Acta Cryst. (2008). E64, o1013 [ doi:10.1107/S1600536808012920 ]
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.
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.
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).
Data collection: CrystalClear (MSC/Rigaku, 2001); cell refinement: CrystalClear (MSC/Rigaku, 2001); data reduction: TEXSAN (MSC/Rigaku , 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and TEXSAN (MSC/Rigaku, 2004).
![[Figure 1]](./hg2398fig1thm.gif)
| Fig. 1. Molecular structure of (I) showing atom-labelling scheme and displacement ellipsoids at the 30% probability level. |
![[Figure 2]](./hg2398fig2thm.gif)
| Fig. 2. Showing hydrogen bonded molecules through N—H···O. |
| C15H11FO2 | F(000) = 504 |
| Mr = 242.24 | Dx = 1.408 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71070 Å |
| Hall symbol: -P 2ybc | Cell parameters from 3252 reflections |
| a = 6.261 (4) Å | θ = 3.1–27.5° |
| b = 23.096 (15) Å | µ = 0.10 mm−1 |
| c = 8.269 (5) Å | T = 123 K |
| β = 107.072 (8)° | Needle, colourless |
| V = 1143.1 (13) Å3 | 0.45 × 0.30 × 0.18 mm |
| Z = 4 |
| Rigaku/MSC Mercury CCD diffractometer | 2399 reflections with I > 2σ(I) |
| Radiation source: Rotating anode | Rint = 0.036 |
| graphite | θmax = 27.5°, θmin = 3.1° |
| ω scans | h = −8→6 |
| 9111 measured reflections | k = −25→29 |
| 2589 independent reflections | l = −10→9 |
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.065 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.155 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.16 | w = 1/[σ2(Fo2) + (0.0616P)2 + 0.7669P] where P = (Fo2 + 2Fc2)/3 |
| 2589 reflections | (Δ/σ)max < 0.001 |
| 167 parameters | Δρmax = 0.55 e Å−3 |
| 0 restraints | Δρmin = −0.28 e Å−3 |
| C15H11FO2 | V = 1143.1 (13) Å3 |
| Mr = 242.24 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 6.261 (4) Å | µ = 0.10 mm−1 |
| b = 23.096 (15) Å | T = 123 K |
| c = 8.269 (5) Å | 0.45 × 0.30 × 0.18 mm |
| β = 107.072 (8)° |
| Rigaku/MSC Mercury CCD diffractometer | 2399 reflections with I > 2σ(I) |
| 9111 measured reflections | Rint = 0.036 |
| 2589 independent reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.065 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.155 | Δρmax = 0.55 e Å−3 |
| S = 1.16 | Δρmin = −0.28 e Å−3 |
| 2589 reflections | Absolute structure: ? |
| 167 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | 0.7742 (3) | 0.03235 (7) | 0.8139 (2) | 0.0188 (4) | |
| O1 | 0.9748 (2) | 0.04569 (6) | 0.83715 (16) | 0.0268 (3) | |
| O2 | 0.7095 (2) | −0.00358 (6) | 0.90952 (16) | 0.0258 (3) | |
| H2 | 0.843 (6) | −0.0202 (16) | 1.006 (5) | 0.089 (12)* | |
| C2 | 0.5982 (3) | 0.05820 (7) | 0.6720 (2) | 0.0188 (4) | |
| C3 | 0.6547 (3) | 0.10173 (8) | 0.5755 (2) | 0.0221 (4) | |
| H3 | 0.8054 | 0.1143 | 0.6002 | 0.027* | |
| C4 | 0.4916 (3) | 0.12671 (8) | 0.4437 (2) | 0.0246 (4) | |
| H4 | 0.5313 | 0.1568 | 0.3796 | 0.030* | |
| C5 | 0.2699 (3) | 0.10851 (8) | 0.4031 (2) | 0.0231 (4) | |
| C6 | 0.2149 (3) | 0.06476 (8) | 0.5012 (2) | 0.0232 (4) | |
| H6 | 0.0645 | 0.0519 | 0.4756 | 0.028* | |
| C7 | 0.3771 (3) | 0.03999 (8) | 0.6354 (2) | 0.0213 (4) | |
| H7 | 0.3374 | 0.0107 | 0.7020 | 0.026* | |
| C8 | 0.1067 (3) | 0.13727 (8) | 0.2605 (2) | 0.0250 (4) | |
| H8 | 0.1586 | 0.1694 | 0.2111 | 0.030* | |
| C9 | −0.1064 (3) | 0.12250 (8) | 0.1943 (2) | 0.0246 (4) | |
| H9 | −0.1587 | 0.0904 | 0.2436 | 0.030* | |
| 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 | −0.0628 | 0.2094 | −0.0148 | 0.030* | |
| C12 | −0.3734 (3) | 0.22120 (8) | −0.1778 (2) | 0.0273 (4) | |
| H12 | −0.3353 | 0.2514 | −0.2424 | 0.033* | |
| 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 | −0.8040 | 0.1451 | −0.1539 | 0.031* | |
| C15 | −0.4898 (3) | 0.13277 (8) | 0.0075 (2) | 0.0241 (4) | |
| H15 | −0.5300 | 0.1023 | 0.0700 | 0.029* | |
| F1 | −0.7470 (2) | 0.22525 (6) | −0.34838 (15) | 0.0419 (4) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0185 (8) | 0.0204 (8) | 0.0175 (8) | 0.0011 (6) | 0.0052 (6) | −0.0007 (6) |
| O1 | 0.0173 (6) | 0.0346 (8) | 0.0269 (7) | 0.0001 (5) | 0.0040 (5) | 0.0061 (5) |
| O2 | 0.0227 (6) | 0.0285 (7) | 0.0251 (6) | 0.0005 (5) | 0.0053 (5) | 0.0084 (5) |
| C2 | 0.0190 (8) | 0.0200 (8) | 0.0165 (8) | 0.0030 (6) | 0.0038 (6) | −0.0018 (6) |
| C3 | 0.0213 (8) | 0.0251 (9) | 0.0195 (8) | 0.0016 (7) | 0.0054 (6) | −0.0001 (6) |
| C4 | 0.0267 (9) | 0.0253 (9) | 0.0219 (8) | 0.0031 (7) | 0.0073 (7) | 0.0034 (7) |
| C5 | 0.0246 (9) | 0.0249 (9) | 0.0175 (8) | 0.0057 (7) | 0.0029 (7) | −0.0022 (6) |
| C6 | 0.0175 (8) | 0.0265 (9) | 0.0237 (8) | 0.0019 (7) | 0.0032 (7) | −0.0034 (7) |
| C7 | 0.0196 (8) | 0.0226 (9) | 0.0211 (8) | 0.0012 (7) | 0.0052 (6) | −0.0003 (6) |
| C8 | 0.0238 (9) | 0.0262 (9) | 0.0234 (8) | 0.0025 (7) | 0.0045 (7) | 0.0031 (7) |
| C9 | 0.0264 (9) | 0.0248 (9) | 0.0221 (8) | 0.0011 (7) | 0.0062 (7) | 0.0004 (7) |
| C10 | 0.0220 (9) | 0.0243 (9) | 0.0187 (8) | 0.0044 (7) | 0.0028 (6) | −0.0041 (6) |
| C11 | 0.0216 (9) | 0.0259 (10) | 0.0265 (9) | −0.0002 (7) | 0.0055 (7) | −0.0057 (7) |
| C12 | 0.0347 (10) | 0.0217 (9) | 0.0265 (9) | 0.0025 (8) | 0.0104 (8) | 0.0006 (7) |
| C13 | 0.0280 (9) | 0.0233 (9) | 0.0215 (8) | 0.0116 (7) | −0.0018 (7) | −0.0012 (7) |
| C14 | 0.0188 (8) | 0.0273 (9) | 0.0290 (9) | 0.0019 (7) | 0.0038 (7) | −0.0072 (7) |
| C15 | 0.0260 (9) | 0.0229 (9) | 0.0232 (8) | 0.0013 (7) | 0.0067 (7) | −0.0006 (7) |
| F1 | 0.0413 (7) | 0.0402 (8) | 0.0330 (7) | 0.0202 (6) | −0.0063 (5) | 0.0036 (5) |
| C1—O1 | 1.252 (2) | C8—C9 | 1.330 (3) |
| C1—O2 | 1.291 (2) | C8—H8 | 0.9500 |
| C1—C2 | 1.479 (2) | C9—C10 | 1.471 (2) |
| O2—H2 | 1.04 (4) | C9—H9 | 0.9500 |
| C2—C3 | 1.392 (3) | C10—C15 | 1.392 (3) |
| C2—C7 | 1.393 (3) | C10—C11 | 1.402 (3) |
| C3—C4 | 1.382 (2) | C11—C12 | 1.390 (3) |
| C3—H3 | 0.9500 | C11—H11 | 0.9500 |
| C4—C5 | 1.394 (3) | C12—C13 | 1.380 (3) |
| C4—H4 | 0.9500 | C12—H12 | 0.9500 |
| C5—C6 | 1.401 (3) | C13—F1 | 1.363 (2) |
| C5—C8 | 1.473 (2) | C13—C14 | 1.369 (3) |
| C6—C7 | 1.389 (2) | C14—C15 | 1.389 (3) |
| C6—H6 | 0.9500 | C14—H14 | 0.9500 |
| C7—H7 | 0.9500 | C15—H15 | 0.9500 |
| O1—C1—O2 | 123.07 (15) | C9—C8—H8 | 116.9 |
| O1—C1—C2 | 120.16 (15) | C5—C8—H8 | 116.9 |
| O2—C1—C2 | 116.78 (15) | C8—C9—C10 | 125.99 (18) |
| C1—O2—H2 | 112 (2) | C8—C9—H9 | 117.0 |
| C3—C2—C7 | 119.79 (15) | C10—C9—H9 | 117.0 |
| C3—C2—C1 | 119.41 (16) | C15—C10—C11 | 118.25 (16) |
| C7—C2—C1 | 120.80 (16) | C15—C10—C9 | 118.07 (17) |
| C4—C3—C2 | 120.05 (17) | C11—C10—C9 | 123.68 (17) |
| C4—C3—H3 | 120.0 | C12—C11—C10 | 120.96 (18) |
| C2—C3—H3 | 120.0 | C12—C11—H11 | 119.5 |
| C3—C4—C5 | 121.11 (18) | C10—C11—H11 | 119.5 |
| C3—C4—H4 | 119.4 | C13—C12—C11 | 118.08 (18) |
| C5—C4—H4 | 119.4 | C13—C12—H12 | 121.0 |
| C4—C5—C6 | 118.38 (16) | C11—C12—H12 | 121.0 |
| C4—C5—C8 | 117.69 (17) | F1—C13—C14 | 118.85 (18) |
| C6—C5—C8 | 123.92 (17) | F1—C13—C12 | 118.02 (18) |
| C7—C6—C5 | 120.88 (17) | C14—C13—C12 | 123.12 (17) |
| C7—C6—H6 | 119.6 | C13—C14—C15 | 118.00 (17) |
| C5—C6—H6 | 119.6 | C13—C14—H14 | 121.0 |
| C6—C7—C2 | 119.77 (17) | C15—C14—H14 | 121.0 |
| C6—C7—H7 | 120.1 | C14—C15—C10 | 121.58 (18) |
| C2—C7—H7 | 120.1 | C14—C15—H15 | 119.2 |
| C9—C8—C5 | 126.22 (18) | C10—C15—H15 | 119.2 |
| O1—C1—C2—C3 | −6.5 (2) | C6—C5—C8—C9 | −7.2 (3) |
| O2—C1—C2—C3 | 173.26 (15) | C5—C8—C9—C10 | −179.93 (17) |
| O1—C1—C2—C7 | 174.23 (16) | C8—C9—C10—C15 | −175.06 (18) |
| O2—C1—C2—C7 | −6.0 (2) | C8—C9—C10—C11 | 5.5 (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—C12 | 179.26 (17) |
| C2—C3—C4—C5 | −1.0 (3) | C10—C11—C12—C13 | 0.4 (3) |
| C3—C4—C5—C6 | 1.1 (3) | C11—C12—C13—F1 | −179.25 (16) |
| C3—C4—C5—C8 | −179.83 (16) | C11—C12—C13—C14 | 0.1 (3) |
| C4—C5—C6—C7 | −0.2 (3) | F1—C13—C14—C15 | 178.64 (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—C10 | 0.9 (3) |
| C3—C2—C7—C6 | 1.0 (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—C9 | 173.72 (19) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2···O1i | 1.04 (4) | 1.57 (4) | 2.610 (2) | 174 (3) |
| Symmetry codes: (i) −x+2, −y, −z+2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2···O1i | 1.04 (4) | 1.57 (4) | 2.610 (2) | 174 (3) |
| Symmetry codes: (i) −x+2, −y, −z+2. |
MKR is grateful to the Higher Education Commission of Pakistan for financial support under the International Support Initiative for Doctoral Fellowships a Gifu University, Japan.
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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.