 2001 [triangle]); cell refinement: CrystalClear; data reduction: TEXSAN (MSC/Rigaku, 2004 [triangle]); program(s) used to solve structure: SIR97 (Altomare et al., 1999 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEPII (Johnson, 1976 [triangle]); software used to prepare material for publication: SHELXL97 and TEXSAN.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808012920/hg2398sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808012920/hg2398Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

MKR is grateful to the Higher Education Commission of Pakistan for financial support under the International Support Initiative for Doctoral Fellowships at Gifu University, Japan.

supplementary crystallographic information

Comment

Carboxylic acids constitute an important class of organic compounds and have been used by the medicinal industry as important drugs (Ribeiro et al., 2008; Frazee & Foraker 2008; Hameed & Rama 2004). The carboxylic acids have also found applications as intermediates in the synthesis of an enormous number of organic compounds, in general (Hussain et al., 2005; Ahmad et al., 2003), and in the synthesis of side chain ligands for polymeric liquid crystals, in particular (Wang et al., 2008; Nazir et al., 2008). The liquid crystalline molecules containing substituents at 4-position behave as well ordered calamitic ligands as a side chain group (Collings & Hird, 1997) in side chain polymeric liquid crysrtals (SCPLCs). The derivatives of 4-(4-substituted styryl)benzoic acids have found applications as side chain groups in SCPLCs (Wang et al., 2008). As a part of a project to synthesize ligands for SCPLCs, the title compound, (E)-4-(4-fluorostyryl)benzoic acid (I), was synthesized by reacting 4-fluorobenzaldehyde with methyl [4-(methoxycarbonyl)benzyl]triphenylphosphonium bromide (Nazir et al., 2008) followed by hydrolysis. In the present article, the crystal structure of (I) is being reported. Bond lengths and angles are within the normal ranges as given for vinylbenzoic acid (Yasuda et al., 2000). The C(1)—O(1) and C(1)—O(2) bond lengths are 1.252 (2) and 1.291 (2) respectively,clearly indicating the partial double bond character of the carboxylate group. The carboxylic acid group subtends a dihedral angle[13.72 (16)°] with the phenyl ring C(2)/C(3)/C(4)/C(5)/C(6)/C(7).The vinyl group is almost coplanar with both the phenyl rings. The torsion angles between the phenyl rings and vinyl group fulfill the condition of coplanarity[near to 0° or 180 °]. Two molecules related by an inversion center form a dimer via two hydrogen bonds composed of two carboxyl groups as shown in Fig. 2.

Experimental

Methyl 4-(4-fluorostyryl)benzoate 0.8g (0.0031moles) and sodium hydroxide 0.126g (0.0031 moles) were dissolved in a mixture of 10 ml of methanol and 30 ml of water, and the mixture refluxed for 3 hours. The reaction mixture was cooled to room temperature and acidified with 6M HCl. The precipitated solid was filtered and recrystallized from hot ethanol. Yield: 76%, m.p: 240-252°C, Rf = 0.22 (n-hexane : ethyl acetate 7 : 3). IR (νmax, KBr, cm-1): 3300-2500, 1715, 1620, 1600, 1580, 1188, 1119, 965,834. 1H-NMR (300 MHz,DMSO-d6): δ 7.25 (2H, d, J = 9.0 Hz),7.28 (1H, d, J= 16.2 Hz), 7.42 (1H, d, J = 16.2 Hz), 7.71-7.67 (4H, m),7.95 (2H, d, J = 8.1 Hz), 12.93 (1H, s). 13C-NMR (75 MHz, DMSO-d6): δ 116.16 (d, J= 23 Hz), 126.90, 127.77, 129.23, 130.08 (d, J = 8 Hz), 131.95, 132.49, 133.71 (d, J = 3 Hz), 141.83, 162.42 (d, J = 246 Hz), 167.54.

Refinement

The O-bound H atom was refined isotropically. All the other H atoms were placed in idealized positions and treated as riding atoms with C—H distance in the range 0.95–0.99 Å and Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C).

Figures

Fig. 1.
Molecular structure of (I) showing atom-labelling scheme and displacement ellipsoids at the 30% probability level.
Fig. 2.
Showing hydrogen bonded molecules through N—H···O.

Crystal data

C15H11FO2F(000) = 504
Mr = 242.24Dx = 1.408 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2ybcCell parameters from 3252 reflections
a = 6.261 (4) Åθ = 3.1–27.5°
b = 23.096 (15) ŵ = 0.10 mm1
c = 8.269 (5) ÅT = 123 K
β = 107.072 (8)°Needle, colourless
V = 1143.1 (13) Å30.45 × 0.30 × 0.18 mm
Z = 4

Data collection

Rigaku/MSC Mercury CCD diffractometer2399 reflections with I > 2σ(I)
Radiation source: Rotating anodeRint = 0.036
graphiteθmax = 27.5°, θmin = 3.1°
ω scansh = −8→6
9111 measured reflectionsk = −25→29
2589 independent reflectionsl = −10→9

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.065Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.155H atoms treated by a mixture of independent and constrained refinement
S = 1.16w = 1/[σ2(Fo2) + (0.0616P)2 + 0.7669P] where P = (Fo2 + 2Fc2)/3
2589 reflections(Δ/σ)max < 0.001
167 parametersΔρmax = 0.55 e Å3
0 restraintsΔρmin = −0.28 e Å3

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 (Å2)

xyzUiso*/Ueq
C10.7742 (3)0.03235 (7)0.8139 (2)0.0188 (4)
O10.9748 (2)0.04569 (6)0.83715 (16)0.0268 (3)
O20.7095 (2)−0.00358 (6)0.90952 (16)0.0258 (3)
H20.843 (6)−0.0202 (16)1.006 (5)0.089 (12)*
C20.5982 (3)0.05820 (7)0.6720 (2)0.0188 (4)
C30.6547 (3)0.10173 (8)0.5755 (2)0.0221 (4)
H30.80540.11430.60020.027*
C40.4916 (3)0.12671 (8)0.4437 (2)0.0246 (4)
H40.53130.15680.37960.030*
C50.2699 (3)0.10851 (8)0.4031 (2)0.0231 (4)
C60.2149 (3)0.06476 (8)0.5012 (2)0.0232 (4)
H60.06450.05190.47560.028*
C70.3771 (3)0.03999 (8)0.6354 (2)0.0213 (4)
H70.33740.01070.70200.026*
C80.1067 (3)0.13727 (8)0.2605 (2)0.0250 (4)
H80.15860.16940.21110.030*
C9−0.1064 (3)0.12250 (8)0.1943 (2)0.0246 (4)
H9−0.15870.09040.24360.030*
C10−0.2687 (3)0.15134 (8)0.0517 (2)0.0224 (4)
C11−0.2127 (3)0.19609 (8)−0.0431 (2)0.0250 (4)
H11−0.06280.2094−0.01480.030*
C12−0.3734 (3)0.22120 (8)−0.1778 (2)0.0273 (4)
H12−0.33530.2514−0.24240.033*
C13−0.5900 (3)0.20104 (8)−0.2150 (2)0.0262 (4)
C14−0.6531 (3)0.15774 (8)−0.1256 (2)0.0257 (4)
H14−0.80400.1451−0.15390.031*
C15−0.4898 (3)0.13277 (8)0.0075 (2)0.0241 (4)
H15−0.53000.10230.07000.029*
F1−0.7470 (2)0.22525 (6)−0.34838 (15)0.0419 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0185 (8)0.0204 (8)0.0175 (8)0.0011 (6)0.0052 (6)−0.0007 (6)
O10.0173 (6)0.0346 (8)0.0269 (7)0.0001 (5)0.0040 (5)0.0061 (5)
O20.0227 (6)0.0285 (7)0.0251 (6)0.0005 (5)0.0053 (5)0.0084 (5)
C20.0190 (8)0.0200 (8)0.0165 (8)0.0030 (6)0.0038 (6)−0.0018 (6)
C30.0213 (8)0.0251 (9)0.0195 (8)0.0016 (7)0.0054 (6)−0.0001 (6)
C40.0267 (9)0.0253 (9)0.0219 (8)0.0031 (7)0.0073 (7)0.0034 (7)
C50.0246 (9)0.0249 (9)0.0175 (8)0.0057 (7)0.0029 (7)−0.0022 (6)
C60.0175 (8)0.0265 (9)0.0237 (8)0.0019 (7)0.0032 (7)−0.0034 (7)
C70.0196 (8)0.0226 (9)0.0211 (8)0.0012 (7)0.0052 (6)−0.0003 (6)
C80.0238 (9)0.0262 (9)0.0234 (8)0.0025 (7)0.0045 (7)0.0031 (7)
C90.0264 (9)0.0248 (9)0.0221 (8)0.0011 (7)0.0062 (7)0.0004 (7)
C100.0220 (9)0.0243 (9)0.0187 (8)0.0044 (7)0.0028 (6)−0.0041 (6)
C110.0216 (9)0.0259 (10)0.0265 (9)−0.0002 (7)0.0055 (7)−0.0057 (7)
C120.0347 (10)0.0217 (9)0.0265 (9)0.0025 (8)0.0104 (8)0.0006 (7)
C130.0280 (9)0.0233 (9)0.0215 (8)0.0116 (7)−0.0018 (7)−0.0012 (7)
C140.0188 (8)0.0273 (9)0.0290 (9)0.0019 (7)0.0038 (7)−0.0072 (7)
C150.0260 (9)0.0229 (9)0.0232 (8)0.0013 (7)0.0067 (7)−0.0006 (7)
F10.0413 (7)0.0402 (8)0.0330 (7)0.0202 (6)−0.0063 (5)0.0036 (5)

Geometric parameters (Å, °)

C1—O11.252 (2)C8—C91.330 (3)
C1—O21.291 (2)C8—H80.9500
C1—C21.479 (2)C9—C101.471 (2)
O2—H21.04 (4)C9—H90.9500
C2—C31.392 (3)C10—C151.392 (3)
C2—C71.393 (3)C10—C111.402 (3)
C3—C41.382 (2)C11—C121.390 (3)
C3—H30.9500C11—H110.9500
C4—C51.394 (3)C12—C131.380 (3)
C4—H40.9500C12—H120.9500
C5—C61.401 (3)C13—F11.363 (2)
C5—C81.473 (2)C13—C141.369 (3)
C6—C71.389 (2)C14—C151.389 (3)
C6—H60.9500C14—H140.9500
C7—H70.9500C15—H150.9500
O1—C1—O2123.07 (15)C9—C8—H8116.9
O1—C1—C2120.16 (15)C5—C8—H8116.9
O2—C1—C2116.78 (15)C8—C9—C10125.99 (18)
C1—O2—H2112 (2)C8—C9—H9117.0
C3—C2—C7119.79 (15)C10—C9—H9117.0
C3—C2—C1119.41 (16)C15—C10—C11118.25 (16)
C7—C2—C1120.80 (16)C15—C10—C9118.07 (17)
C4—C3—C2120.05 (17)C11—C10—C9123.68 (17)
C4—C3—H3120.0C12—C11—C10120.96 (18)
C2—C3—H3120.0C12—C11—H11119.5
C3—C4—C5121.11 (18)C10—C11—H11119.5
C3—C4—H4119.4C13—C12—C11118.08 (18)
C5—C4—H4119.4C13—C12—H12121.0
C4—C5—C6118.38 (16)C11—C12—H12121.0
C4—C5—C8117.69 (17)F1—C13—C14118.85 (18)
C6—C5—C8123.92 (17)F1—C13—C12118.02 (18)
C7—C6—C5120.88 (17)C14—C13—C12123.12 (17)
C7—C6—H6119.6C13—C14—C15118.00 (17)
C5—C6—H6119.6C13—C14—H14121.0
C6—C7—C2119.77 (17)C15—C14—H14121.0
C6—C7—H7120.1C14—C15—C10121.58 (18)
C2—C7—H7120.1C14—C15—H15119.2
C9—C8—C5126.22 (18)C10—C15—H15119.2
O1—C1—C2—C3−6.5 (2)C6—C5—C8—C9−7.2 (3)
O2—C1—C2—C3173.26 (15)C5—C8—C9—C10−179.93 (17)
O1—C1—C2—C7174.23 (16)C8—C9—C10—C15−175.06 (18)
O2—C1—C2—C7−6.0 (2)C8—C9—C10—C115.5 (3)
C7—C2—C3—C4−0.1 (3)C15—C10—C11—C12−0.1 (3)
C1—C2—C3—C4−179.31 (16)C9—C10—C11—C12179.26 (17)
C2—C3—C4—C5−1.0 (3)C10—C11—C12—C130.4 (3)
C3—C4—C5—C61.1 (3)C11—C12—C13—F1−179.25 (16)
C3—C4—C5—C8−179.83 (16)C11—C12—C13—C140.1 (3)
C4—C5—C6—C7−0.2 (3)F1—C13—C14—C15178.64 (16)
C8—C5—C6—C7−179.19 (17)C12—C13—C14—C15−0.7 (3)
C5—C6—C7—C2−0.9 (3)C13—C14—C15—C100.9 (3)
C3—C2—C7—C61.0 (3)C11—C10—C15—C14−0.5 (3)
C1—C2—C7—C6−179.80 (15)C9—C10—C15—C14−179.93 (16)
C4—C5—C8—C9173.72 (19)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2···O1i1.04 (4)1.57 (4)2.610 (2)174 (3)

Symmetry codes: (i) −x+2, −y, −z+2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HG2398).

References

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