8-Meth­oxy-2H-chromene-3-carbaldehyde

Koh, D.

doi:10.1107/S1600536812047319

organic compounds

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Volume 68| Part 12| December 2012| Page o3419

doi:10.1107/S1600536812047319

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8-Methoxy-2H-chromene-3-carbaldehyde

Dongsoo Koh ^a ^*

^aDepartment of Applied Chemistry, Dongduk Women's University, Seoul 136-714, Republic of Korea
^*Correspondence e-mail: dskoh@dongduk.ac.kr

(Received 14 November 2012; accepted 17 November 2012; online 24 November 2012)

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

C₁₁H₁₀O₃
M_r = 190.19
Orthorhombic, P b c a
a = 6.8940 (6) Å
b = 13.2079 (11) Å
c = 20.0964 (16) Å
V = 1829.9 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 200 K
0.23 × 0.21 × 0.19 mm

Data collection

Bruker SMART CCD diffractometer
12690 measured reflections
2276 independent reflections
1194 reflections with I > 2σ(I)
R_int = 0.056

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.158
S = 0.92
2276 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000 ); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812047319/lh5559sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812047319/lh5559Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812047319/lh5559Isup3.cml

checkCIF report

Comment top

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).

Related literature top

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 top

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 chromatography 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).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: 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).

Figures top

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Part of the crystal structure with weak intermolecular C—H···O hydrogen bonds shown as dashed lines.

8-Methoxy-2H-chromene-3-carbaldehyde top

Crystal data top

C₁₁H₁₀O₃	F(000) = 800
M_r = 190.19	D_x = 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

Data collection top

Bruker SMART CCD diffractometer	1194 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.056
Graphite monochromator	θ_max = 28.3°, θ_min = 2.0°
ϕ and ω scans	h = −9→9
12690 measured reflections	k = −17→16
2276 independent reflections	l = −26→19

Refinement top

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(F_o²) + (0.0862P)²] where P = (F_o² + 2F_c²)/3
2276 reflections	(Δ/σ)_max = 0.001
128 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₁H₁₀O₃	V = 1829.9 (3) Å³
M_r = 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

Data collection top

Bruker SMART CCD diffractometer	1194 reflections with I > 2σ(I)
12690 measured reflections	R_int = 0.056
2276 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.158	H-atom parameters constrained
S = 0.92	Δρ_max = 0.28 e Å⁻³
2276 reflections	Δρ_min = −0.28 e Å⁻³
128 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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
M_r	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
R_int	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
Δρ_max, Δρ_min (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).

Hydrogen-bond geometry (Å, º) top

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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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page o3419

doi:10.1107/S1600536812047319

Open

access