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access3-Anilinothiocarbonyl-4-hydroxychromen-2-one
aDepartment of Physics, University of Jammu, Jammu Tawi 180 006, India, bSchool of Applied Physics and Mathematics, Shri Mata Vaishno Devi University, Jammu 182 121, India, and cDepartment of Chemistry, Aligarh Muslim University, Aligarh, Uttar Pradesh 202 002, India
*Correspondence e-mail: rk_paper@rediffmail.com
The geometrical parameters of the title compound, C16H11NO3S, are in the usual ranges. The two aromatic residues are not coplanar and are twisted by a dihedral angle of 66.63 (6)°. The is stabilized by N—H⋯O and O—H⋯S interactions.
Related literature
For literature on see: Campbell (1959![[Campbell, N. (1959). Chemistry of Carbon Compounds, edited by E. H. Rodd, Vol. 6, Part 4B, p. 875. Amsterdam: Elsevier. ]](../../../../../../logos/arrows/e_arr.gif "Campbell, N. (1959). Chemistry of Carbon Compounds, edited by E. H. Rodd, Vol. 6, Part 4B, p. 875. Amsterdam: Elsevier.")
); Murray et al. (1982); Wolska et al. (1990); Harvey (1999); Matern et al. (1999); Yang et al. (1992); Tsai et al. (2000).
![[Scheme 1]](jh2075scheme1.gif)
Experimental
Crystal data
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Data collection
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Refinement
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Data collection: CrysAlisPro (Oxford Diffraction, 2007); cell CrysAlisPro; data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Supporting information
contains datablocks global, I. DOI: 10.1107/S1600536809011246/jh2075sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536809011246/jh2075Isup2.hkl
Scheme1: The mixture of 4-hydroxy coumarin, phenylisothiocyanate was taken in THF.The base Na2CO3 was also added to it. The reaction mixture was refluxed on water bath for three hours. Progress of the reaction was monitored by TLC. After completion the reaction mixture was poured into water and worked up with ether and then in ethyl acetate. The ether layer showed the presence of three compounds from which the title compound (I) was separated by followed by crystallization from chloroform-methanol as white crystalline solid. Melting point: 421–423 K.
All H atoms were located from difference Fourier map and refined isotopically with distance restraints 0.86–1.05 Å.
Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell CrysAlis PRO (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./jh2075fig1thm.gif) | Fig. 1. View of (I) (50% probability displacement ellipsoids) |
![[Figure 2]](./jh2075fig2thm.gif) | Fig. 2. Depiction of X—H···A interactions in the title compound(I) |
![[Figure 3]](./jh2075fig3thm.gif) | Fig. 3. The synthesis of the title compound. |
| C16H11NO3S | F(000) = 616 |
| Mr = 297.33 | Dx = 1.465 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| a = 14.8059 (9) Å | Cell parameters from 2320 reflections |
| b = 5.5245 (4) Å | θ = 2.9–32.3° |
| c = 17.4438 (12) Å | µ = 0.25 mm−1 |
| β = 109.091 (7)° | T = 293 K |
| V = 1348.34 (16) Å3 | Rectangular, yellow |
| Z = 4 | 0.30 × 0.24 × 0.18 mm |
| Oxford Diffraction Xcalibur diffractometer | 2320 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.036 |
| Graphite monochromator | θmax = 32.3°, θmin = 2.9° |
| ω–2θ scans | h = −20→21 |
| 11450 measured reflections | k = −8→5 |
| 4408 independent reflections | l = −25→26 |
| Refinement on F2 | 0 constraints |
| Least-squares matrix: full | All H-atom parameters refined |
| R[F2 > 2σ(F2)] = 0.049 | w = 1/[σ2(Fo2) + (0.0645P)2] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.134 | (Δ/σ)max < 0.001 |
| S = 1.01 | Δρmax = 0.24 e Å−3 |
| 4408 reflections | Δρmin = −0.23 e Å−3 |
| 235 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 0 restraints | Extinction coefficient: 0.0079 (18) |
| C16H11NO3S | V = 1348.34 (16) Å3 |
| Mr = 297.33 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 14.8059 (9) Å | µ = 0.25 mm−1 |
| b = 5.5245 (4) Å | T = 293 K |
| c = 17.4438 (12) Å | 0.30 × 0.24 × 0.18 mm |
| β = 109.091 (7)° |
| Oxford Diffraction Xcalibur diffractometer | 2320 reflections with I > 2σ(I) |
| 11450 measured reflections | Rint = 0.036 |
| 4408 independent reflections |
| R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
| wR(F2) = 0.134 | All H-atom parameters refined |
| S = 1.01 | Δρmax = 0.24 e Å−3 |
| 4408 reflections | Δρmin = −0.23 e Å−3 |
| 235 parameters |
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. |
| x | y | z | Uiso*/Ueq | ||
| H3 | −0.2431 (14) | −0.089 (4) | −0.0463 (12) | 0.058 (6)* | |
| H1 | −0.1035 (12) | 0.344 (4) | 0.1367 (11) | 0.044 (5)* | |
| H4 | −0.1108 (14) | −0.346 (4) | −0.0190 (11) | 0.053 (6)* | |
| H2 | −0.2420 (15) | 0.255 (4) | 0.0323 (13) | 0.060 (6)* | |
| H1A | 0.2933 (15) | −0.272 (4) | 0.2272 (13) | 0.066 (7)* | |
| H14 | 0.6547 (16) | −0.057 (4) | 0.4609 (13) | 0.074 (6)* | |
| H12 | 0.4091 (17) | −0.402 (5) | 0.3868 (13) | 0.080 (8)* | |
| H15 | 0.5906 (18) | 0.239 (5) | 0.3553 (16) | 0.095 (9)* | |
| H16 | 0.4290 (17) | 0.200 (5) | 0.2686 (16) | 0.084 (8)* | |
| H13 | 0.5615 (19) | −0.365 (5) | 0.4674 (16) | 0.099 (9)* | |
| H3A | 0.127 (2) | 0.298 (5) | 0.2783 (16) | 0.102 (9)* | |
| S1 | 0.24977 (3) | 0.22219 (9) | 0.33460 (3) | 0.05005 (18) | |
| C8 | 0.14300 (10) | −0.0442 (3) | 0.20025 (9) | 0.0319 (3) | |
| O1 | 0.04858 (8) | −0.2950 (2) | 0.08806 (7) | 0.0400 (3) | |
| O2 | 0.19660 (8) | −0.3959 (2) | 0.14831 (7) | 0.0497 (3) | |
| C10 | 0.23535 (11) | 0.0021 (3) | 0.26441 (9) | 0.0349 (4) | |
| O3 | 0.06066 (9) | 0.2954 (2) | 0.23189 (8) | 0.0470 (3) | |
| C6 | −0.02392 (11) | 0.0583 (3) | 0.12239 (9) | 0.0329 (4) | |
| C7 | 0.06394 (11) | 0.1047 (3) | 0.18839 (9) | 0.0338 (4) | |
| N1 | 0.30848 (10) | −0.1395 (3) | 0.26561 (9) | 0.0452 (4) | |
| C5 | −0.02859 (11) | −0.1432 (3) | 0.07446 (9) | 0.0333 (4) | |
| C1 | −0.10418 (12) | 0.2061 (3) | 0.10584 (12) | 0.0423 (4) | |
| C4 | −0.10991 (12) | −0.2023 (4) | 0.01022 (11) | 0.0420 (4) | |
| C9 | 0.13442 (12) | −0.2508 (3) | 0.14694 (10) | 0.0351 (4) | |
| C11 | 0.40436 (12) | −0.1113 (4) | 0.32054 (11) | 0.0449 (4) | |
| C2 | −0.18535 (13) | 0.1526 (4) | 0.04245 (12) | 0.0494 (5) | |
| C3 | −0.18805 (13) | −0.0511 (4) | −0.00491 (11) | 0.0484 (5) | |
| C16 | 0.45938 (15) | 0.0776 (4) | 0.31041 (15) | 0.0619 (6) | |
| C12 | 0.44115 (17) | −0.2784 (5) | 0.37918 (17) | 0.0725 (7) | |
| C15 | 0.55294 (16) | 0.0988 (5) | 0.36243 (18) | 0.0735 (7) | |
| C14 | 0.58922 (15) | −0.0672 (5) | 0.42249 (17) | 0.0769 (8) | |
| C13 | 0.53483 (19) | −0.2533 (5) | 0.4308 (2) | 0.0947 (11) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0422 (3) | 0.0555 (3) | 0.0476 (3) | −0.0063 (2) | 0.00809 (19) | −0.0194 (2) |
| C8 | 0.0336 (8) | 0.0328 (8) | 0.0296 (8) | −0.0035 (7) | 0.0105 (6) | −0.0054 (7) |
| O1 | 0.0368 (6) | 0.0394 (7) | 0.0388 (6) | 0.0011 (5) | 0.0053 (5) | −0.0093 (5) |
| O2 | 0.0435 (7) | 0.0478 (8) | 0.0498 (7) | 0.0107 (6) | 0.0044 (5) | −0.0145 (6) |
| C10 | 0.0351 (8) | 0.0355 (9) | 0.0351 (8) | −0.0044 (7) | 0.0128 (6) | −0.0023 (7) |
| O3 | 0.0429 (7) | 0.0470 (8) | 0.0490 (7) | 0.0045 (6) | 0.0122 (6) | −0.0170 (6) |
| C6 | 0.0341 (8) | 0.0331 (9) | 0.0323 (8) | −0.0012 (7) | 0.0119 (6) | 0.0017 (7) |
| C7 | 0.0366 (8) | 0.0337 (9) | 0.0335 (8) | −0.0050 (7) | 0.0149 (6) | −0.0015 (7) |
| N1 | 0.0335 (7) | 0.0466 (9) | 0.0490 (9) | −0.0002 (7) | 0.0047 (6) | −0.0124 (8) |
| C5 | 0.0334 (8) | 0.0325 (9) | 0.0344 (8) | −0.0012 (7) | 0.0113 (6) | 0.0034 (7) |
| C1 | 0.0434 (10) | 0.0391 (10) | 0.0451 (10) | 0.0058 (8) | 0.0154 (8) | 0.0049 (9) |
| C4 | 0.0413 (9) | 0.0444 (11) | 0.0373 (9) | −0.0086 (8) | 0.0087 (7) | −0.0007 (8) |
| C9 | 0.0342 (8) | 0.0365 (9) | 0.0338 (8) | −0.0028 (7) | 0.0099 (6) | −0.0032 (7) |
| C11 | 0.0334 (8) | 0.0442 (11) | 0.0521 (11) | −0.0010 (8) | 0.0072 (8) | −0.0101 (9) |
| C2 | 0.0370 (9) | 0.0545 (13) | 0.0525 (11) | 0.0086 (9) | 0.0088 (8) | 0.0123 (10) |
| C3 | 0.0347 (9) | 0.0594 (13) | 0.0439 (10) | −0.0065 (9) | 0.0030 (8) | 0.0094 (9) |
| C16 | 0.0458 (11) | 0.0608 (14) | 0.0740 (15) | −0.0072 (11) | 0.0124 (10) | 0.0046 (12) |
| C12 | 0.0509 (12) | 0.0590 (15) | 0.0860 (17) | −0.0148 (11) | −0.0073 (11) | 0.0140 (13) |
| C15 | 0.0425 (11) | 0.0662 (16) | 0.110 (2) | −0.0167 (12) | 0.0226 (12) | −0.0133 (15) |
| C14 | 0.0402 (11) | 0.0640 (16) | 0.103 (2) | −0.0036 (11) | −0.0091 (12) | −0.0183 (15) |
| C13 | 0.0616 (15) | 0.0752 (18) | 0.105 (2) | −0.0106 (14) | −0.0302 (15) | 0.0220 (16) |
| S1—C10 | 1.6889 (17) | C1—H1 | 0.929 (19) |
| S1—H3A | 1.81 (3) | C4—C3 | 1.381 (3) |
| C8—C7 | 1.390 (2) | C4—H4 | 0.94 (2) |
| C8—C9 | 1.452 (2) | C11—C12 | 1.353 (3) |
| C8—C10 | 1.479 (2) | C11—C16 | 1.370 (3) |
| O1—C9 | 1.3696 (19) | C2—C3 | 1.389 (3) |
| O1—C5 | 1.3737 (19) | C2—H2 | 0.98 (2) |
| O2—C9 | 1.215 (2) | C3—H3 | 0.919 (19) |
| C10—N1 | 1.330 (2) | C16—C15 | 1.391 (3) |
| O3—C7 | 1.308 (2) | C16—H16 | 0.99 (3) |
| O3—H3A | 1.05 (3) | C12—C13 | 1.392 (3) |
| C6—C5 | 1.381 (2) | C12—H12 | 0.86 (3) |
| C6—C1 | 1.392 (2) | C15—C14 | 1.363 (4) |
| C6—C7 | 1.450 (2) | C15—H15 | 0.98 (3) |
| N1—C11 | 1.438 (2) | C14—C13 | 1.343 (4) |
| N1—H1A | 0.97 (2) | C14—H14 | 0.98 (2) |
| C5—C4 | 1.389 (2) | C13—H13 | 0.88 (3) |
| C1—C2 | 1.373 (3) | ||
| C10—S1—H3A | 84.7 (8) | O2—C9—O1 | 114.13 (14) |
| C7—C8—C9 | 118.50 (14) | O2—C9—C8 | 126.81 (15) |
| C7—C8—C10 | 122.40 (14) | O1—C9—C8 | 119.06 (14) |
| C9—C8—C10 | 119.10 (14) | C12—C11—C16 | 120.52 (19) |
| C9—O1—C5 | 122.43 (13) | C12—C11—N1 | 119.68 (18) |
| N1—C10—C8 | 117.17 (15) | C16—C11—N1 | 119.71 (18) |
| N1—C10—S1 | 120.18 (12) | C1—C2—C3 | 120.06 (18) |
| C8—C10—S1 | 122.65 (12) | C1—C2—H2 | 119.6 (13) |
| C7—O3—H3A | 104.8 (15) | C3—C2—H2 | 120.3 (12) |
| C5—C6—C1 | 118.51 (15) | C4—C3—C2 | 121.14 (17) |
| C5—C6—C7 | 118.51 (14) | C4—C3—H3 | 119.0 (13) |
| C1—C6—C7 | 122.98 (16) | C2—C3—H3 | 119.9 (13) |
| O3—C7—C8 | 125.40 (14) | C11—C16—C15 | 119.2 (2) |
| O3—C7—C6 | 114.13 (14) | C11—C16—H16 | 118.0 (14) |
| C8—C7—C6 | 120.45 (15) | C15—C16—H16 | 122.7 (15) |
| C10—N1—C11 | 124.58 (16) | C11—C12—C13 | 119.4 (2) |
| C10—N1—H1A | 115.4 (13) | C11—C12—H12 | 123.2 (15) |
| C11—N1—H1A | 120.0 (13) | C13—C12—H12 | 117.4 (15) |
| O1—C5—C6 | 120.90 (14) | C14—C15—C16 | 120.2 (2) |
| O1—C5—C4 | 116.65 (15) | C14—C15—H15 | 121.9 (15) |
| C6—C5—C4 | 122.44 (15) | C16—C15—H15 | 117.9 (15) |
| C2—C1—C6 | 120.24 (19) | C13—C14—C15 | 119.9 (2) |
| C2—C1—H1 | 118.9 (11) | C13—C14—H14 | 117.6 (13) |
| C6—C1—H1 | 120.8 (11) | C15—C14—H14 | 122.5 (13) |
| C3—C4—C5 | 117.60 (18) | C14—C13—C12 | 120.8 (3) |
| C3—C4—H4 | 123.0 (12) | C14—C13—H13 | 118.1 (18) |
| C5—C4—H4 | 119.3 (12) | C12—C13—H13 | 120.9 (18) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···O2 | 0.96 (2) | 1.77 (2) | 2.5923 (19) | 141 (2) |
| O3—H3A···S1 | 1.05 (2) | 1.81 (3) | 2.8163 (15) | 159 (2) |
Experimental details
| Crystal data | |
| Chemical formula | C16H11NO3S |
| Mr | 297.33 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 293 |
| a, b, c (Å) | 14.8059 (9), 5.5245 (4), 17.4438 (12) |
| β (°) | 109.091 (7) |
| V (Å3) | 1348.34 (16) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.25 |
| Crystal size (mm) | 0.30 × 0.24 × 0.18 |
| Data collection | |
| Diffractometer | Oxford Diffraction Xcalibur diffractometer |
| Absorption correction | – |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 11450, 4408, 2320 |
| Rint | 0.036 |
| (sin θ/λ)max (Å−1) | 0.752 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.134, 1.01 |
| No. of reflections | 4408 |
| No. of parameters | 235 |
| H-atom treatment | All H-atom parameters refined |
| Δρmax, Δρmin (e Å−3) | 0.24, −0.23 |
Computer programs: CrysAlis PRO (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SHELXS86 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···O2 | 0.96 (2) | 1.77 (2) | 2.5923 (19) | 141 (2) |
| O3—H3A···S1 | 1.05 (2) | 1.81 (3) | 2.8163 (15) | 159 (2) |
Acknowledgements
The authors are thankful to the Department of Science and Technology of the Government of India for funding under research project SR/S2/CMP-47/2003.
References
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
Coumarins belong to a group of compounds known as benzopyrones, all of which consist of a benzene ring joined to a pyrone moiety.
Coumarins are found to have a wide spectrum of biological activity, e.g. antithronbotic effect, vascodilating effect on vessel, tonic influence on capillary blood vessels, reduction of blood pressure, antispastic and photosensitizing effect (Wolska et al., 1990).
Interestingly, coumarins exhibit inhibitory effect on DNA gyrase, which may be linked to anti-HIV (human immuno deficiency virus) activity (Matern et al., 1999).
Coumarins are also found to exhibit anti-malarial activity (Yang et al., 1992).
Recently Collinin, isolated from Zathoxylum Schinifolium, has been found to exhibit anti-HBV (hepatitis B virus) activity (Tsai et al., 2000).
Owing to the general importance of these coumarin analogues we report herein the synthesis and crystal structure of a new coumarin 3-anilinothiocarbonyl-4-hydroxychromen-2-one, (I).
The geometrical parameters (i.e. bond distances and angles) of (I) are in the usual ranges. The two aromatic residues are not coplanar and are twisted by a dihedral angle of 66.63 (6)°. The crystal structure is stabilized by X—H···A interactions.