Acta Cryst. (2009). E65, o500 [ doi:10.1107/S1600536809004152 ]
In the molecule of the title compound, C16H11FOS, the benzene ring is oriented at a dihedral angle of 89.68 (3)° with respect to the planar [maximum deviation 0.009 (2) Å] isocoumarin ring system. An intramolecular C-H
S interaction results in the formation of a planar five-membered ring. In the crystal structure, intermolecular C-HO hydrogen bonds link the molecules into chains parallel to the c axis. A ![[pi]](/logos/entities/pi_rmgif.gif)
- contact between the isocoumarin rings [centroid-centroid distance = 3.818 (3) Å] may further stabilize the structure.
As shown in Scheme 2, the title compound was synthesized by refluxing 3-(4-fluorobenzyl)-1H-isochromen-1-one (0.5 g, 1.8 mmol) with Lawesson's reagent (0.89 g, 2.2 mmol) in dry toluene for 4 h. Pure thioisocoumarin was obtained by recrystalization in methanol (yield; 90%, m.p. 665-667 K).
H atoms were positioned geometrically, with 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).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).
![[Figure 1]](./hk2617fig1thm.gif)
| Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. |
![[Figure 2]](./hk2617fig2thm.gif)
| Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines. |
![[Figure 3]](./hk2617fig3thm.gif)
| Fig. 3. The formation of the title compound. |
| C16H11FOS | F(000) = 560 |
| Mr = 270.31 | Dx = 1.361 Mg m−3 |
| Monoclinic, P21/c | Melting point: 392(2) K |
| Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
| a = 8.7346 (6) Å | Cell parameters from 1423 reflections |
| b = 17.9516 (11) Å | θ = 4.2–25.4° |
| c = 8.4481 (5) Å | µ = 0.25 mm−1 |
| β = 95.026 (1)° | T = 294 K |
| V = 1319.57 (14) Å3 | Block, yellow |
| Z = 4 | 0.30 × 0.25 × 0.20 mm |
| Bruker SMART CCD area-detector diffractometer | 3188 independent reflections |
| Radiation source: fine-focus sealed tube | 2655 reflections with I > 2σ(I) |
| graphite | Rint = 0.016 |
| φ and ω scans | θmax = 28.3°, θmin = 2.6° |
| Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −11→11 |
| Tmin = 0.805, Tmax = 0.952 | k = −23→22 |
| 7856 measured reflections | l = −8→11 |
| 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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.150 | H-atom parameters constrained |
| S = 1.03 | w = 1/[σ2(Fo2) + (0.0856P)2 + 0.2983P] where P = (Fo2 + 2Fc2)/3 |
| 3188 reflections | (Δ/σ)max < 0.001 |
| 172 parameters | Δρmax = 0.34 e Å−3 |
| 0 restraints | Δρmin = −0.29 e Å−3 |
| C16H11FOS | V = 1319.57 (14) Å3 |
| Mr = 270.31 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 8.7346 (6) Å | µ = 0.25 mm−1 |
| b = 17.9516 (11) Å | T = 294 K |
| c = 8.4481 (5) Å | 0.30 × 0.25 × 0.20 mm |
| β = 95.026 (1)° |
| Bruker SMART CCD area-detector diffractometer | 3188 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2001) | 2655 reflections with I > 2σ(I) |
| Tmin = 0.805, Tmax = 0.952 | Rint = 0.016 |
| 7856 measured reflections | θmax = 28.3° |
| R[F2 > 2σ(F2)] = 0.046 | H-atom parameters constrained |
| wR(F2) = 0.150 | Δρmax = 0.34 e Å−3 |
| S = 1.03 | Δρmin = −0.29 e Å−3 |
| 3188 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 | ||
| S1 | 0.07012 (6) | 0.65948 (3) | 0.36335 (6) | 0.0646 (2) | |
| O1 | 0.20272 (15) | 0.53300 (6) | 0.37410 (13) | 0.0506 (3) | |
| F1 | 0.51024 (16) | 0.13358 (7) | 0.29180 (19) | 0.0845 (4) | |
| C1 | 0.0938 (2) | 0.63191 (10) | −0.0010 (2) | 0.0563 (4) | |
| H1A | 0.0472 | 0.6745 | 0.0350 | 0.068* | |
| C2 | 0.1045 (3) | 0.62201 (12) | −0.1609 (2) | 0.0665 (5) | |
| H2A | 0.0656 | 0.6581 | −0.2326 | 0.080* | |
| C3 | 0.1727 (3) | 0.55866 (12) | −0.2156 (2) | 0.0706 (6) | |
| H3A | 0.1785 | 0.5521 | −0.3241 | 0.085* | |
| C4 | 0.2320 (3) | 0.50543 (11) | −0.1113 (2) | 0.0656 (5) | |
| H4A | 0.2784 | 0.4633 | −0.1496 | 0.079* | |
| C5 | 0.2234 (2) | 0.51390 (9) | 0.05279 (18) | 0.0483 (4) | |
| C6 | 0.15271 (18) | 0.57814 (8) | 0.10781 (17) | 0.0439 (3) | |
| C7 | 0.14344 (18) | 0.58791 (9) | 0.27669 (18) | 0.0446 (3) | |
| C8 | 0.2707 (2) | 0.46929 (8) | 0.32005 (19) | 0.0482 (4) | |
| C9 | 0.2829 (2) | 0.45929 (9) | 0.1661 (2) | 0.0523 (4) | |
| H9A | 0.3304 | 0.4166 | 0.1313 | 0.063* | |
| C10 | 0.3182 (3) | 0.41971 (10) | 0.4583 (2) | 0.0615 (5) | |
| H10A | 0.2320 | 0.4141 | 0.5222 | 0.074* | |
| H10B | 0.4006 | 0.4438 | 0.5237 | 0.074* | |
| C11 | 0.3716 (2) | 0.34333 (9) | 0.4123 (2) | 0.0515 (4) | |
| C12 | 0.5239 (3) | 0.32831 (12) | 0.3957 (3) | 0.0741 (6) | |
| H12A | 0.5961 | 0.3662 | 0.4129 | 0.089* | |
| C13 | 0.5718 (2) | 0.25794 (14) | 0.3540 (3) | 0.0799 (7) | |
| H13A | 0.6748 | 0.2483 | 0.3421 | 0.096* | |
| C14 | 0.4648 (2) | 0.20356 (10) | 0.3309 (2) | 0.0585 (4) | |
| C15 | 0.3136 (2) | 0.21543 (11) | 0.3461 (3) | 0.0671 (5) | |
| H15A | 0.2425 | 0.1771 | 0.3292 | 0.081* | |
| C16 | 0.2677 (2) | 0.28622 (11) | 0.3875 (3) | 0.0644 (5) | |
| H16A | 0.1644 | 0.2952 | 0.3987 | 0.077* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0761 (4) | 0.0604 (3) | 0.0583 (3) | 0.0200 (2) | 0.0112 (2) | −0.0054 (2) |
| O1 | 0.0702 (8) | 0.0431 (6) | 0.0390 (5) | 0.0077 (5) | 0.0071 (5) | −0.0006 (4) |
| F1 | 0.0826 (9) | 0.0557 (7) | 0.1132 (11) | 0.0188 (6) | −0.0030 (8) | −0.0146 (7) |
| C1 | 0.0629 (11) | 0.0529 (9) | 0.0526 (9) | 0.0022 (8) | 0.0028 (7) | 0.0071 (7) |
| C2 | 0.0840 (14) | 0.0661 (11) | 0.0485 (9) | −0.0040 (10) | −0.0003 (9) | 0.0157 (9) |
| C3 | 0.1044 (17) | 0.0684 (12) | 0.0396 (8) | −0.0116 (11) | 0.0106 (9) | 0.0040 (8) |
| C4 | 0.1026 (16) | 0.0520 (9) | 0.0441 (9) | −0.0023 (10) | 0.0173 (9) | −0.0040 (7) |
| C5 | 0.0635 (10) | 0.0415 (7) | 0.0408 (7) | −0.0063 (7) | 0.0093 (7) | −0.0009 (6) |
| C6 | 0.0473 (8) | 0.0431 (7) | 0.0412 (7) | −0.0052 (6) | 0.0042 (6) | 0.0012 (6) |
| C7 | 0.0462 (8) | 0.0438 (7) | 0.0437 (7) | −0.0001 (6) | 0.0043 (6) | 0.0000 (6) |
| C8 | 0.0623 (10) | 0.0364 (7) | 0.0460 (8) | 0.0016 (6) | 0.0053 (7) | −0.0004 (6) |
| C9 | 0.0713 (11) | 0.0383 (7) | 0.0484 (8) | 0.0032 (7) | 0.0110 (7) | −0.0020 (6) |
| C10 | 0.0910 (14) | 0.0465 (9) | 0.0466 (9) | 0.0090 (9) | 0.0037 (8) | 0.0035 (7) |
| C11 | 0.0653 (10) | 0.0424 (8) | 0.0464 (8) | 0.0041 (7) | 0.0019 (7) | 0.0069 (6) |
| C12 | 0.0598 (12) | 0.0560 (11) | 0.1061 (18) | −0.0107 (9) | 0.0047 (11) | −0.0067 (11) |
| C13 | 0.0506 (11) | 0.0685 (13) | 0.121 (2) | 0.0047 (9) | 0.0111 (12) | −0.0073 (13) |
| C14 | 0.0621 (11) | 0.0453 (8) | 0.0666 (11) | 0.0093 (7) | −0.0027 (8) | −0.0016 (8) |
| C15 | 0.0561 (11) | 0.0462 (9) | 0.0976 (15) | −0.0034 (8) | −0.0018 (10) | −0.0022 (9) |
| C16 | 0.0508 (10) | 0.0538 (10) | 0.0891 (14) | 0.0065 (8) | 0.0080 (9) | 0.0029 (9) |
| C1—C2 | 1.373 (3) | C8—C10 | 1.498 (2) |
| C1—C6 | 1.400 (2) | C9—H9A | 0.9300 |
| C1—H1A | 0.9300 | C10—C11 | 1.510 (2) |
| C2—C3 | 1.382 (3) | C10—H10A | 0.9700 |
| C2—H2A | 0.9300 | C10—H10B | 0.9700 |
| C3—C4 | 1.370 (3) | C11—C16 | 1.373 (3) |
| C3—H3A | 0.9300 | C11—C12 | 1.376 (3) |
| C4—C5 | 1.403 (2) | C12—C13 | 1.386 (3) |
| C4—H4A | 0.9300 | C12—H12A | 0.9300 |
| C5—C6 | 1.406 (2) | C13—C14 | 1.353 (3) |
| C5—C9 | 1.435 (2) | C13—H13A | 0.9300 |
| C6—C7 | 1.447 (2) | C14—C15 | 1.355 (3) |
| C7—O1 | 1.3573 (19) | C14—F1 | 1.367 (2) |
| C7—S1 | 1.6367 (16) | C15—C16 | 1.387 (3) |
| C8—C9 | 1.327 (2) | C15—H15A | 0.9300 |
| C8—O1 | 1.3843 (18) | C16—H16A | 0.9300 |
| C2—C1—C6 | 120.26 (18) | C5—C9—H9A | 119.8 |
| C2—C1—H1A | 119.9 | C8—C10—C11 | 114.22 (15) |
| C6—C1—H1A | 119.9 | C8—C10—H10A | 108.7 |
| C1—C2—C3 | 120.26 (18) | C11—C10—H10A | 108.7 |
| C1—C2—H2A | 119.9 | C8—C10—H10B | 108.7 |
| C3—C2—H2A | 119.9 | C11—C10—H10B | 108.7 |
| C4—C3—C2 | 120.55 (17) | H10A—C10—H10B | 107.6 |
| C4—C3—H3A | 119.7 | C16—C11—C12 | 118.03 (17) |
| C2—C3—H3A | 119.7 | C16—C11—C10 | 120.16 (18) |
| C3—C4—C5 | 120.66 (18) | C12—C11—C10 | 121.81 (18) |
| C3—C4—H4A | 119.7 | C11—C12—C13 | 121.35 (19) |
| C5—C4—H4A | 119.7 | C11—C12—H12A | 119.3 |
| C4—C5—C6 | 118.58 (15) | C13—C12—H12A | 119.3 |
| C4—C5—C9 | 122.49 (16) | C14—C13—C12 | 118.3 (2) |
| C6—C5—C9 | 118.92 (14) | C14—C13—H13A | 120.8 |
| C1—C6—C5 | 119.68 (15) | C12—C13—H13A | 120.8 |
| C1—C6—C7 | 121.00 (15) | C13—C14—C15 | 122.61 (18) |
| C5—C6—C7 | 119.31 (14) | C13—C14—F1 | 119.12 (18) |
| O1—C7—C6 | 117.29 (13) | C15—C14—F1 | 118.27 (18) |
| O1—C7—S1 | 116.25 (11) | C14—C15—C16 | 118.29 (18) |
| C6—C7—S1 | 126.45 (12) | C14—C15—H15A | 120.9 |
| C9—C8—O1 | 120.60 (14) | C16—C15—H15A | 120.9 |
| C9—C8—C10 | 130.03 (16) | C11—C16—C15 | 121.39 (18) |
| O1—C8—C10 | 109.36 (13) | C11—C16—H16A | 119.3 |
| C8—C9—C5 | 120.38 (15) | C15—C16—H16A | 119.3 |
| C8—C9—H9A | 119.8 | C7—O1—C8 | 123.49 (12) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C1—H1A···S1 | 0.93 | 2.78 | 3.142 (2) | 105 |
| C3—H3A···O1i | 0.93 | 2.60 | 3.529 (2) | 178 |
| Symmetry codes: (i) x, y, z−1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C1—H1A···S1 | 0.93 | 2.78 | 3.142 (2) | 105 |
| C3—H3A···O1i | 0.93 | 2.60 | 3.529 (2) | 178 |
| Symmetry codes: (i) x, y, z−1. |
The authors gratefully acknowledge the financial support of the Higher Education Commission, Islamabad, Pakistan.
Abid, O., Rama, N. H., Qadeer, G., Khan, G. S. & Lu, X.-M. (2006). Acta Cryst. E62, o2895–o2896.
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
Barry, R. D. (1964). Chem. Rev. 64, 239–241.
Bruker (2001). SMART and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2002). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Powers, J. C., Asgian, J. L., Ekici, D. & James, K. E. (2002). Chem. Rev. 102, 4639–4643.
Rossi, R., Carpita, A., Bellina, F., Stabile, P. & Mannina, L. (2003). Tetrahedron, 59, 2067–2081.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.
Sturtz, G., Meepagala, K. & Wedge, D. (2002). J. Agric. Food Chem. 50, 6979–6984.
Thomas, L. & Jens, B. J. (1999). Nat. Prod. 62, 1182–1187.
The isocoumarin nucleus is an abundant structural motif in natural products (Barry, 1964). Many constituents of the steadily growing class of known isocoumarins exhibit valuable biological properties such as antifungal (Sturtz et al., 2002), antitumor or cytotoxic, anti-inflammatory, anti-allergic (Rossi et al., 2003) and enzyme inhibitory (Powers et al., 2002) activities. Naturally occurring halo-isocoumarins and their halogeno-3,4-dihydroiscoumarin derivatives are very rare. However, a few examples of naturally occurring chlorine containing isocoumarins are known (Thomas & Jens, 1999). In view of the importance of this class of compounds, the title compound, an isocoumarine derivative containing 4-fluorobenzyl substituent has been synthesized, and we report herein its crystal structure.
In the molecule of the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges, and comparable with the corresponding values in 3-(2-chlorobenzyl)isocoumarin (Abid et al., 2006). Rings A (C1-C6), B (O1/C5-C9) and C (C11-C16) are, of course, planar and the dihedral angles between them are A/B = 0.29 (3)°, A/C = 89.77 (4)° and B/C = 89.53 (3)°. The intramolecular C-H···S interaction (Table 1) results in the formation of a planar five-membered ring D (S1/C1/C6/C7/H1A).
In the crystal structure, intermolecular C-H···O hydrogen bonds (Table 1) link the molecules into chains parallel to the c-axis (Fig. 2), in which they may be effective in the stabilization of the structure. The π-π contact between the isocoumarine rings, Cg1—Cg2i [symmetry code: (i) -x, -y, 1 - z, where Cg1 and Cg2 are centroids of the rings A (C1-C6) and B (O1/C5-C9), respectively] may further stabilize the structure, with centroid-centroid distance of 3.818 (3) Å.