Acta Cryst. (2008). E64, o2267 [ doi:10.1107/S160053680803540X ]
In the title compound, C15H11FO3, the aromatic rings are oriented at a dihedral angle of 69.26 (3)°. In the crystal structure, inversion dimers arise from pairs of intermolecular O-H
O hydrogen bonds, and C-HO hydrogen bonds further consolidate the packing. There are also C-H![[pi]](/logos/entities/pi_rmgif.gif)
contacts between the benzoic acid and 2-fluorobenzene rings.
3-(2-Fluorophenyl)isocoumarin (6.4 mmol) was dissolved in ethanol (25 ml) and potassium hydroxide (30 ml 5%) was added. The mixture refluxed for about 5 h. After cooling the solvent was evaporated under reduced pressure. Cold water (20 ml) was added and the reaction mixture acidified with hydrochloric acid (5%). The precipitated keto acid was filtered, washed, dried and recrystalized from hot ethanol (yield; 87%, m.p. 404-405 K).
H atoms were positioned geometrically, with O-H = 0.82 Å (for OH) and C-H = 0.93 and 0.97 Å for aromatic and methylene H, respectively, and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C,O).
Data collection: COLLECT (Hooft, 1998); cell refinement: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997); data reduction: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./hk2566fig1thm.gif)
| Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. |
![[Figure 2]](./hk2566fig2thm.gif)
| Fig. 2. A partial packing diagram. Hydrogen bonds are shown as dashed lines. |
![[Figure 3]](./hk2566fig3thm.gif)
| Fig. 3. The formation of the title compound. |
| C15H11FO3 | F(000) = 536 |
| Mr = 258.24 | Dx = 1.371 Mg m−3 |
| Monoclinic, P21/c | Melting point: 404(1) K |
| Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
| a = 8.3011 (6) Å | Cell parameters from 8503 reflections |
| b = 15.3232 (8) Å | θ = 1–27.5° |
| c = 9.9078 (10) Å | µ = 0.11 mm−1 |
| β = 96.942 (8)° | T = 150 K |
| V = 1251.02 (17) Å3 | Block, colorless |
| Z = 4 | 0.52 × 0.38 × 0.31 mm |
| Bruker–Nonius Kappa CCD area-detector diffractometer | 2782 independent reflections |
| Radiation source: fine-focus sealed tube | 2117 reflections with I > 2σ(I) |
| graphite | Rint = 0.040 |
| Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.5° |
| φ and ω scans | h = −9→10 |
| Absorption correction: gaussian (Coppens, 1970) | k = −18→19 |
| Tmin = 0.962, Tmax = 0.975 | l = −12→12 |
| 8420 measured reflections |
| 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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.136 | H-atom parameters constrained |
| S = 1.12 | w = 1/[σ2(Fo2) + (0.0382P)2 + 0.8217P] where P = (Fo2 + 2Fc2)/3 |
| 2782 reflections | (Δ/σ)max < 0.001 |
| 172 parameters | Δρmax = 0.23 e Å−3 |
| 0 restraints | Δρmin = −0.29 e Å−3 |
| C15H11FO3 | V = 1251.02 (17) Å3 |
| Mr = 258.24 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 8.3011 (6) Å | µ = 0.11 mm−1 |
| b = 15.3232 (8) Å | T = 150 K |
| c = 9.9078 (10) Å | 0.52 × 0.38 × 0.31 mm |
| β = 96.942 (8)° |
| Bruker–Nonius Kappa CCD area-detector diffractometer | 2782 independent reflections |
| Absorption correction: gaussian (Coppens, 1970) | 2117 reflections with I > 2σ(I) |
| Tmin = 0.962, Tmax = 0.975 | Rint = 0.040 |
| 8420 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.053 | H-atom parameters constrained |
| wR(F2) = 0.136 | Δρmax = 0.23 e Å−3 |
| S = 1.12 | Δρmin = −0.29 e Å−3 |
| 2782 reflections | Absolute structure: ? |
| 172 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 | ||
| F1 | 0.15542 (18) | −0.18437 (8) | 0.10130 (16) | 0.0594 (4) | |
| O1 | 0.3928 (2) | −0.00007 (12) | 0.35571 (16) | 0.0573 (5) | |
| O2 | 0.61607 (19) | 0.07728 (11) | 0.40921 (15) | 0.0504 (4) | |
| H2 | 0.6161 | 0.0506 | 0.4809 | 0.061* | |
| O3 | 0.0632 (2) | 0.07181 (10) | 0.1708 (2) | 0.0626 (5) | |
| C1 | 0.4909 (2) | 0.05329 (13) | 0.3244 (2) | 0.0361 (4) | |
| C2 | 0.4762 (2) | 0.09750 (12) | 0.1908 (2) | 0.0326 (4) | |
| C3 | 0.3662 (2) | 0.06805 (12) | 0.08185 (19) | 0.0316 (4) | |
| C4 | 0.3530 (3) | 0.11624 (15) | −0.0370 (2) | 0.0410 (5) | |
| H4 | 0.2814 | 0.0979 | −0.1111 | 0.049* | |
| C5 | 0.4429 (3) | 0.19136 (15) | −0.0483 (2) | 0.0477 (6) | |
| H5 | 0.4292 | 0.2236 | −0.1284 | 0.057* | |
| C6 | 0.5523 (3) | 0.21865 (14) | 0.0580 (2) | 0.0468 (5) | |
| H6 | 0.6140 | 0.2686 | 0.0499 | 0.056* | |
| C7 | 0.5704 (3) | 0.17144 (13) | 0.1770 (2) | 0.0397 (5) | |
| H7 | 0.6464 | 0.1889 | 0.2485 | 0.048* | |
| C8 | 0.2660 (2) | −0.01340 (13) | 0.0886 (2) | 0.0335 (4) | |
| H8A | 0.3338 | −0.0593 | 0.1325 | 0.040* | |
| H8B | 0.2282 | −0.0325 | −0.0032 | 0.040* | |
| C9 | 0.1223 (2) | 0.00021 (12) | 0.1651 (2) | 0.0344 (4) | |
| C10 | 0.0483 (2) | −0.07466 (12) | 0.2322 (2) | 0.0330 (4) | |
| C11 | 0.0665 (2) | −0.16193 (13) | 0.2005 (2) | 0.0395 (5) | |
| C12 | −0.0064 (3) | −0.22847 (15) | 0.2627 (3) | 0.0520 (6) | |
| H12 | 0.0071 | −0.2862 | 0.2371 | 0.062* | |
| C13 | −0.1001 (3) | −0.20839 (18) | 0.3633 (3) | 0.0599 (7) | |
| H13 | −0.1490 | −0.2527 | 0.4079 | 0.072* | |
| C14 | −0.1213 (3) | −0.12269 (19) | 0.3988 (3) | 0.0603 (7) | |
| H14 | −0.1854 | −0.1092 | 0.4667 | 0.072* | |
| C15 | −0.0491 (3) | −0.05654 (16) | 0.3331 (2) | 0.0469 (5) | |
| H15 | −0.0654 | 0.0011 | 0.3573 | 0.056* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| F1 | 0.0607 (9) | 0.0356 (7) | 0.0886 (11) | −0.0018 (6) | 0.0356 (8) | −0.0117 (7) |
| O1 | 0.0577 (10) | 0.0698 (12) | 0.0414 (9) | −0.0320 (9) | −0.0064 (7) | 0.0151 (8) |
| O2 | 0.0525 (9) | 0.0544 (10) | 0.0422 (8) | −0.0221 (8) | −0.0034 (7) | 0.0060 (7) |
| O3 | 0.0532 (10) | 0.0293 (8) | 0.1121 (15) | 0.0072 (7) | 0.0381 (10) | 0.0056 (9) |
| C1 | 0.0367 (10) | 0.0344 (10) | 0.0375 (10) | −0.0062 (8) | 0.0057 (8) | −0.0028 (8) |
| C2 | 0.0350 (10) | 0.0281 (9) | 0.0369 (10) | 0.0002 (7) | 0.0126 (8) | −0.0010 (7) |
| C3 | 0.0277 (9) | 0.0324 (10) | 0.0365 (10) | 0.0044 (7) | 0.0108 (8) | 0.0008 (8) |
| C4 | 0.0351 (10) | 0.0487 (12) | 0.0402 (11) | 0.0050 (9) | 0.0086 (8) | 0.0075 (9) |
| C5 | 0.0467 (12) | 0.0463 (12) | 0.0538 (13) | 0.0066 (10) | 0.0210 (11) | 0.0179 (10) |
| C6 | 0.0495 (13) | 0.0339 (11) | 0.0614 (14) | −0.0047 (9) | 0.0245 (11) | 0.0058 (10) |
| C7 | 0.0410 (11) | 0.0350 (11) | 0.0455 (12) | −0.0050 (8) | 0.0146 (9) | −0.0054 (9) |
| C8 | 0.0329 (10) | 0.0320 (10) | 0.0360 (10) | −0.0013 (8) | 0.0050 (8) | −0.0019 (8) |
| C9 | 0.0309 (9) | 0.0291 (10) | 0.0432 (11) | 0.0000 (8) | 0.0046 (8) | −0.0005 (8) |
| C10 | 0.0293 (9) | 0.0331 (10) | 0.0363 (10) | −0.0006 (7) | 0.0023 (7) | 0.0001 (8) |
| C11 | 0.0325 (10) | 0.0343 (10) | 0.0522 (13) | 0.0020 (8) | 0.0068 (9) | 0.0013 (9) |
| C12 | 0.0460 (12) | 0.0328 (11) | 0.0772 (17) | −0.0012 (9) | 0.0074 (12) | 0.0106 (11) |
| C13 | 0.0589 (15) | 0.0561 (15) | 0.0653 (16) | −0.0107 (12) | 0.0103 (13) | 0.0231 (13) |
| C14 | 0.0649 (17) | 0.0703 (18) | 0.0504 (14) | −0.0106 (13) | 0.0257 (12) | 0.0032 (12) |
| C15 | 0.0514 (13) | 0.0455 (12) | 0.0459 (12) | −0.0052 (10) | 0.0142 (10) | −0.0059 (10) |
| F1—C11 | 1.343 (2) | C8—H8A | 0.9700 |
| O1—C1 | 1.220 (2) | C8—H8B | 0.9700 |
| O2—C1 | 1.308 (2) | C9—O3 | 1.206 (2) |
| O2—H2 | 0.8199 | C9—C8 | 1.503 (3) |
| C2—C1 | 1.479 (3) | C9—C10 | 1.495 (3) |
| C2—C3 | 1.402 (3) | C10—C11 | 1.386 (3) |
| C2—C7 | 1.393 (3) | C10—C15 | 1.388 (3) |
| C3—C4 | 1.383 (3) | C11—C12 | 1.370 (3) |
| C3—C8 | 1.506 (3) | C12—C13 | 1.371 (4) |
| C4—C5 | 1.384 (3) | C12—H12 | 0.9299 |
| C4—H4 | 0.9300 | C13—H13 | 0.9300 |
| C5—C6 | 1.370 (3) | C14—C13 | 1.376 (4) |
| C5—H5 | 0.9300 | C14—H14 | 0.9300 |
| C6—H6 | 0.9299 | C15—C14 | 1.380 (3) |
| C7—C6 | 1.376 (3) | C15—H15 | 0.9300 |
| C7—H7 | 0.9300 | ||
| C1—O2—H2 | 109.5 | C9—C8—H8B | 109.1 |
| O1—C1—O2 | 121.87 (19) | C3—C8—H8B | 109.1 |
| O1—C1—C2 | 123.30 (18) | H8A—C8—H8B | 107.8 |
| O2—C1—C2 | 114.80 (17) | O3—C9—C10 | 119.08 (18) |
| C7—C2—C3 | 120.47 (18) | O3—C9—C8 | 120.14 (18) |
| C7—C2—C1 | 118.31 (18) | C10—C9—C8 | 120.77 (16) |
| C3—C2—C1 | 121.18 (17) | C11—C10—C15 | 116.41 (19) |
| C4—C3—C2 | 117.49 (18) | C11—C10—C9 | 125.32 (18) |
| C4—C3—C8 | 119.50 (18) | C15—C10—C9 | 118.26 (18) |
| C2—C3—C8 | 123.00 (17) | F1—C11—C12 | 116.77 (19) |
| C3—C4—C5 | 121.6 (2) | F1—C11—C10 | 119.81 (18) |
| C3—C4—H4 | 119.2 | C12—C11—C10 | 123.4 (2) |
| C5—C4—H4 | 119.2 | C11—C12—C13 | 118.7 (2) |
| C6—C5—C4 | 120.4 (2) | C11—C12—H12 | 120.7 |
| C6—C5—H5 | 119.7 | C13—C12—H12 | 120.6 |
| C4—C5—H5 | 119.9 | C12—C13—C14 | 120.1 (2) |
| C5—C6—C7 | 119.4 (2) | C12—C13—H13 | 120.0 |
| C5—C6—H6 | 120.4 | C14—C13—H13 | 119.9 |
| C7—C6—H6 | 120.2 | C13—C14—C15 | 120.2 (2) |
| C6—C7—C2 | 120.5 (2) | C13—C14—H14 | 120.0 |
| C6—C7—H7 | 119.7 | C15—C14—H14 | 119.8 |
| C2—C7—H7 | 119.8 | C14—C15—C10 | 121.1 (2) |
| C9—C8—C3 | 112.56 (16) | C14—C15—H15 | 119.5 |
| C9—C8—H8A | 109.1 | C10—C15—H15 | 119.4 |
| C3—C8—H8A | 109.1 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2···O1i | 0.82 | 1.80 | 2.621 (3) | 175 |
| C12—H12···O3ii | 0.93 | 2.46 | 3.178 (3) | 134 |
| C4—H4···Cg2iii | 0.93 | 2.72 | 3.535 (3) | 146 |
| C13—H13···Cg1ii | 0.93 | 3.06 | 3.868 (3) | 146 |
| Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, y−1/2, −z+1/2; (iii) −x, −y, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2···O1i | 0.82 | 1.80 | 2.621 (3) | 175 |
| C12—H12···O3ii | 0.93 | 2.46 | 3.178 (3) | 134 |
| C4—H4···Cg2iii | 0.93 | 2.72 | 3.535 (3) | 146 |
| C13—H13···Cg1ii | 0.93 | 3.06 | 3.868 (3) | 146 |
| Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, y−1/2, −z+1/2; (iii) −x, −y, −z. |
M. Tariq Mahmood Babar is grateful to the Higher Education Commission of Pakistan for financial support under the National Support Initiative Program for Pre-doctoral Fellowships at Quaid-i-Azam University.
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The title compound is an important intermediate in the conversion of isocoumarin to 3,4-dihydroisocoumarin. Derivatives of isocoumarin and 3,4-dihydroisocoumarin display a broad range of biological activity (Hill, 1986; Napolitano, 1997). 3,4-Dihydroisocoumarins are an important class of naturally occurring, biologically active gamma-lactones. Numbers of such dihydroisocoumarins have various uses, ranging from sweetening agents to bactericides, antimalarial, antituberclous, antifungal, antiulcergenic and antitumour (Oikawa et al., 1997; Kongsaeree et al., 2003).
In the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (C2-C7) and B (C10-C15) are, of course, planar and they are oriented at a dihedral angle of 69.26 (3)°. The (O1/O2/C1) moiety is oriented with respect to rings A and B at dihedral angles of 14.54 (4)° and 76.12 (3)°, respectively.
In the crystal structure, intermolecular O-H···O and C-H···O hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure. There also exist C—H···π contacts (Table 1) between the benzoic acid and 2-fluorobenzene rings.