organic compounds
6-Methoxy-4-methyl-2H-chromen-2-one
aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and bSchool of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, People's Republic of China
*Correspondence e-mail: hkfun@usm.my
The whole molecule of the title coumarin derivative, C11H10O3, is approximately planar, with a maximum deviation of 0.116 (3) Å from the least-squares plane defined by all non-H atoms. In the crystal, adjacent molecules are linked into chains along [011] via intermolecular C—H⋯O hydrogen bonds.
Related literature
For general background to and applications of the title coumarin derivative, see: Grimm & Girard (2006); Maresca et al. (2010); Parvez & Hadda (2010); Raj & Wenge (1998); Yao & Deng (2000). For related coumarin structures, see: Asad et al. (2010); Saidi et al. (2007). For bond-length data, see: Allen et al. (1987).
Experimental
Crystal data
|
Refinement
|
Data collection: APEX2 (Bruker, 2009); cell SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009).
Supporting information
https://doi.org/10.1107/S1600536810051652/is2642sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810051652/is2642Isup2.hkl
The title compound was obtained in the photoreaction of 4-(chloromethyl)-6-methoxy-2H-chromen-2-one in visible light. The compound was purified by flash
Good quality single crystals suitable for X-ray analysis were obtained from slow evaporation of a 1:1 solution of acetone and petroleum ether.All hydrogen atoms were placed in their calculated positions, with C—H = 0.93 or 0.96 Å, and refined using a riding model, with Uiso(H) = 1.2 or 1.5Ueq(C). The rotating group model was applied to the methyl groups.
Coumarin is the mother-nuclear structure of many natural products and the importance of coumarin and its analogous compounds which exhibit useful pharmaceutical activities are well-known. Some substituted coumarin and their derivatives have been reported as food constituents, anti-oxidants, stabilizers, immunomodulatory substances, inhibitors of some enzymes, fluorescent markers in analysis, lasers, and in clinical use (Parvez & Hadda, 2010; Maresca et al., 2010; Grimm & Girard, 2006). In addition, 4-substituted
have shown many pharmaceutical activities such as anti-bacterial, anti-fungal, anthelmintic, insecticidal, hypnotic and other biological activities, and most precisely 4-methyl-coumarins have been correlated to several beneficial pharmacological effects too (Yao & Deng, 2000; Raj & Wenge, 1998). In view of the importance of the coumarin derivatives, the of the title compound is reported in this paper.The title coumarin derivative (Fig. 1) has an approximately planar molecular structure, with the methoxy-O atom (C10) deviating -0.116 (3) Å from the least-squares plane defined by all non-hydrogen atoms. All bond lengths (Allen et al., 1987) and angles are within normal ranges and are comparable to those related coumarin structures (Asad et al., 2010; Saidi et al., 2007). In the crystal packing (Fig. 2), adjacent molecules are linked into one-dimensional chains propagating along the [011] direction via intermolecular C8—H8A···O2 hydrogen bonds.
For general background to and applications of the title coumarin derivative, see: Grimm & Girard (2006); Maresca et al. (2010); Parvez & Hadda (2010); Raj & Wenge (1998); Yao & Deng (2000). For related coumarin structures, see: Asad et al. (2010); Saidi et al. (2007). For bond-length data, see: Allen et al. (1987).
Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).C11H10O3 | Z = 2 |
Mr = 190.19 | F(000) = 200 |
Triclinic, P1 | Dx = 1.372 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.2554 (2) Å | Cell parameters from 3241 reflections |
b = 8.0880 (2) Å | θ = 2.6–30.0° |
c = 8.5450 (2) Å | µ = 0.10 mm−1 |
α = 112.988 (1)° | T = 293 K |
β = 90.234 (1)° | Plate, yellow |
γ = 93.873 (1)° | 0.40 × 0.35 × 0.06 mm |
V = 460.31 (2) Å3 |
Bruker SMART APEXII CCD area-detector diffractometer | 2793 independent reflections |
Radiation source: fine-focus sealed tube | 1675 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
φ and ω scans | θmax = 30.6°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −10→10 |
Tmin = 0.962, Tmax = 0.994 | k = −11→11 |
10271 measured reflections | l = −11→12 |
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)] = 0.066 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.218 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0991P)2 + 0.086P] where P = (Fo2 + 2Fc2)/3 |
2793 reflections | (Δ/σ)max < 0.001 |
129 parameters | Δρmax = 0.70 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C11H10O3 | γ = 93.873 (1)° |
Mr = 190.19 | V = 460.31 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.2554 (2) Å | Mo Kα radiation |
b = 8.0880 (2) Å | µ = 0.10 mm−1 |
c = 8.5450 (2) Å | T = 293 K |
α = 112.988 (1)° | 0.40 × 0.35 × 0.06 mm |
β = 90.234 (1)° |
Bruker SMART APEXII CCD area-detector diffractometer | 2793 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 1675 reflections with I > 2σ(I) |
Tmin = 0.962, Tmax = 0.994 | Rint = 0.021 |
10271 measured reflections |
R[F2 > 2σ(F2)] = 0.066 | 0 restraints |
wR(F2) = 0.218 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.70 e Å−3 |
2793 reflections | Δρmin = −0.20 e Å−3 |
129 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 | ||
O1 | 0.19469 (16) | 0.53037 (17) | 0.87871 (16) | 0.0508 (4) | |
O2 | 0.6197 (2) | 1.09931 (18) | 1.34611 (17) | 0.0638 (4) | |
O3 | 0.1468 (2) | 0.2933 (2) | 0.63843 (19) | 0.0679 (5) | |
C1 | 0.3087 (2) | 0.6718 (2) | 0.9894 (2) | 0.0417 (4) | |
C2 | 0.2327 (3) | 0.7819 (3) | 1.1396 (2) | 0.0512 (5) | |
H2A | 0.1101 | 0.7603 | 1.1617 | 0.061* | |
C3 | 0.3402 (3) | 0.9229 (3) | 1.2551 (2) | 0.0527 (5) | |
H3A | 0.2901 | 0.9974 | 1.3559 | 0.063* | |
C4 | 0.5250 (3) | 0.9555 (2) | 1.2222 (2) | 0.0472 (4) | |
C5 | 0.5999 (2) | 0.8469 (2) | 1.0726 (2) | 0.0438 (4) | |
H5A | 0.7225 | 0.8696 | 1.0510 | 0.053* | |
C6 | 0.4917 (2) | 0.7016 (2) | 0.9521 (2) | 0.0384 (4) | |
C7 | 0.5603 (2) | 0.5807 (2) | 0.7919 (2) | 0.0414 (4) | |
C8 | 0.4450 (2) | 0.4441 (2) | 0.6875 (2) | 0.0463 (4) | |
H8A | 0.4895 | 0.3663 | 0.5851 | 0.056* | |
C9 | 0.2564 (3) | 0.4127 (2) | 0.7264 (2) | 0.0475 (4) | |
C10 | 0.8119 (3) | 1.1270 (3) | 1.3272 (3) | 0.0695 (6) | |
H10C | 0.8624 | 1.2287 | 1.4242 | 0.104* | |
H10D | 0.8317 | 1.1495 | 1.2260 | 0.104* | |
H10A | 0.8718 | 1.0217 | 1.3187 | 0.104* | |
C11 | 0.7558 (3) | 0.6091 (3) | 0.7459 (3) | 0.0573 (5) | |
H11D | 0.7824 | 0.5119 | 0.6419 | 0.086* | |
H11A | 0.8387 | 0.6128 | 0.8352 | 0.086* | |
H11B | 0.7713 | 0.7209 | 0.7311 | 0.086* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0352 (6) | 0.0577 (8) | 0.0514 (8) | 0.0001 (5) | 0.0021 (5) | 0.0132 (6) |
O2 | 0.0694 (10) | 0.0531 (8) | 0.0488 (8) | 0.0036 (7) | −0.0011 (7) | −0.0017 (6) |
O3 | 0.0523 (8) | 0.0717 (9) | 0.0622 (9) | −0.0130 (7) | −0.0092 (7) | 0.0103 (8) |
C1 | 0.0368 (8) | 0.0467 (9) | 0.0413 (9) | 0.0056 (7) | 0.0016 (7) | 0.0164 (7) |
C2 | 0.0411 (9) | 0.0600 (11) | 0.0516 (11) | 0.0141 (8) | 0.0130 (8) | 0.0193 (9) |
C3 | 0.0579 (11) | 0.0553 (11) | 0.0413 (10) | 0.0187 (9) | 0.0120 (8) | 0.0125 (8) |
C4 | 0.0541 (11) | 0.0434 (9) | 0.0394 (9) | 0.0087 (8) | −0.0003 (8) | 0.0104 (7) |
C5 | 0.0400 (9) | 0.0467 (9) | 0.0416 (9) | 0.0039 (7) | 0.0031 (7) | 0.0139 (7) |
C6 | 0.0362 (8) | 0.0418 (8) | 0.0367 (8) | 0.0073 (6) | 0.0023 (6) | 0.0141 (7) |
C7 | 0.0384 (9) | 0.0457 (9) | 0.0387 (9) | 0.0068 (7) | 0.0042 (7) | 0.0145 (7) |
C8 | 0.0461 (10) | 0.0480 (9) | 0.0388 (9) | 0.0059 (7) | 0.0031 (7) | 0.0102 (7) |
C9 | 0.0429 (9) | 0.0511 (10) | 0.0440 (10) | 0.0006 (8) | −0.0033 (7) | 0.0144 (8) |
C10 | 0.0654 (14) | 0.0596 (12) | 0.0646 (14) | −0.0073 (10) | −0.0111 (11) | 0.0060 (10) |
C11 | 0.0466 (10) | 0.0633 (12) | 0.0508 (11) | 0.0045 (9) | 0.0119 (8) | 0.0100 (9) |
O1—C9 | 1.377 (2) | C5—H5A | 0.9300 |
O1—C1 | 1.381 (2) | C6—C7 | 1.450 (2) |
O2—C4 | 1.367 (2) | C7—C8 | 1.348 (2) |
O2—C10 | 1.417 (3) | C7—C11 | 1.500 (2) |
O3—C9 | 1.206 (2) | C8—C9 | 1.438 (3) |
C1—C2 | 1.387 (2) | C8—H8A | 0.9300 |
C1—C6 | 1.394 (2) | C10—H10C | 0.9600 |
C2—C3 | 1.370 (3) | C10—H10D | 0.9600 |
C2—H2A | 0.9300 | C10—H10A | 0.9600 |
C3—C4 | 1.400 (3) | C11—H11D | 0.9600 |
C3—H3A | 0.9300 | C11—H11A | 0.9600 |
C4—C5 | 1.376 (2) | C11—H11B | 0.9600 |
C5—C6 | 1.407 (2) | ||
C9—O1—C1 | 121.54 (14) | C8—C7—C11 | 121.52 (15) |
C4—O2—C10 | 117.77 (15) | C6—C7—C11 | 119.97 (15) |
O1—C1—C2 | 116.85 (15) | C7—C8—C9 | 123.28 (16) |
O1—C1—C6 | 121.51 (15) | C7—C8—H8A | 118.4 |
C2—C1—C6 | 121.65 (16) | C9—C8—H8A | 118.4 |
C3—C2—C1 | 119.36 (17) | O3—C9—O1 | 116.69 (17) |
C3—C2—H2A | 120.3 | O3—C9—C8 | 126.37 (18) |
C1—C2—H2A | 120.3 | O1—C9—C8 | 116.95 (15) |
C2—C3—C4 | 120.41 (16) | O2—C10—H10C | 109.5 |
C2—C3—H3A | 119.8 | O2—C10—H10D | 109.5 |
C4—C3—H3A | 119.8 | H10C—C10—H10D | 109.5 |
O2—C4—C5 | 124.24 (17) | O2—C10—H10A | 109.5 |
O2—C4—C3 | 115.58 (16) | H10C—C10—H10A | 109.5 |
C5—C4—C3 | 120.18 (17) | H10D—C10—H10A | 109.5 |
C4—C5—C6 | 120.30 (16) | C7—C11—H11D | 109.5 |
C4—C5—H5A | 119.8 | C7—C11—H11A | 109.5 |
C6—C5—H5A | 119.8 | H11D—C11—H11A | 109.5 |
C1—C6—C5 | 118.10 (15) | C7—C11—H11B | 109.5 |
C1—C6—C7 | 118.22 (15) | H11D—C11—H11B | 109.5 |
C5—C6—C7 | 123.68 (15) | H11A—C11—H11B | 109.5 |
C8—C7—C6 | 118.51 (15) | ||
C9—O1—C1—C2 | −179.81 (14) | C2—C1—C6—C7 | −179.76 (15) |
C9—O1—C1—C6 | −0.2 (3) | C4—C5—C6—C1 | −0.1 (3) |
O1—C1—C2—C3 | 179.14 (15) | C4—C5—C6—C7 | −179.79 (14) |
C6—C1—C2—C3 | −0.4 (3) | C1—C6—C7—C8 | −0.8 (2) |
C1—C2—C3—C4 | −0.1 (3) | C5—C6—C7—C8 | 178.89 (15) |
C10—O2—C4—C5 | −6.8 (3) | C1—C6—C7—C11 | 179.31 (16) |
C10—O2—C4—C3 | 173.65 (17) | C5—C6—C7—C11 | −1.0 (3) |
C2—C3—C4—O2 | −179.84 (16) | C6—C7—C8—C9 | 0.4 (3) |
C2—C3—C4—C5 | 0.6 (3) | C11—C7—C8—C9 | −179.67 (17) |
O2—C4—C5—C6 | −179.97 (15) | C1—O1—C9—O3 | 179.91 (15) |
C3—C4—C5—C6 | −0.4 (3) | C1—O1—C9—C8 | −0.2 (3) |
O1—C1—C6—C5 | −178.98 (14) | C7—C8—C9—O3 | 179.99 (18) |
C2—C1—C6—C5 | 0.6 (3) | C7—C8—C9—O1 | 0.1 (3) |
O1—C1—C6—C7 | 0.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8A···O2i | 0.93 | 2.56 | 3.471 (2) | 165 |
Symmetry code: (i) x, y−1, z−1. |
Experimental details
Crystal data | |
Chemical formula | C11H10O3 |
Mr | 190.19 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.2554 (2), 8.0880 (2), 8.5450 (2) |
α, β, γ (°) | 112.988 (1), 90.234 (1), 93.873 (1) |
V (Å3) | 460.31 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.40 × 0.35 × 0.06 |
Data collection | |
Diffractometer | Bruker SMART APEXII CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2009) |
Tmin, Tmax | 0.962, 0.994 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10271, 2793, 1675 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.716 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.066, 0.218, 1.09 |
No. of reflections | 2793 |
No. of parameters | 129 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.70, −0.20 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8A···O2i | 0.93 | 2.56 | 3.471 (2) | 165 |
Symmetry code: (i) x, y−1, z−1. |
Acknowledgements
HKF and JHG thank Universiti Sains Malaysia (USM) for a Research University Grant (No. 1001/PFIZIK/811160). Financial support from the Fok Ying Tung Education Foundation (114012) is also acknowledged.
References
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Coumarin is the mother-nuclear structure of many natural products and the importance of coumarin and its analogous compounds which exhibit useful pharmaceutical activities are well-known. Some substituted coumarin and their derivatives have been reported as food constituents, anti-oxidants, stabilizers, immunomodulatory substances, inhibitors of some enzymes, fluorescent markers in analysis, lasers, and in clinical use (Parvez & Hadda, 2010; Maresca et al., 2010; Grimm & Girard, 2006). In addition, 4-substituted coumarins have shown many pharmaceutical activities such as anti-bacterial, anti-fungal, anthelmintic, insecticidal, hypnotic and other biological activities, and most precisely 4-methyl-coumarins have been correlated to several beneficial pharmacological effects too (Yao & Deng, 2000; Raj & Wenge, 1998). In view of the importance of the coumarin derivatives, the crystal structure of the title compound is reported in this paper.
The title coumarin derivative (Fig. 1) has an approximately planar molecular structure, with the methoxy-O atom (C10) deviating -0.116 (3) Å from the least-squares plane defined by all non-hydrogen atoms. All bond lengths (Allen et al., 1987) and angles are within normal ranges and are comparable to those related coumarin structures (Asad et al., 2010; Saidi et al., 2007). In the crystal packing (Fig. 2), adjacent molecules are linked into one-dimensional chains propagating along the [011] direction via intermolecular C8—H8A···O2 hydrogen bonds.