Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801014799/ya6060sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801014799/ya6060Isup2.hkl |
CCDC reference: 175358
Key indicators
- Single-crystal X-ray study
- T = 200 K
- Mean (C-C) = 0.003 Å
- R factor = 0.042
- wR factor = 0.118
- Data-to-parameter ratio = 12.2
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
The previously unknown 4-(1-chloroethyl)-7-hydroxycoumarin, (II), was prepared by the addition of resorcinol (25.41 g, 0.231 mol) and ethyl 2-(2-chloropropionyl)-2-ethoxycarbonyl acetate (58.0 g, 0.231 mol) to ice-cooled concentrated H2SO4 (45 ml). The reaction mixture was maintained at room temperature for 20 h and ice-cooled water was added. (II) precipitated out, was filtered off and crystallized from alcohol as colourless needles (16.5 g, 32% yield), m.p. 429–431 K. The title compound (I) (560 mg, 91% yield) was obtained by the acetylation of (II) (500 mg, 0.228 mol) using acetic anhydride and pyridine. It crystallized from ethyl acetate/petroleum ether as colourless needles, m.p. 410 K.
The temperature of the crystal during the X-ray diffraction experiment was controlled using an Oxford Cryosystems Cryostream Cooler (Cosier & Glazer, 1986). H atoms were added at calculated positions and refined using a riding model. Anisotropic displacement parameters were used for all non-H atoms; H atoms were given isotropic displacement parameters equal to 1.2 (or 1.5 for methyl H atoms) times the equivalent isotropic displacement parameter of their parent atoms.
Data collection: SMART (Siemens, 1994); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXTL/PC (Siemens, 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC; software used to prepare material for publication: SHELXTL/PC.
Fig. 1. View of the title molecule showing the atomic numbering. Displacement ellipsoids are drawn at the 50% probability level for non-H atoms. H atoms are shown as spheres of arbitrary radii. |
C13H11ClO4 | Z = 2 |
Mr = 266.67 | F(000) = 276 |
Triclinic, P1 | Dx = 1.480 Mg m−3 |
a = 4.1204 (6) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.7106 (17) Å | Cell parameters from 1852 reflections |
c = 13.842 (2) Å | θ = 1.5–25.1° |
α = 97.450 (4)° | µ = 0.32 mm−1 |
β = 94.291 (4)° | T = 200 K |
γ = 97.184 (4)° | Plate, colourless |
V = 598.39 (16) Å3 | 0.40 × 0.24 × 0.06 mm |
Siemens SMART CCD area-detector diffractometer | 2010 independent reflections |
Radiation source: normal-focus sealed tube | 1570 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
Detector resolution: 8.192 pixels mm-1 | θmax = 25.1°, θmin = 1.5° |
ω scans | h = −4→4 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −8→12 |
Tmin = 0.882, Tmax = 0.981 | l = −16→13 |
2931 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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.118 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0746P)2] where P = (Fo2 + 2Fc2)/3 |
2010 reflections | (Δ/σ)max < 0.001 |
165 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
C13H11ClO4 | γ = 97.184 (4)° |
Mr = 266.67 | V = 598.39 (16) Å3 |
Triclinic, P1 | Z = 2 |
a = 4.1204 (6) Å | Mo Kα radiation |
b = 10.7106 (17) Å | µ = 0.32 mm−1 |
c = 13.842 (2) Å | T = 200 K |
α = 97.450 (4)° | 0.40 × 0.24 × 0.06 mm |
β = 94.291 (4)° |
Siemens SMART CCD area-detector diffractometer | 2010 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1570 reflections with I > 2σ(I) |
Tmin = 0.882, Tmax = 0.981 | Rint = 0.017 |
2931 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.118 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.27 e Å−3 |
2010 reflections | Δρmin = −0.22 e Å−3 |
165 parameters |
Experimental. Spectroscopic data: UV (MeOH) λmax(nm): 317, 284 and 202; IR(KBr) νmax/cm-1: 2925, 2372, 1780, 1725, 1618, 1375, 1267, 1208, 1135, 1008, 879, 722, 652 and 608; 1H NMR (300 MHz, CDCl3): δ 1.91 (3H, d, J = 6.7 Hz, C-2'H), 2.34 (3H, s, OCOCH3), 5.26 (1H, q, J = 6.7 Hz, C-1'H), 6.59 (1H, s, C-3H), 7.11 (1H, dd, J = 8.7 Hz, J = 2.2 Hz, C-6H), 7.16 (1H, d, J = 2.2 Hz, C-8H) and 7.75 (1H, d, J = 8.7 Hz, C-5H); 13C NMR (75 MHz, CDCl3): δ 21.52 (C-2'), 23.97 (CH3CO), 51.76 (C-1'), 111.37, 113.24, 118.73 and 125.61 (C-3, C-6, C-8, and C-10), 153.64, 154.16 and 155.03 (C-4, C-5, C-7 and C-9), 160.77 (C-2) and 169.03 (CH3CO); EIMS, m/z (% rel. int.): 267 [M+](10), 224 (24), 196 (11), 189 (18), 161 (100), 149 (4), 139 (4), 131 (16), 115 (14), 103 (32), 89 (15), 77 (37), 63(250 and 51 (31). |
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 | ||
Cl1 | 0.14201 (15) | 0.53214 (6) | 0.35411 (5) | 0.0381 (2) | |
O1 | 0.1272 (4) | 0.97031 (15) | 0.23696 (11) | 0.0313 (4) | |
O2 | −0.0669 (4) | 1.06399 (17) | 0.36699 (12) | 0.0424 (5) | |
O3 | 0.5333 (4) | 0.79658 (17) | −0.05180 (11) | 0.0380 (5) | |
O4 | 0.1831 (6) | 0.6210 (2) | −0.10865 (14) | 0.0648 (7) | |
C2 | 0.0688 (6) | 0.9766 (2) | 0.33315 (17) | 0.0301 (6) | |
C3 | 0.1717 (5) | 0.8785 (2) | 0.38602 (17) | 0.0288 (5) | |
H3A | 0.1405 | 0.8829 | 0.4536 | 0.035* | |
C4 | 0.3103 (5) | 0.7809 (2) | 0.34296 (16) | 0.0255 (5) | |
C5 | 0.5160 (5) | 0.6815 (2) | 0.18604 (17) | 0.0307 (6) | |
H5A | 0.5829 | 0.6136 | 0.2170 | 0.037* | |
C6 | 0.5667 (6) | 0.6851 (2) | 0.08929 (17) | 0.0324 (6) | |
H6A | 0.6660 | 0.6205 | 0.0536 | 0.039* | |
C7 | 0.4696 (6) | 0.7850 (2) | 0.04503 (16) | 0.0321 (6) | |
C8 | 0.3268 (6) | 0.8801 (2) | 0.09454 (16) | 0.0311 (6) | |
H8A | 0.2641 | 0.9484 | 0.0631 | 0.037* | |
C9 | 0.2770 (5) | 0.8737 (2) | 0.19140 (16) | 0.0270 (5) | |
C10 | 0.3681 (5) | 0.7755 (2) | 0.24028 (16) | 0.0255 (5) | |
C11 | 0.3726 (6) | 0.7071 (2) | −0.12457 (17) | 0.0355 (6) | |
C12 | 0.4652 (7) | 0.7363 (3) | −0.22172 (18) | 0.0429 (7) | |
H12A | 0.4231 | 0.6585 | −0.2691 | 0.064* | |
H12B | 0.6990 | 0.7701 | −0.2166 | 0.064* | |
H12C | 0.3344 | 0.7996 | −0.2435 | 0.064* | |
C1' | 0.4119 (5) | 0.6784 (2) | 0.39946 (16) | 0.0281 (5) | |
H1'A | 0.6398 | 0.6650 | 0.3845 | 0.034* | |
C2' | 0.4116 (6) | 0.7044 (2) | 0.50969 (16) | 0.0332 (6) | |
H2'A | 0.5541 | 0.7841 | 0.5346 | 0.050* | |
H2'B | 0.4934 | 0.6345 | 0.5391 | 0.050* | |
H2'C | 0.1873 | 0.7114 | 0.5267 | 0.050* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0396 (4) | 0.0272 (4) | 0.0482 (4) | 0.0074 (3) | 0.0032 (3) | 0.0050 (3) |
O1 | 0.0395 (9) | 0.0274 (9) | 0.0290 (10) | 0.0105 (8) | 0.0046 (7) | 0.0050 (7) |
O2 | 0.0588 (12) | 0.0343 (11) | 0.0387 (10) | 0.0221 (9) | 0.0111 (9) | 0.0037 (8) |
O3 | 0.0516 (11) | 0.0362 (10) | 0.0238 (9) | −0.0028 (8) | 0.0074 (8) | 0.0022 (7) |
O4 | 0.0863 (16) | 0.0591 (15) | 0.0378 (12) | −0.0275 (13) | −0.0014 (10) | 0.0054 (10) |
C2 | 0.0342 (13) | 0.0251 (13) | 0.0301 (13) | 0.0034 (11) | 0.0034 (10) | 0.0008 (10) |
C3 | 0.0308 (12) | 0.0317 (13) | 0.0243 (12) | 0.0050 (11) | 0.0027 (10) | 0.0043 (10) |
C4 | 0.0204 (11) | 0.0270 (13) | 0.0283 (12) | 0.0024 (10) | −0.0001 (9) | 0.0032 (10) |
C5 | 0.0311 (12) | 0.0294 (14) | 0.0314 (14) | 0.0059 (11) | 0.0005 (10) | 0.0033 (10) |
C6 | 0.0349 (13) | 0.0334 (14) | 0.0284 (13) | 0.0062 (11) | 0.0052 (10) | −0.0007 (11) |
C7 | 0.0323 (13) | 0.0356 (15) | 0.0256 (13) | −0.0039 (11) | 0.0027 (10) | 0.0016 (11) |
C8 | 0.0367 (13) | 0.0268 (13) | 0.0294 (13) | 0.0028 (11) | −0.0001 (10) | 0.0048 (10) |
C9 | 0.0262 (12) | 0.0247 (12) | 0.0287 (13) | 0.0035 (10) | 0.0003 (9) | 0.0000 (10) |
C10 | 0.0232 (11) | 0.0272 (13) | 0.0252 (12) | 0.0029 (10) | −0.0010 (9) | 0.0028 (10) |
C11 | 0.0444 (15) | 0.0304 (15) | 0.0308 (15) | 0.0070 (12) | 0.0022 (11) | 0.0002 (11) |
C12 | 0.0577 (17) | 0.0417 (17) | 0.0290 (14) | 0.0082 (14) | 0.0069 (12) | 0.0005 (12) |
C1' | 0.0260 (12) | 0.0299 (13) | 0.0296 (13) | 0.0073 (10) | 0.0028 (10) | 0.0045 (10) |
C2' | 0.0403 (13) | 0.0377 (15) | 0.0249 (13) | 0.0149 (12) | 0.0008 (10) | 0.0083 (11) |
Cl1—C1' | 1.814 (2) | C6—C7 | 1.386 (4) |
O1—C2 | 1.365 (3) | C6—H6A | 0.950 |
O1—C9 | 1.378 (3) | C7—C8 | 1.372 (3) |
O2—C2 | 1.210 (3) | C8—C9 | 1.381 (3) |
O3—C11 | 1.365 (3) | C8—H8A | 0.9500 |
O3—C7 | 1.403 (3) | C9—C10 | 1.396 (3) |
O4—C11 | 1.186 (3) | C11—C12 | 1.486 (3) |
C2—C3 | 1.444 (3) | C12—H12A | 0.980 |
C3—C4 | 1.346 (3) | C12—H12B | 0.980 |
C3—H3A | 0.950 | C12—H12C | 0.980 |
C4—C10 | 1.454 (3) | C1'—C2' | 1.515 (3) |
C4—C1' | 1.510 (3) | C1'—H1'A | 1.000 |
C5—C6 | 1.375 (3) | C2'—H2'A | 0.980 |
C5—C10 | 1.405 (3) | C2'—H2'B | 0.980 |
C5—H5A | 0.950 | C2'—H2'C | 0.980 |
C2—O1—C9 | 121.49 (18) | C8—C9—C10 | 122.7 (2) |
C11—O3—C7 | 118.12 (19) | C9—C10—C5 | 116.7 (2) |
O2—C2—O1 | 117.1 (2) | C9—C10—C4 | 117.6 (2) |
O2—C2—C3 | 125.3 (2) | C5—C10—C4 | 125.7 (2) |
O1—C2—C3 | 117.6 (2) | O4—C11—O3 | 122.4 (2) |
C4—C3—C2 | 122.4 (2) | O4—C11—C12 | 127.1 (2) |
C4—C3—H3A | 118.8 | O3—C11—C12 | 110.5 (2) |
C2—C3—H3A | 118.8 | C11—C12—H12A | 109.5 |
C3—C4—C10 | 119.1 (2) | C11—C12—H12B | 109.5 |
C3—C4—C1' | 121.4 (2) | H12A—C12—H12B | 109.5 |
C10—C4—C1' | 119.45 (19) | C11—C12—H12C | 109.5 |
C6—C5—C10 | 121.8 (2) | H12A—C12—H12C | 109.5 |
C6—C5—H5A | 119.1 | H12B—C12—H12C | 109.5 |
C10—C5—H5A | 119.1 | C4—C1'—C2' | 116.3 (2) |
C5—C6—C7 | 118.5 (2) | C4—C1'—Cl1 | 108.00 (15) |
C5—C6—H6A | 120.7 | C2'—C1'—Cl1 | 109.01 (17) |
C7—C6—H6A | 120.7 | C4—C1'—H1'A | 107.7 |
C8—C7—C6 | 122.2 (2) | C2'—C1'—H1'A | 107.7 |
C8—C7—O3 | 117.1 (2) | Cl1—C1'—H1'A | 107.7 |
C6—C7—O3 | 120.5 (2) | C1'—C2'—H2'A | 109.5 |
C7—C8—C9 | 118.0 (2) | C1'—C2'—H2'B | 109.5 |
C7—C8—H8A | 121.0 | H2'A—C2'—H2'B | 109.5 |
C9—C8—H8A | 121.0 | C1'—C2'—H2'C | 109.5 |
O1—C9—C8 | 115.5 (2) | H2'A—C2'—H2'C | 109.5 |
O1—C9—C10 | 121.8 (2) | H2'B—C2'—H2'C | 109.5 |
C9—O1—C2—O2 | −179.3 (2) | O1—C9—C10—C5 | 179.36 (19) |
C9—O1—C2—C3 | 0.4 (3) | C8—C9—C10—C5 | 0.1 (3) |
O2—C2—C3—C4 | 177.4 (2) | O1—C9—C10—C4 | −2.2 (3) |
O1—C2—C3—C4 | −2.3 (3) | C8—C9—C10—C4 | 178.5 (2) |
C2—C3—C4—C10 | 1.9 (3) | C6—C5—C10—C9 | −0.5 (3) |
C2—C3—C4—C1' | −179.2 (2) | C6—C5—C10—C4 | −178.8 (2) |
C10—C5—C6—C7 | 0.3 (4) | C3—C4—C10—C9 | 0.4 (3) |
C5—C6—C7—C8 | 0.3 (4) | C1'—C4—C10—C9 | −178.62 (19) |
C5—C6—C7—O3 | 176.3 (2) | C3—C4—C10—C5 | 178.6 (2) |
C11—O3—C7—C8 | −116.4 (2) | C1'—C4—C10—C5 | −0.4 (3) |
C11—O3—C7—C6 | 67.4 (3) | C7—O3—C11—O4 | 0.1 (4) |
C6—C7—C8—C9 | −0.7 (3) | C7—O3—C11—C12 | 178.8 (2) |
O3—C7—C8—C9 | −176.9 (2) | C3—C4—C1'—C2' | −11.5 (3) |
C2—O1—C9—C8 | −178.82 (19) | C10—C4—C1'—C2' | 167.4 (2) |
C2—O1—C9—C10 | 1.8 (3) | C3—C4—C1'—Cl1 | 111.3 (2) |
C7—C8—C9—O1 | −178.82 (19) | C10—C4—C1'—Cl1 | −69.7 (2) |
C7—C8—C9—C10 | 0.5 (3) |
Experimental details
Crystal data | |
Chemical formula | C13H11ClO4 |
Mr | 266.67 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 200 |
a, b, c (Å) | 4.1204 (6), 10.7106 (17), 13.842 (2) |
α, β, γ (°) | 97.450 (4), 94.291 (4), 97.184 (4) |
V (Å3) | 598.39 (16) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.32 |
Crystal size (mm) | 0.40 × 0.24 × 0.06 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.882, 0.981 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2931, 2010, 1570 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.118, 1.00 |
No. of reflections | 2010 |
No. of parameters | 165 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.22 |
Computer programs: SMART (Siemens, 1994), SAINT (Siemens, 1995), SAINT, SHELXTL/PC (Siemens, 1994), SHELXL97 (Sheldrick, 1997), SHELXTL/PC.
C11—O3—C7—C8 | −116.4 (2) | C10—C4—C1'—C2' | 167.4 (2) |
C7—O3—C11—O4 | 0.1 (4) | C10—C4—C1'—Cl1 | −69.7 (2) |
C7—O3—C11—C12 | 178.8 (2) |
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Coumarins are of considerable general importance (Campbell, 1959) and are prominent in natural products chemistry (Dean, 1963; Murray et al., 1982). They have been found to possess a wide variety of uses in the perfumery industry, as flavour enhancers, sunscreens, laser dyes (Khalfan et al., 1987) and in the pharmaceutical industry (Hooper et al., 1982; Morris & Russell, 1971). Our recent work showed pronounced activity of 4-methylcoumarins against Herpes simplex and Vascular stomatitis viruses (Parmar et al., 1996). Encouraged by these findings, we have synthesized a series of coumarins for structure–activity studies. This paper reports the synthesis and structure of the new coumarin, 7-acetoxy-4-(1-chloroethyl)coumarin, (I).
The molecular structure of (I) is illustrated in Fig. 1. A l l bond lengths and angles are largely unremarkable. The inclinations of the planes of the acetoxy and chloroethyl substituents (defined by the O3/C11/O4/C12 and Cl1/C1'/C2' atoms) with respect to the coumarin ring system are 65.76 (7) and 63.52 (9)°, respectively.