Crystal structure of 1-(8-meth­oxy-2H-chromen-3-yl)ethanone

Koh, D.

doi:10.1107/S1600536814016808

organic compounds

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Volume 70| Part 9| September 2014| Pages o936-o937

doi:10.1107/S1600536814016808

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Crystal structure of 1-(8-methoxy-2H-chromen-3-yl)ethanone

Dongsoo Koh ^a ^*

^aDepartment of Applied Chemistry, Dongduk Women's University, 23-1 Wolkok-dong, Sungbuk-ku, Seoul, 136-714, Republic of Korea
^*Correspondence e-mail: dskoh@dongduk.ac.kr

Edited by E. R. T. Tiekink, University of Malaya, Malaysia (Received 16 July 2014; accepted 21 July 2014; online 1 August 2014)

In the structure of the title compound, C₁₂H₁₂O₃, the dihydropyran ring is fused with the benzene ring. The dihydropyran ring is in a half-chair conformation, with the ring O and methylene C atoms positioned 1.367 (3) and 1.504 (4) Å, respectively, on either side of the mean plane formed by the other four atoms. The methoxy group is coplanar with the benzene ring to which it is connected [C_b—Cb—O_m—C_m torsion angle = −0.2 (4)°; b = benzene and m = methoxy], and similarly the aldehyde is coplanar with respect to the double bond of the dihydropyran ring [C_dh—C_dh—C_a—O_a = −178.1 (3)°; dh = dihydropyran and a = aldehyde]. In the crystal, molecules are linked by weak methyl–methoxy C—H⋯O hydrogen bonds into supramolecular chains along the a-axis direction.

Keywords: crystal structure; hydrogen bonding; dihydropyran ring; chromenes.

CCDC reference: 1015076

1. Related literature

For the synthesis and biological properties of chromene derivatives, see: Choi et al. (2014 ); Mun et al. (2012 ); Yoon et al. (2012 ). For the chromene group in natural products, see: Starks et al. (2014 ); Escandón-Rivera et al. (2012 ). For related structures, see: Yan & Zhang (2013 ): Yusufzai et al. (2012 ).

2. Experimental

2.1. Crystal data

C₁₂H₁₂O₃
M_r = 204.22
Orthorhombic, P 2₁ 2₁ 2₁
a = 5.1000 (4) Å
b = 12.7455 (9) Å
c = 15.130 (1) Å
V = 983.48 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 173 K
0.26 × 0.20 × 0.04 mm

2.2. Data collection

Bruker SMART CCD area-detector diffractometer
7256 measured reflections
2439 independent reflections
1943 reflections with I > 2σ(I)
R_int = 0.029

2.3. Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.148
S = 1.15
2439 reflections
138 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11A⋯O2ⁱ	0.98	2.56	3.429 (4)	148
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 1015076

Crystal structure: contains datablocks I, New_Global_Publ_Block, global. DOI: 10.1107/S1600536814016808/tk5330sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814016808/tk5330Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814016808/tk5330Isup3.cml

checkCIF report

Experimental top

Synthesis and crystallization top

To a solution of 2-hydroxy-3-methoxy-benzaldehyde (750 mg, 5 mmol) in 1,4-dioxane (15 ml) was added excess amount of methyl vinyl ketone (0.7 mL, 8 mmol) and potassium carbonate (700 mg, 5 mmol) at room temperature. The reaction mixture was refluxed for 12 h and TLC showed no evidence for the starting material. After cooling to room temperature, the mixture was poured into iced water (40 ml) and extracted with methylene chloride (3 x 20 ml) and the combined organic layers were dried under MgSO₄. Filtration, evaporation of filtrate gave residue which was purified by flash chromatography to give the titled compound (22%). Recrystallization from its ethanol solution gave crystals (M.pt: 375–376 K).

Refinement top

The H atoms were placed in calculated positions and refined as riding with C—H = 0.95 Å, and with U_iso(H) = 1.2U_eq(C).

Results and discussion top

Chromenes have been shown to be potential pharmaceuticals which show anti-inflammatory (Choi et al., 2014) and anticancer (Mun et al., 2012) activities. Especially, the 2H-chromene skeleton is a core structure of oxygen heterocycles in many natural products having versatile biological activities (Starks et al., 2014; Escandón-Rivera et al., 2012). In continuation of our research interest to develop novel chromene derivatives (Yoon et al., 2012), the title compound was synthesized and its crystal structure was determined (Fig. 1). In the chromene compound, the dihydropyran ring is fused with the benzene ring and is in a half-chair conformation with atoms C1 and O1 positioned 1.367 (3) and 1.504 (4) Å, respectively, on either side of the mean plane formed by the other four atoms (C2/C3/C4/C5). In the crystal, weak C—H—-O hydrogen bonds link molecules along [100] (Fig. 2). Examples of structures of chromene compounds have been published (Yan et al., 2013; Yusufzai et al., 2012).

Related literature top

For the synthesis and biological properties of chromene derivatives, see: Choi et al. (2014); Mun et al. (2012); Yoon et al. (2012). For the chromene group in natural products, see: Starks et al. (2014); Escandón-Rivera et al. (2012). For related structures, see: Yan et al. (2013): Yusufzai et al. (2012).

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atom labelling scheme and 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.

1-(8-Methoxy-2H-chromen-3-yl)ethanone top

Crystal data top

C₁₂H₁₂O₃	F(000) = 432
M_r = 204.22	D_x = 1.379 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 4995 reflections
a = 5.1000 (4) Å	θ = 2.7–28.3°
b = 12.7455 (9) Å	µ = 0.10 mm⁻¹
c = 15.130 (1) Å	T = 173 K
V = 983.48 (12) Å³	Block, white
Z = 4	0.26 × 0.20 × 0.04 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1943 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.029
Graphite monochromator	θ_max = 28.3°, θ_min = 2.1°
ϕ and ω scans	h = −4→6
7256 measured reflections	k = −16→16
2439 independent reflections	l = −20→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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.148	H-atom parameters constrained
S = 1.15	w = 1/[σ²(F_o²) + (0.0443P)² + 0.8069P] where P = (F_o² + 2F_c²)/3
2439 reflections	(Δ/σ)_max < 0.001
138 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₁₂H₁₂O₃	V = 983.48 (12) Å³
M_r = 204.22	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 5.1000 (4) Å	µ = 0.10 mm⁻¹
b = 12.7455 (9) Å	T = 173 K
c = 15.130 (1) Å	0.26 × 0.20 × 0.04 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1943 reflections with I > 2σ(I)
7256 measured reflections	R_int = 0.029
2439 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.148	H-atom parameters constrained
S = 1.15	Δρ_max = 0.30 e Å⁻³
2439 reflections	Δρ_min = −0.36 e Å⁻³
138 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	0.2139 (4)	0.13132 (13)	0.78457 (12)	0.0369 (5)
C1	0.0935 (6)	0.1378 (2)	0.69905 (18)	0.0382 (6)
H1A	−0.0596	0.0900	0.6976	0.046*
H1B	0.2202	0.1130	0.6541	0.046*
C2	0.0045 (5)	0.2465 (2)	0.67470 (17)	0.0317 (5)
C3	0.1318 (5)	0.32861 (19)	0.70942 (16)	0.0315 (5)
H3	0.0841	0.3977	0.6921	0.038*
C4	0.3416 (5)	0.31384 (19)	0.77314 (16)	0.0290 (5)
C5	0.3744 (5)	0.21278 (18)	0.80743 (16)	0.0304 (5)
C6	0.5662 (5)	0.19364 (19)	0.87130 (17)	0.0323 (6)
C7	0.7236 (6)	0.27498 (19)	0.90030 (17)	0.0327 (5)
H7	0.8543	0.2621	0.9437	0.039*
C8	0.6916 (6)	0.3759 (2)	0.86613 (17)	0.0335 (6)
H8	0.8013	0.4314	0.8860	0.040*
C9	0.5011 (5)	0.39520 (19)	0.80357 (17)	0.0320 (5)
H9	0.4783	0.4642	0.7811	0.038*
C10	−0.2116 (5)	0.2531 (2)	0.61005 (18)	0.0357 (6)
O2	−0.3175 (4)	0.17219 (16)	0.58488 (14)	0.0471 (5)
C11	−0.2923 (6)	0.3576 (2)	0.57362 (18)	0.0414 (7)
H11A	−0.1666	0.3797	0.5283	0.062*
H11B	−0.2956	0.4095	0.6214	0.062*
H11C	−0.4673	0.3519	0.5473	0.062*
O3	0.5790 (4)	0.09230 (15)	0.90143 (14)	0.0430 (5)
C12	0.7723 (6)	0.0714 (2)	0.9676 (2)	0.0435 (7)
H12A	0.9471	0.0861	0.9437	0.065*
H12B	0.7620	−0.0025	0.9853	0.065*
H12C	0.7403	0.1162	1.0191	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0406 (10)	0.0278 (9)	0.0424 (10)	−0.0065 (8)	−0.0104 (9)	0.0029 (7)
C1	0.0443 (15)	0.0297 (12)	0.0405 (13)	−0.0008 (12)	−0.0109 (13)	−0.0034 (11)
C2	0.0296 (12)	0.0307 (12)	0.0350 (12)	0.0021 (10)	0.0010 (10)	−0.0026 (10)
C3	0.0318 (13)	0.0285 (12)	0.0341 (12)	0.0045 (10)	0.0022 (11)	−0.0001 (10)
C4	0.0286 (12)	0.0268 (11)	0.0316 (12)	0.0013 (10)	0.0034 (10)	−0.0018 (9)
C5	0.0336 (13)	0.0257 (11)	0.0318 (12)	−0.0022 (10)	0.0013 (11)	−0.0016 (9)
C6	0.0347 (13)	0.0272 (12)	0.0349 (12)	0.0009 (10)	−0.0002 (11)	0.0018 (10)
C7	0.0335 (13)	0.0334 (13)	0.0311 (12)	−0.0017 (10)	−0.0015 (11)	−0.0003 (10)
C8	0.0379 (14)	0.0285 (12)	0.0342 (12)	−0.0044 (11)	0.0000 (11)	−0.0013 (10)
C9	0.0348 (13)	0.0261 (11)	0.0351 (12)	0.0023 (10)	0.0034 (11)	−0.0016 (10)
C10	0.0340 (13)	0.0400 (14)	0.0330 (12)	0.0047 (12)	0.0014 (11)	−0.0041 (11)
O2	0.0446 (12)	0.0441 (12)	0.0527 (12)	−0.0028 (10)	−0.0110 (10)	−0.0106 (9)
C11	0.0437 (16)	0.0451 (15)	0.0354 (13)	0.0064 (14)	−0.0037 (12)	0.0011 (11)
O3	0.0498 (12)	0.0285 (9)	0.0508 (11)	−0.0036 (9)	−0.0161 (10)	0.0082 (8)
C12	0.0464 (17)	0.0345 (14)	0.0497 (16)	0.0006 (13)	−0.0131 (14)	0.0096 (12)

Geometric parameters (Å, º) top

O1—C5	1.366 (3)	C7—C8	1.396 (3)
O1—C1	1.435 (3)	C7—H7	0.9500
C1—C2	1.504 (4)	C8—C9	1.378 (4)
C1—H1A	0.9900	C8—H8	0.9500
C1—H1B	0.9900	C9—H9	0.9500
C2—C3	1.339 (4)	C10—O2	1.224 (3)
C2—C10	1.476 (4)	C10—C11	1.499 (4)
C3—C4	1.452 (4)	C11—H11A	0.9800
C3—H3	0.9500	C11—H11B	0.9800
C4—C9	1.396 (3)	C11—H11C	0.9800
C4—C5	1.399 (3)	O3—C12	1.430 (3)
C5—C6	1.397 (3)	C12—H12A	0.9800
C6—O3	1.371 (3)	C12—H12B	0.9800
C6—C7	1.383 (4)	C12—H12C	0.9800

C5—O1—C1	116.2 (2)	C8—C7—H7	119.8
O1—C1—C2	113.8 (2)	C9—C8—C7	120.1 (2)
O1—C1—H1A	108.8	C9—C8—H8	120.0
C2—C1—H1A	108.8	C7—C8—H8	120.0
O1—C1—H1B	108.8	C8—C9—C4	120.3 (2)
C2—C1—H1B	108.8	C8—C9—H9	119.8
H1A—C1—H1B	107.7	C4—C9—H9	119.8
C3—C2—C10	125.3 (2)	O2—C10—C2	119.2 (2)
C3—C2—C1	118.5 (2)	O2—C10—C11	120.8 (2)
C10—C2—C1	116.1 (2)	C2—C10—C11	119.9 (2)
C2—C3—C4	121.1 (2)	C10—C11—H11A	109.5
C2—C3—H3	119.5	C10—C11—H11B	109.5
C4—C3—H3	119.5	H11A—C11—H11B	109.5
C9—C4—C5	119.5 (2)	C10—C11—H11C	109.5
C9—C4—C3	123.5 (2)	H11A—C11—H11C	109.5
C5—C4—C3	117.0 (2)	H11B—C11—H11C	109.5
O1—C5—C6	117.5 (2)	C6—O3—C12	116.2 (2)
O1—C5—C4	122.3 (2)	O3—C12—H12A	109.5
C6—C5—C4	120.1 (2)	O3—C12—H12B	109.5
O3—C6—C7	125.0 (2)	H12A—C12—H12B	109.5
O3—C6—C5	115.3 (2)	O3—C12—H12C	109.5
C7—C6—C5	119.7 (2)	H12A—C12—H12C	109.5
C6—C7—C8	120.4 (2)	H12B—C12—H12C	109.5
C6—C7—H7	119.8

C5—O1—C1—C2	−39.4 (3)	O1—C5—C6—C7	−176.4 (2)
O1—C1—C2—C3	28.1 (4)	C4—C5—C6—C7	−0.1 (4)
O1—C1—C2—C10	−154.7 (2)	O3—C6—C7—C8	−179.0 (3)
C10—C2—C3—C4	179.7 (2)	C5—C6—C7—C8	0.0 (4)
C1—C2—C3—C4	−3.5 (4)	C6—C7—C8—C9	0.5 (4)
C2—C3—C4—C9	172.2 (2)	C7—C8—C9—C4	−0.9 (4)
C2—C3—C4—C5	−10.5 (4)	C5—C4—C9—C8	0.8 (4)
C1—O1—C5—C6	−156.5 (2)	C3—C4—C9—C8	178.1 (2)
C1—O1—C5—C4	27.3 (3)	C3—C2—C10—O2	−178.1 (3)
C9—C4—C5—O1	175.8 (2)	C1—C2—C10—O2	5.0 (4)
C3—C4—C5—O1	−1.7 (4)	C3—C2—C10—C11	4.2 (4)
C9—C4—C5—C6	−0.3 (4)	C1—C2—C10—C11	−172.7 (2)
C3—C4—C5—C6	−177.7 (2)	C7—C6—O3—C12	−0.2 (4)
O1—C5—C6—O3	2.8 (3)	C5—C6—O3—C12	−179.3 (2)
C4—C5—C6—O3	179.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···O2ⁱ	0.98	2.56	3.429 (4)	148

Symmetry code: (i) x+1/2, −y+1/2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···O2ⁱ	0.98	2.56	3.429 (4)	148

Symmetry code: (i) x+1/2, −y+1/2, −z+1.

Acknowledgements

The author acknowledges financial support from Dongduk Women's University.

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 9| September 2014| Pages o936-o937

doi:10.1107/S1600536814016808

Open

access