organic compounds
8-Methoxy-2H-chromene-3-carbaldehyde
aDepartment of Applied Chemistry, Dongduk Women's University, Seoul 136-714, Republic of Korea
*Correspondence e-mail: dskoh@dongduk.ac.kr
In the title molecule, C11H10O3, the fused dihydropyran ring is in a half-chair conformation with the O atom and the methylene C atom positioned 0.1318 (13) and 0.143 (2) Å, respectively, on either side of the mean plane formed by the other four atoms. In the crystal, weak C—H⋯O hydrogen bonds link molecules along [001].
Related literature
For the synthesis and biological properties of chromene derivatives, see: Mun et al. (2012); Kallikat et al. (2011); Zhang et al. (2009); Gebhardt et al. (2007); Yoon et al. (2012). For the chromene group in natural products, see: Escandón-Rivera et al. (2012); Chen et al. (2008). For related structures, see: Yusufzai et al. (2012); Betz et al. (2011); Bardajee et al. (2007).
Experimental
Crystal data
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Data collection
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Refinement
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Data collection: SMART (Bruker, 2000); cell SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Supporting information
10.1107/S1600536812047319/lh5559sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812047319/lh5559Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812047319/lh5559Isup3.cml
To a solution of 2-hydroxy-3-methoxy-benzaldehyde (1.52 g, 10 mmol) in 20 ml of 1,4-dioxane was added excess amount of acrolein (840 mg, 15 mmol) and potassium carbonate (1.4 g, 10 mmol) at room temperature. The reaction mixture was refluxed for 8 h and TLC showed no starting material of 2-hydroxy-3-methoxy-benzaldehyde. After cooling to room temperature, the mixture was poured into iced water (40 ml) and extracted with diethylether (3 × 30 ml) and combined organic layers were dried under MgSO4. Filtration, evaporation of filtrate gave residue which was purified by flash
to give the title compound (1.21 g, 82%). Recrystallization of a solution of the title compound in ethanol gave pale yellow crystals (mp: 352-353K).The H atoms were placed in calculated positions and refined as riding with C–H = 0.95 A [Uiso(H) = 1.2 Ueq(C)].
Data collection: SMART (Bruker, 2000); cell
SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C11H10O3 | F(000) = 800 |
Mr = 190.19 | Dx = 1.381 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 3190 reflections |
a = 6.8940 (6) Å | θ = 3.1–28.2° |
b = 13.2079 (11) Å | µ = 0.10 mm−1 |
c = 20.0964 (16) Å | T = 200 K |
V = 1829.9 (3) Å3 | Block, pale yellow |
Z = 8 | 0.23 × 0.21 × 0.19 mm |
Bruker SMART CCD diffractometer | 1194 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.056 |
Graphite monochromator | θmax = 28.3°, θmin = 2.0° |
ϕ and ω scans | h = −9→9 |
12690 measured reflections | k = −17→16 |
2276 independent reflections | l = −26→19 |
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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.158 | H-atom parameters constrained |
S = 0.92 | w = 1/[σ2(Fo2) + (0.0862P)2] where P = (Fo2 + 2Fc2)/3 |
2276 reflections | (Δ/σ)max = 0.001 |
128 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
C11H10O3 | V = 1829.9 (3) Å3 |
Mr = 190.19 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 6.8940 (6) Å | µ = 0.10 mm−1 |
b = 13.2079 (11) Å | T = 200 K |
c = 20.0964 (16) Å | 0.23 × 0.21 × 0.19 mm |
Bruker SMART CCD diffractometer | 1194 reflections with I > 2σ(I) |
12690 measured reflections | Rint = 0.056 |
2276 independent reflections |
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.158 | H-atom parameters constrained |
S = 0.92 | Δρmax = 0.28 e Å−3 |
2276 reflections | Δρmin = −0.28 e Å−3 |
128 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 | 0.1026 (2) | 0.40157 (12) | 0.04444 (7) | 0.0583 (5) | |
C1 | 0.1052 (3) | 0.47227 (17) | 0.08309 (9) | 0.0456 (5) | |
H1 | 0.1013 | 0.5387 | 0.0651 | 0.055* | |
C2 | 0.1139 (2) | 0.46201 (14) | 0.15445 (8) | 0.0351 (4) | |
C3 | 0.1208 (3) | 0.35793 (14) | 0.18379 (8) | 0.0381 (5) | |
H3A | 0.0257 | 0.3148 | 0.1601 | 0.046* | |
H3B | 0.2512 | 0.3291 | 0.1757 | 0.046* | |
O2 | 0.08111 (19) | 0.35301 (9) | 0.25332 (6) | 0.0438 (4) | |
C4 | 0.1089 (2) | 0.43707 (13) | 0.29215 (8) | 0.0318 (4) | |
C5 | 0.1082 (2) | 0.42242 (14) | 0.36068 (9) | 0.0340 (4) | |
O3 | 0.09121 (18) | 0.32461 (10) | 0.38224 (6) | 0.0450 (4) | |
C6 | 0.0786 (3) | 0.30827 (18) | 0.45209 (9) | 0.0530 (6) | |
H6A | 0.1980 | 0.3320 | 0.4735 | 0.080* | |
H6B | 0.0616 | 0.2358 | 0.4609 | 0.080* | |
H6C | −0.0324 | 0.3458 | 0.4700 | 0.080* | |
C7 | 0.1241 (2) | 0.50626 (15) | 0.40230 (9) | 0.0394 (5) | |
H7 | 0.1240 | 0.4974 | 0.4492 | 0.047* | |
C8 | 0.1403 (3) | 0.60283 (15) | 0.37558 (9) | 0.0449 (5) | |
H8 | 0.1496 | 0.6597 | 0.4043 | 0.054* | |
C9 | 0.1428 (3) | 0.61667 (15) | 0.30801 (9) | 0.0400 (5) | |
H9 | 0.1565 | 0.6829 | 0.2902 | 0.048* | |
C10 | 0.1255 (2) | 0.53375 (13) | 0.26518 (8) | 0.0325 (4) | |
C11 | 0.1184 (2) | 0.54390 (14) | 0.19384 (9) | 0.0351 (4) | |
H11 | 0.1170 | 0.6095 | 0.1745 | 0.042* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0741 (11) | 0.0674 (11) | 0.0334 (8) | 0.0080 (8) | −0.0032 (7) | −0.0087 (7) |
C1 | 0.0500 (12) | 0.0538 (14) | 0.0330 (11) | 0.0056 (9) | −0.0001 (9) | 0.0023 (9) |
C2 | 0.0338 (10) | 0.0450 (12) | 0.0266 (10) | −0.0007 (8) | 0.0004 (7) | 0.0008 (8) |
C3 | 0.0505 (12) | 0.0364 (11) | 0.0274 (10) | −0.0032 (8) | 0.0029 (8) | −0.0036 (7) |
O2 | 0.0709 (10) | 0.0331 (8) | 0.0275 (7) | −0.0052 (6) | 0.0046 (6) | −0.0021 (5) |
C4 | 0.0335 (10) | 0.0324 (10) | 0.0294 (10) | 0.0004 (7) | 0.0009 (7) | −0.0034 (7) |
C5 | 0.0367 (10) | 0.0368 (11) | 0.0285 (10) | 0.0030 (8) | 0.0018 (7) | 0.0038 (7) |
O3 | 0.0620 (9) | 0.0394 (8) | 0.0335 (8) | 0.0043 (6) | 0.0047 (6) | 0.0069 (6) |
C6 | 0.0680 (14) | 0.0563 (14) | 0.0347 (11) | 0.0109 (11) | 0.0086 (9) | 0.0144 (9) |
C7 | 0.0438 (11) | 0.0480 (12) | 0.0264 (9) | 0.0043 (9) | −0.0004 (7) | −0.0029 (8) |
C8 | 0.0536 (12) | 0.0419 (12) | 0.0392 (11) | −0.0009 (9) | 0.0001 (9) | −0.0124 (9) |
C9 | 0.0501 (12) | 0.0333 (11) | 0.0365 (10) | 0.0001 (8) | 0.0021 (8) | −0.0017 (8) |
C10 | 0.0313 (9) | 0.0359 (11) | 0.0304 (10) | 0.0011 (7) | 0.0012 (7) | −0.0011 (7) |
C11 | 0.0379 (10) | 0.0359 (11) | 0.0315 (10) | 0.0001 (8) | 0.0004 (7) | 0.0058 (7) |
O1—C1 | 1.215 (2) | O3—C6 | 1.423 (2) |
C1—C2 | 1.442 (2) | C6—H6A | 0.9800 |
C1—H1 | 0.9500 | C6—H6B | 0.9800 |
C2—C11 | 1.341 (3) | C6—H6C | 0.9800 |
C2—C3 | 1.497 (3) | C7—C8 | 1.388 (3) |
C3—O2 | 1.425 (2) | C7—H7 | 0.9500 |
C3—H3A | 0.9900 | C8—C9 | 1.370 (2) |
C3—H3B | 0.9900 | C8—H8 | 0.9500 |
O2—C4 | 1.370 (2) | C9—C10 | 1.398 (2) |
C4—C5 | 1.391 (2) | C9—H9 | 0.9500 |
C4—C10 | 1.392 (2) | C10—C11 | 1.441 (2) |
C5—O3 | 1.368 (2) | C11—H11 | 0.9500 |
C5—C7 | 1.392 (3) | ||
O1—C1—C2 | 124.4 (2) | O3—C6—H6B | 109.5 |
O1—C1—H1 | 117.8 | H6A—C6—H6B | 109.5 |
C2—C1—H1 | 117.8 | O3—C6—H6C | 109.5 |
C11—C2—C1 | 120.83 (18) | H6A—C6—H6C | 109.5 |
C11—C2—C3 | 120.50 (16) | H6B—C6—H6C | 109.5 |
C1—C2—C3 | 118.66 (16) | C8—C7—C5 | 120.32 (17) |
O2—C3—C2 | 114.96 (14) | C8—C7—H7 | 119.8 |
O2—C3—H3A | 108.5 | C5—C7—H7 | 119.8 |
C2—C3—H3A | 108.5 | C9—C8—C7 | 120.46 (18) |
O2—C3—H3B | 108.5 | C9—C8—H8 | 119.8 |
C2—C3—H3B | 108.5 | C7—C8—H8 | 119.8 |
H3A—C3—H3B | 107.5 | C8—C9—C10 | 120.29 (18) |
C4—O2—C3 | 119.63 (13) | C8—C9—H9 | 119.9 |
O2—C4—C5 | 116.79 (16) | C10—C9—H9 | 119.9 |
O2—C4—C10 | 122.21 (16) | C4—C10—C9 | 119.08 (17) |
C5—C4—C10 | 120.89 (16) | C4—C10—C11 | 118.04 (16) |
O3—C5—C4 | 116.44 (16) | C9—C10—C11 | 122.86 (17) |
O3—C5—C7 | 124.61 (16) | C2—C11—C10 | 120.88 (17) |
C4—C5—C7 | 118.95 (17) | C2—C11—H11 | 119.6 |
C5—O3—C6 | 117.45 (15) | C10—C11—H11 | 119.6 |
O3—C6—H6A | 109.5 | ||
O1—C1—C2—C11 | 179.25 (18) | C4—C5—C7—C8 | 0.1 (2) |
O1—C1—C2—C3 | 0.2 (3) | C5—C7—C8—C9 | −0.7 (3) |
C11—C2—C3—O2 | 15.8 (2) | C7—C8—C9—C10 | 1.2 (3) |
C1—C2—C3—O2 | −165.19 (15) | O2—C4—C10—C9 | 176.48 (15) |
C2—C3—O2—C4 | −23.3 (2) | C5—C4—C10—C9 | 0.4 (2) |
C3—O2—C4—C5 | −166.65 (15) | O2—C4—C10—C11 | −1.8 (2) |
C3—O2—C4—C10 | 17.1 (2) | C5—C4—C10—C11 | −177.88 (14) |
O2—C4—C5—O3 | 3.7 (2) | C8—C9—C10—C4 | −1.1 (3) |
C10—C4—C5—O3 | 179.99 (15) | C8—C9—C10—C11 | 177.14 (16) |
O2—C4—C5—C7 | −176.19 (15) | C1—C2—C11—C10 | 179.49 (15) |
C10—C4—C5—C7 | 0.1 (2) | C3—C2—C11—C10 | −1.5 (2) |
C4—C5—O3—C6 | −176.38 (15) | C4—C10—C11—C2 | −6.0 (2) |
C7—C5—O3—C6 | 3.5 (2) | C9—C10—C11—C2 | 175.80 (17) |
O3—C5—C7—C8 | −179.85 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6B···O1i | 0.98 | 2.49 | 3.340 (3) | 145 |
Symmetry code: (i) x, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C11H10O3 |
Mr | 190.19 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 200 |
a, b, c (Å) | 6.8940 (6), 13.2079 (11), 20.0964 (16) |
V (Å3) | 1829.9 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.23 × 0.21 × 0.19 |
Data collection | |
Diffractometer | Bruker SMART CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12690, 2276, 1194 |
Rint | 0.056 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.158, 0.92 |
No. of reflections | 2276 |
No. of parameters | 128 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.28 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6B···O1i | 0.98 | 2.49 | 3.340 (3) | 145.1 |
Symmetry code: (i) x, −y+1/2, z+1/2. |
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Chromenes have been important heterocyclic components in biologically active pharmaceuticals which show anti-inflammatory (Gebhardt et al. 2007) and anticancer (Mun et al., 2012) activities. The 2H-chromene skeleton is a core structure of oxygen heterocycles in many natural products having biological activities (Escandón-Rivera et al., 2012; Chen et al., 2008). In a continuation of our research interest to develop novel chalcone derivatives containing heterocycles (Yoon et al., 2012) the crystal structure of the title compound was determined.
The molecular structure of the title compound is shown in Fig. 1. The fused dihydropyran ring is in a half-chair conformation with atoms O2 and C3 positioned 0.1318 (13) and 0.143 (2)Å respectively, either side of the mean plane of the other four atoms (C2/C4/C10/C11). In the crystal, weak C—H···O hydrogen bonds link molecules along [001] (Fig. 2). Examples of structures of chromene compounds have been published (Yusufzai et al., 2012; Betz et al., 2011; Bardajee et al., 2007).