Acta Cryst. (2007). E63, o3708 [ doi:10.1107/S1600536807037683 ]
In the title compound, C13H14OS, a derivative of thioisocoumarin, the packing is stabilized by weak C-H
S, C-H![[pi]](http://journals.iucr.org/logos/entities/pi_rmgif.gif)
and - [separation 3.7481 (12) Å] interactions.
The title compound was synthesized from a mixture of 3-butyl isocoumarin (1 mmol) and Lawesson's reagent (1.2 mmol). The mixture was placed in a glass tube fitted with a tightened rubber septum and was refluxed at 393 K in the presence of toluene solvent under a nitrogen atmosphere. The completion of the reaction was monitored by TLC using a hexane:ethylacetate (9:1 v/v) mixture. After the completion of reaction,the mixture was dissolved in dichloromethane and adsorbed on silica gel·The compound was purified by column chromatography using a mixture of hexane/ethyl acetate (9:1 v/v). Yellow crystals of (I) were recrystalized from ether.
All the H atoms were located and refined isotropically resulting in C—H bond lengths of 0.89 (2)–0.97 (2) Å.
Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and CAMERON (Watkin et al., 1993); software used to prepare material for publication: PLATON (Spek, 2003).
![[Figure 1]](./hb2499fig1thm.gif)
| Fig. 1. View of the molecular structure of (I) showing 50% displacement ellipsoids (H atoms are shown as spheres of arbitrary radius). |
![[Figure 2]](./hb2499fig2thm.gif)
| Fig. 2. Packing diagram of (I) viewed down the c axis. The dotted lines indicate intermolecular C—H···π and π···π stacking interactions. |
| C13H14OS | Z = 2 |
| Mr = 218.31 | F000 = 232 |
| Triclinic, P1 | Dx = 1.264 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation λ = 0.71073 Å |
| a = 7.8699 (6) Å | Cell parameters from 2281 reflections |
| b = 8.5840 (6) Å | θ = 2.7–25.3º |
| c = 9.8083 (7) Å | µ = 0.25 mm−1 |
| α = 82.032 (1)º | T = 290 (2) K |
| β = 76.713 (1)º | Plate, yellow |
| γ = 62.924 (1)º | 0.20 × 0.11 × 0.05 mm |
| V = 573.75 (7) Å3 |
| Bruker SMART CCD area-detector diffractometer | 2249 independent reflections |
| Radiation source: fine-focus sealed tube | 1777 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.014 |
| T = 290(2) K | θmax = 26.0º |
| ω scans | θmin = 2.1º |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→9 |
| Tmin = 0.938, Tmax = 0.988 | k = −10→10 |
| 6031 measured reflections | l = −12→12 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.041 | All H-atom parameters refined |
| wR(F2) = 0.107 | w = 1/[σ2(Fo2) + (0.0594P)2 + 0.0575P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.05 | (Δ/σ)max < 0.001 |
| 2249 reflections | Δρmax = 0.17 e Å−3 |
| 192 parameters | Δρmin = −0.21 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C13H14OS | γ = 62.924 (1)º |
| Mr = 218.31 | V = 573.75 (7) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 7.8699 (6) Å | Mo Kα |
| b = 8.5840 (6) Å | µ = 0.25 mm−1 |
| c = 9.8083 (7) Å | T = 290 (2) K |
| α = 82.032 (1)º | 0.20 × 0.11 × 0.05 mm |
| β = 76.713 (1)º |
| Bruker SMART CCD area-detector diffractometer | 2249 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1777 reflections with I > 2σ(I) |
| Tmin = 0.938, Tmax = 0.988 | Rint = 0.014 |
| 6031 measured reflections |
| R[F2 > 2σ(F2)] = 0.041 | 192 parameters |
| wR(F2) = 0.107 | All H-atom parameters refined |
| S = 1.05 | Δρmax = 0.17 e Å−3 |
| 2249 reflections | Δρmin = −0.21 e Å−3 |
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 > 2sigma(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 | 0.43615 (8) | 0.25638 (6) | −0.32536 (5) | 0.0693 (2) | |
| O1 | 0.30654 (16) | 0.27779 (13) | −0.06157 (11) | 0.0519 (3) | |
| C1 | 0.3570 (2) | 0.3626 (2) | −0.17997 (17) | 0.0487 (4) | |
| C2 | 0.3340 (2) | 0.53771 (19) | −0.16539 (16) | 0.0473 (4) | |
| C3 | 0.3829 (3) | 0.6351 (2) | −0.28165 (19) | 0.0558 (4) | |
| C4 | 0.3587 (3) | 0.8002 (2) | −0.2656 (2) | 0.0618 (5) | |
| C5 | 0.2869 (3) | 0.8736 (2) | −0.1350 (2) | 0.0632 (5) | |
| C6 | 0.2392 (3) | 0.7808 (2) | −0.0203 (2) | 0.0582 (4) | |
| C7 | 0.2605 (2) | 0.6114 (2) | −0.03317 (17) | 0.0490 (4) | |
| C8 | 0.2109 (3) | 0.5103 (2) | 0.08443 (19) | 0.0522 (4) | |
| C9 | 0.2350 (2) | 0.3500 (2) | 0.06889 (17) | 0.0485 (4) | |
| C10 | 0.1948 (3) | 0.2248 (2) | 0.17760 (18) | 0.0530 (4) | |
| C11 | 0.1120 (3) | 0.2967 (2) | 0.32359 (18) | 0.0515 (4) | |
| C12 | 0.0685 (3) | 0.1694 (2) | 0.43241 (19) | 0.0588 (5) | |
| C13 | −0.0232 (4) | 0.2464 (3) | 0.5754 (2) | 0.0713 (6) | |
| H3 | 0.429 (3) | 0.585 (3) | −0.368 (2) | 0.066 (5)* | |
| H4 | 0.395 (3) | 0.857 (3) | −0.341 (2) | 0.067 (6)* | |
| H5 | 0.274 (3) | 0.990 (3) | −0.127 (2) | 0.074 (6)* | |
| H6 | 0.196 (3) | 0.824 (3) | 0.065 (2) | 0.068 (6)* | |
| H8 | 0.165 (3) | 0.557 (2) | 0.170 (2) | 0.063 (5)* | |
| H10A | 0.316 (3) | 0.124 (2) | 0.1765 (17) | 0.055 (5)* | |
| H10B | 0.106 (3) | 0.193 (2) | 0.1454 (19) | 0.066 (5)* | |
| H11A | 0.201 (2) | 0.328 (2) | 0.3513 (17) | 0.052 (4)* | |
| H11B | −0.010 (3) | 0.403 (3) | 0.3205 (19) | 0.063 (5)* | |
| H12A | 0.189 (3) | 0.066 (3) | 0.438 (2) | 0.069 (5)* | |
| H12B | −0.015 (3) | 0.136 (3) | 0.397 (2) | 0.081 (6)* | |
| H13A | 0.054 (3) | 0.288 (3) | 0.611 (2) | 0.095 (7)* | |
| H13B | −0.139 (4) | 0.348 (3) | 0.566 (3) | 0.099 (8)* | |
| H13C | −0.053 (3) | 0.171 (3) | 0.645 (3) | 0.100 (8)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0912 (4) | 0.0545 (3) | 0.0547 (3) | −0.0277 (3) | −0.0019 (2) | −0.0138 (2) |
| O1 | 0.0646 (7) | 0.0413 (6) | 0.0495 (6) | −0.0236 (5) | −0.0082 (5) | −0.0040 (5) |
| C1 | 0.0479 (9) | 0.0433 (8) | 0.0517 (9) | −0.0163 (7) | −0.0117 (7) | −0.0012 (7) |
| C2 | 0.0477 (8) | 0.0418 (8) | 0.0514 (9) | −0.0176 (7) | −0.0136 (7) | 0.0007 (7) |
| C3 | 0.0620 (10) | 0.0541 (10) | 0.0501 (10) | −0.0251 (8) | −0.0116 (8) | 0.0024 (8) |
| C4 | 0.0695 (12) | 0.0543 (10) | 0.0646 (12) | −0.0320 (9) | −0.0169 (9) | 0.0135 (9) |
| C5 | 0.0739 (12) | 0.0456 (9) | 0.0746 (13) | −0.0297 (9) | −0.0166 (10) | 0.0003 (9) |
| C6 | 0.0725 (12) | 0.0439 (9) | 0.0599 (11) | −0.0270 (8) | −0.0103 (9) | −0.0055 (8) |
| C7 | 0.0521 (9) | 0.0416 (8) | 0.0529 (9) | −0.0192 (7) | −0.0124 (7) | −0.0016 (7) |
| C8 | 0.0639 (10) | 0.0459 (9) | 0.0478 (9) | −0.0257 (8) | −0.0079 (8) | −0.0040 (7) |
| C9 | 0.0529 (9) | 0.0439 (8) | 0.0484 (9) | −0.0205 (7) | −0.0096 (7) | −0.0037 (7) |
| C10 | 0.0611 (11) | 0.0424 (9) | 0.0574 (10) | −0.0253 (8) | −0.0100 (8) | −0.0007 (7) |
| C11 | 0.0562 (10) | 0.0446 (9) | 0.0566 (10) | −0.0257 (8) | −0.0084 (8) | −0.0017 (7) |
| C12 | 0.0722 (12) | 0.0466 (10) | 0.0577 (11) | −0.0296 (9) | −0.0046 (9) | −0.0027 (8) |
| C13 | 0.0934 (16) | 0.0656 (13) | 0.0614 (12) | −0.0470 (13) | 0.0032 (11) | −0.0091 (10) |
| S1—C1 | 1.6396 (16) | C8—C9 | 1.326 (2) |
| O1—C1 | 1.361 (2) | C8—H8 | 0.904 (19) |
| O1—C9 | 1.3817 (19) | C9—C10 | 1.493 (2) |
| C1—C2 | 1.453 (2) | C10—C11 | 1.518 (2) |
| C2—C7 | 1.402 (2) | C10—H10A | 0.950 (17) |
| C2—C3 | 1.405 (2) | C10—H10B | 0.98 (2) |
| C3—C4 | 1.368 (3) | C11—C12 | 1.516 (2) |
| C3—H3 | 0.92 (2) | C11—H11A | 0.954 (18) |
| C4—C5 | 1.387 (3) | C11—H11B | 0.985 (19) |
| C4—H4 | 0.89 (2) | C12—C13 | 1.510 (3) |
| C5—C6 | 1.368 (3) | C12—H12A | 0.97 (2) |
| C5—H5 | 0.97 (2) | C12—H12B | 0.97 (2) |
| C6—C7 | 1.407 (2) | C13—H13A | 0.97 (2) |
| C6—H6 | 0.89 (2) | C13—H13B | 0.95 (3) |
| C7—C8 | 1.436 (2) | C13—H13C | 0.94 (3) |
| C1—O1—C9 | 123.44 (12) | C8—C9—C10 | 128.69 (15) |
| O1—C1—C2 | 117.11 (14) | O1—C9—C10 | 110.82 (13) |
| O1—C1—S1 | 116.27 (11) | C9—C10—C11 | 113.79 (14) |
| C2—C1—S1 | 126.61 (13) | C9—C10—H10A | 105.7 (10) |
| C7—C2—C3 | 119.31 (15) | C11—C10—H10A | 110.4 (10) |
| C7—C2—C1 | 119.49 (14) | C9—C10—H10B | 106.5 (11) |
| C3—C2—C1 | 121.20 (15) | C11—C10—H10B | 111.4 (11) |
| C4—C3—C2 | 120.19 (18) | H10A—C10—H10B | 108.7 (15) |
| C4—C3—H3 | 121.6 (13) | C12—C11—C10 | 113.22 (14) |
| C2—C3—H3 | 118.2 (13) | C12—C11—H11A | 109.4 (10) |
| C3—C4—C5 | 120.79 (18) | C10—C11—H11A | 109.4 (10) |
| C3—C4—H4 | 117.8 (13) | C12—C11—H11B | 107.9 (11) |
| C5—C4—H4 | 121.3 (13) | C10—C11—H11B | 108.4 (11) |
| C6—C5—C4 | 120.01 (17) | H11A—C11—H11B | 108.4 (15) |
| C6—C5—H5 | 121.2 (12) | C13—C12—C11 | 112.48 (16) |
| C4—C5—H5 | 118.8 (12) | C13—C12—H12A | 109.5 (11) |
| C5—C6—C7 | 120.73 (18) | C11—C12—H12A | 108.4 (12) |
| C5—C6—H6 | 121.3 (14) | C13—C12—H12B | 112.2 (12) |
| C7—C6—H6 | 118.0 (14) | C11—C12—H12B | 106.3 (13) |
| C2—C7—C6 | 118.97 (15) | H12A—C12—H12B | 107.7 (17) |
| C2—C7—C8 | 118.61 (14) | C12—C13—H13A | 113.6 (14) |
| C6—C7—C8 | 122.42 (16) | C12—C13—H13B | 107.5 (15) |
| C9—C8—C7 | 120.86 (16) | H13A—C13—H13B | 104 (2) |
| C9—C8—H8 | 120.5 (12) | C12—C13—H13C | 114.5 (15) |
| C7—C8—H8 | 118.6 (12) | H13A—C13—H13C | 108 (2) |
| C8—C9—O1 | 120.49 (15) | H13B—C13—H13C | 109 (2) |
| C9—O1—C1—C2 | 0.4 (2) | C1—C2—C7—C8 | 0.2 (2) |
| C9—O1—C1—S1 | −179.15 (11) | C5—C6—C7—C2 | 0.8 (3) |
| O1—C1—C2—C7 | −0.6 (2) | C5—C6—C7—C8 | −179.58 (17) |
| S1—C1—C2—C7 | 178.82 (12) | C2—C7—C8—C9 | 0.5 (2) |
| O1—C1—C2—C3 | 179.74 (14) | C6—C7—C8—C9 | −179.20 (16) |
| S1—C1—C2—C3 | −0.8 (2) | C7—C8—C9—O1 | −0.8 (3) |
| C7—C2—C3—C4 | −0.1 (3) | C7—C8—C9—C10 | 179.12 (16) |
| C1—C2—C3—C4 | 179.51 (16) | C1—O1—C9—C8 | 0.3 (2) |
| C2—C3—C4—C5 | 0.4 (3) | C1—O1—C9—C10 | −179.55 (14) |
| C3—C4—C5—C6 | −0.1 (3) | C8—C9—C10—C11 | 1.2 (3) |
| C4—C5—C6—C7 | −0.5 (3) | O1—C9—C10—C11 | −178.92 (14) |
| C3—C2—C7—C6 | −0.4 (2) | C9—C10—C11—C12 | 178.94 (16) |
| C1—C2—C7—C6 | 179.91 (15) | C10—C11—C12—C13 | −177.06 (19) |
| C3—C2—C7—C8 | 179.89 (14) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C3—H3···S1 | 0.92 (2) | 2.77 (2) | 3.1621 (18) | 106.7 (16) |
| C10—H10B···Cgi | 0.98 (2) | 2.98 (2) | 3.813 (3) | 144.1 (13) |
| Symmetry codes: (i) −x, −y+1, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C3—H3···S1 | 0.92 (2) | 2.77 (2) | 3.1621 (18) | 106.7 (16) |
| C10—H10B···Cgi | 0.98 (2) | 2.98 (2) | 3.813 (3) | 144.1 (13) |
| Symmetry codes: (i) −x, −y+1, −z. |
The authors thank the Department of Science and Technology, India, for the use of the CCD facility setup under the IRHPA–DST program at the IISc.
Barry, R. D. (1964). Chem. Rev. 64, 229–260.
Bruker (2000). SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA. [Please check added reference and amend as necessary]
Bruker (2004). SMART (Version 5.628) and SAINT (Version 6.45a). Bruker AXS Inc., Madison, Wisconsin, USA.
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Saeed, A., Ritch, J. S. & Parvez, M. (2007). Acta Cryst. E63, o1701–o1703.
Saeed, A., van der Eide, E. F. & Parvez, M. (2006). Acta Cryst. E62, o3262–o3263.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.
Watkin, D. J., Pearce, L. & Prout, C. K. (1993). CAMERON. Chemical Crystallography Laboratory, University of Oxford, England.
Thioisocoumarin compounds are widely used in medicinal chemistry and are commonly found in higher plants, marine organisms and in a variety of fungi, lichens and bacteria (Barry, 1964; Napolitano,1997).
In the thioisocoumarin derivative title compound, (I), (Fig. 1), the dihedral angle between the isocoumarin moiety and the n-butyl side chain is 1.90°. The n-butyl group adopts an all trans configuration.
The crystal structure is stabilized by an acute C—H···S intramolecular interaction, an intermolecular C—H···π bond (Table 1) along with an aromatic π···π interaction with a separation of 3.7481 (12) Å (symmetry code: 1 − x, 1 − y, −z) between the centroids of the aromatic rings.
It is noteworthy that in the related 3-butyl-1H isochromene-1-one (ref, date), the molecules are held together only via C—H···O interactions.