journal menu
organic compounds
Supporting information
 | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807032631/at2334sup1.cif |
 | Structure factor file (CIF format) https://doi.org/10.1107/S1600536807032631/at2334Isup2.hkl |
CCDC reference: 657807
![[sigma]](http://journals.iucr.org/logos/entities/sigma_rmgif.gif){kind=small}
(C-C) = 0.004 Å
Alert level C
Alert level G
The title compound was prepared by solvent free pechmann reaction with sulfuric acid as catalyst. To a solution of p-cresol (2.3 g, 20 mmol) and ethyl acetoacetate (2.6 g, 20 mmol), the 75% sulfuric acid(50 ml) was slowly added at 283 K with stirring for 1 h. Then the mixture was moved to oil-bath and continuously stirred for 18 h at 318 K. The reaction mixture was poured into ice-water. The solid obtained was filtered off, washed with 5% sodium hydroxide solution until no color appears in the aqueous layer and dried at room temperature. The products were further purified by recrystallizing the crude product with methanol. Colourless crystals of (I) suitable for X-ray structure analysis were obtained by slowly evaporating from dichloromethane and petroleum ether.
All H atoms were positioned geometrically and refined using riding on their parent atoms, with C—H = 0.93Å and Uiso(H) = 1.2Ueq for Csp2—H, and C—H = 0.96Å and Uiso(H) = 1.5Ueq for Csp3—H.
Coumarins and their derivatives form an important class of compounds which are widely used as additives in food, perfumes, cosmetics, pharmaceuticals and optical brighteners (Chavan et al., 2002; Alexander et al., 2005; Smitha et al., 2004). We report here the crystal structure of the title compound (I).
In the molecule of (I), the torsion angles of C10—C4—C5—C6 and C11—C7—C8—C9 are 179.3 (2)° and 179.6 (3)°, repectively, indicating that the two C atoms of methyl groups don't significantly deviate from the coumarin moiety. So the whole molecule except the H atoms assumes a planar structrue with an r.m.s deviation of 0.0202 (3) Å. C9 atom of the carbonyl group has a distorted trigonal geometry with O2—C9—O1 [116.3 (2)°] and O2—C9—C8 [126.5 (3)°] deviating significantly from the ideal sp2 value of 120°.
For related literature, see: Alexander et al. (2005); Chavan et al. (2002); Smitha & Reddy (2004).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
![[Figure 1]](http://journals.iucr.org/e/issues/2007/08/00/at2334/at2334fig1thm.gif)
| Fig. 1. View of the molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 35% probability level. |
| C11H10O2 | F(000) = 368 |
| Mr = 174.19 | Dx = 1.371 Mg m−3 |
| Monoclinic, P21/c | Melting point: 428 K |
| Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
| a = 7.056 (4) Å | Cell parameters from 786 reflections |
| b = 8.854 (4) Å | θ = 2.8–25.6° |
| c = 13.976 (6) Å | µ = 0.09 mm−1 |
| β = 104.80 (2)° | T = 293 K |
| V = 844.2 (7) Å3 | Needle, colourless |
| Z = 4 | 0.16 × 0.14 × 0.08 mm |
| Bruker SMART CCD area-detector diffractometer | 1500 independent reflections |
| Radiation source: fine-focus sealed tube | 788 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.045 |
| φ and ω scans | θmax = 25.0°, θmin = 2.8° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→5 |
| Tmin = 0.985, Tmax = 0.993 | k = −10→8 |
| 4292 measured reflections | l = −16→16 |
| 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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.156 | H-atom parameters constrained |
| S = 1.01 | w = 1/[σ2(Fo2) + (0.0629P)2 + 0.2401P] where P = (Fo2 + 2Fc2)/3 |
| 1500 reflections | (Δ/σ)max = 0.003 |
| 120 parameters | Δρmax = 0.18 e Å−3 |
| 0 restraints | Δρmin = −0.18 e Å−3 |
| C11H10O2 | V = 844.2 (7) Å3 |
| Mr = 174.19 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 7.056 (4) Å | µ = 0.09 mm−1 |
| b = 8.854 (4) Å | T = 293 K |
| c = 13.976 (6) Å | 0.16 × 0.14 × 0.08 mm |
| β = 104.80 (2)° |
| Bruker SMART CCD area-detector diffractometer | 1500 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 788 reflections with I > 2σ(I) |
| Tmin = 0.985, Tmax = 0.993 | Rint = 0.045 |
| 4292 measured reflections |
| R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
| wR(F2) = 0.156 | H-atom parameters constrained |
| S = 1.01 | Δρmax = 0.18 e Å−3 |
| 1500 reflections | Δρmin = −0.18 e Å−3 |
| 120 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. |
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 | ||
| O1 | 0.3485 (3) | 0.56831 (19) | 1.16838 (12) | 0.0500 (5) | |
| O2 | 0.4079 (3) | 0.4494 (2) | 1.30820 (13) | 0.0703 (7) | |
| C1 | 0.2949 (4) | 0.5693 (3) | 1.06742 (17) | 0.0413 (7) | |
| C2 | 0.2896 (4) | 0.7070 (3) | 1.02378 (19) | 0.0522 (8) | |
| H2 | 0.3227 | 0.7939 | 1.0618 | 0.063* | |
| C3 | 0.2351 (4) | 0.7149 (3) | 0.9238 (2) | 0.0540 (8) | |
| H3 | 0.2297 | 0.8088 | 0.8934 | 0.065* | |
| C4 | 0.1873 (4) | 0.5878 (3) | 0.86554 (18) | 0.0465 (7) | |
| C5 | 0.1987 (4) | 0.4517 (3) | 0.91231 (17) | 0.0451 (7) | |
| H5 | 0.1682 | 0.3647 | 0.8742 | 0.054* | |
| C6 | 0.2538 (3) | 0.4381 (3) | 1.01418 (16) | 0.0377 (6) | |
| C7 | 0.2727 (4) | 0.2988 (3) | 1.06670 (18) | 0.0417 (7) | |
| C8 | 0.3269 (4) | 0.3024 (3) | 1.16491 (18) | 0.0483 (7) | |
| H8 | 0.3413 | 0.2113 | 1.1992 | 0.058* | |
| C9 | 0.3641 (4) | 0.4381 (3) | 1.21995 (19) | 0.0481 (7) | |
| C10 | 0.1255 (4) | 0.5999 (4) | 0.75576 (18) | 0.0650 (9) | |
| H10A | 0.1319 | 0.5022 | 0.7270 | 0.098* | |
| H10B | 0.2112 | 0.6683 | 0.7337 | 0.098* | |
| H10C | −0.0065 | 0.6372 | 0.7357 | 0.098* | |
| C11 | 0.2342 (5) | 0.1527 (3) | 1.01272 (19) | 0.0608 (9) | |
| H11A | 0.2636 | 0.0708 | 1.0592 | 0.091* | |
| H11B | 0.3153 | 0.1452 | 0.9673 | 0.091* | |
| H11C | 0.0988 | 0.1477 | 0.9768 | 0.091* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0636 (13) | 0.0453 (11) | 0.0393 (10) | −0.0017 (9) | 0.0098 (9) | −0.0044 (8) |
| O2 | 0.0945 (17) | 0.0780 (15) | 0.0352 (11) | −0.0032 (12) | 0.0107 (10) | −0.0027 (9) |
| C1 | 0.0390 (16) | 0.0451 (16) | 0.0401 (14) | 0.0025 (12) | 0.0104 (12) | 0.0000 (12) |
| C2 | 0.061 (2) | 0.0418 (16) | 0.0529 (17) | −0.0006 (14) | 0.0129 (14) | −0.0025 (13) |
| C3 | 0.0587 (19) | 0.0419 (17) | 0.0617 (18) | 0.0080 (14) | 0.0160 (15) | 0.0149 (14) |
| C4 | 0.0431 (16) | 0.0553 (18) | 0.0416 (14) | 0.0045 (13) | 0.0116 (12) | 0.0106 (13) |
| C5 | 0.0422 (16) | 0.0501 (17) | 0.0413 (14) | 0.0005 (12) | 0.0072 (12) | −0.0029 (12) |
| C6 | 0.0336 (14) | 0.0408 (15) | 0.0384 (14) | 0.0009 (11) | 0.0085 (11) | 0.0017 (11) |
| C7 | 0.0418 (16) | 0.0412 (16) | 0.0427 (15) | 0.0000 (12) | 0.0118 (12) | −0.0005 (11) |
| C8 | 0.0542 (18) | 0.0424 (16) | 0.0479 (16) | 0.0012 (13) | 0.0125 (13) | 0.0078 (12) |
| C9 | 0.0499 (17) | 0.0533 (18) | 0.0404 (15) | 0.0012 (13) | 0.0104 (13) | 0.0023 (13) |
| C10 | 0.063 (2) | 0.085 (2) | 0.0449 (17) | 0.0104 (17) | 0.0100 (15) | 0.0186 (15) |
| C11 | 0.081 (2) | 0.0426 (17) | 0.0579 (17) | −0.0051 (15) | 0.0167 (15) | −0.0018 (13) |
| O1—C9 | 1.349 (3) | C5—H5 | 0.9300 |
| O1—C1 | 1.364 (3) | C6—C7 | 1.425 (3) |
| O2—C9 | 1.197 (3) | C7—C8 | 1.328 (3) |
| C1—C2 | 1.359 (3) | C7—C11 | 1.487 (3) |
| C1—C6 | 1.370 (3) | C8—C9 | 1.415 (3) |
| C2—C3 | 1.353 (3) | C8—H8 | 0.9300 |
| C2—H2 | 0.9300 | C10—H10A | 0.9600 |
| C3—C4 | 1.379 (4) | C10—H10B | 0.9600 |
| C3—H3 | 0.9300 | C10—H10C | 0.9600 |
| C4—C5 | 1.363 (3) | C11—H11A | 0.9600 |
| C4—C10 | 1.488 (3) | C11—H11B | 0.9600 |
| C5—C6 | 1.382 (3) | C11—H11C | 0.9600 |
| C9—O1—C1 | 121.4 (2) | C8—C7—C11 | 120.8 (2) |
| C2—C1—O1 | 116.0 (2) | C6—C7—C11 | 120.7 (2) |
| C2—C1—C6 | 122.6 (2) | C7—C8—C9 | 123.2 (2) |
| O1—C1—C6 | 121.4 (2) | C7—C8—H8 | 118.4 |
| C3—C2—C1 | 118.5 (3) | C9—C8—H8 | 118.4 |
| C3—C2—H2 | 120.7 | O2—C9—O1 | 116.3 (2) |
| C1—C2—H2 | 120.7 | O2—C9—C8 | 126.5 (3) |
| C2—C3—C4 | 122.0 (3) | O1—C9—C8 | 117.2 (2) |
| C2—C3—H3 | 119.0 | C4—C10—H10A | 109.5 |
| C4—C3—H3 | 119.0 | C4—C10—H10B | 109.5 |
| C5—C4—C3 | 117.6 (2) | H10A—C10—H10B | 109.5 |
| C5—C4—C10 | 121.6 (3) | C4—C10—H10C | 109.5 |
| C3—C4—C10 | 120.8 (3) | H10A—C10—H10C | 109.5 |
| C4—C5—C6 | 122.5 (2) | H10B—C10—H10C | 109.5 |
| C4—C5—H5 | 118.7 | C7—C11—H11A | 109.5 |
| C6—C5—H5 | 118.7 | C7—C11—H11B | 109.5 |
| C1—C6—C5 | 116.8 (2) | H11A—C11—H11B | 109.5 |
| C1—C6—C7 | 118.4 (2) | C7—C11—H11C | 109.5 |
| C5—C6—C7 | 124.8 (2) | H11A—C11—H11C | 109.5 |
| C8—C7—C6 | 118.4 (2) | H11B—C11—H11C | 109.5 |
| C9—O1—C1—C2 | −178.2 (2) | C4—C5—C6—C1 | 0.8 (4) |
| C9—O1—C1—C6 | 0.3 (3) | C4—C5—C6—C7 | −178.4 (2) |
| O1—C1—C2—C3 | −179.2 (2) | C1—C6—C7—C8 | 0.8 (4) |
| C6—C1—C2—C3 | 2.3 (4) | C5—C6—C7—C8 | 180.0 (2) |
| C1—C2—C3—C4 | −0.7 (4) | C1—C6—C7—C11 | −178.7 (2) |
| C2—C3—C4—C5 | −0.7 (4) | C5—C6—C7—C11 | 0.5 (4) |
| C2—C3—C4—C10 | 179.2 (2) | C6—C7—C8—C9 | 1.0 (4) |
| C3—C4—C5—C6 | 0.6 (4) | C11—C7—C8—C9 | −179.6 (3) |
| C10—C4—C5—C6 | −179.3 (2) | C1—O1—C9—O2 | −178.4 (2) |
| C2—C1—C6—C5 | −2.3 (4) | C1—O1—C9—C8 | 1.5 (4) |
| O1—C1—C6—C5 | 179.3 (2) | C7—C8—C9—O2 | 177.8 (3) |
| C2—C1—C6—C7 | 177.0 (2) | C7—C8—C9—O1 | −2.1 (4) |
| O1—C1—C6—C7 | −1.4 (4) |
Experimental details
| Crystal data | |
| Chemical formula | C11H10O2 |
| Mr | 174.19 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 293 |
| a, b, c (Å) | 7.056 (4), 8.854 (4), 13.976 (6) |
| β (°) | 104.80 (2) |
| V (Å3) | 844.2 (7) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.09 |
| Crystal size (mm) | 0.16 × 0.14 × 0.08 |
| Data collection | |
| Diffractometer | Bruker SMART CCD area-detector |
| Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
| Tmin, Tmax | 0.985, 0.993 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 4292, 1500, 788 |
| Rint | 0.045 |
| (sin θ/λ)max (Å−1) | 0.595 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.156, 1.01 |
| No. of reflections | 1500 |
| No. of parameters | 120 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.18, −0.18 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
| O2—C9—O1 | 116.3 (2) | O2—C9—C8 | 126.5 (3) |
| C2—C3—C4—C10 | 179.2 (2) | C1—C6—C7—C11 | −178.7 (2) |
| C10—C4—C5—C6 | −179.3 (2) | C11—C7—C8—C9 | −179.6 (3) |
Coumarins and their derivatives form an important class of compounds which are widely used as additives in food, perfumes, cosmetics, pharmaceuticals and optical brighteners (Chavan et al., 2002; Alexander et al., 2005; Smitha et al., 2004). We report here the crystal structure of the title compound (I).
In the molecule of (I), the torsion angles of C10—C4—C5—C6 and C11—C7—C8—C9 are 179.3 (2)° and 179.6 (3)°, repectively, indicating that the two C atoms of methyl groups don't significantly deviate from the coumarin moiety. So the whole molecule except the H atoms assumes a planar structrue with an r.m.s deviation of 0.0202 (3) Å. C9 atom of the carbonyl group has a distorted trigonal geometry with O2—C9—O1 [116.3 (2)°] and O2—C9—C8 [126.5 (3)°] deviating significantly from the ideal sp2 value of 120°.