1-(5-Hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)ethan-1-one

Liu, B.; Chen, G.; Cen, C.; Song, X.; Han, C.

doi:10.1107/S1600536810018374

organic compounds

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ISSN: 2056-9890

Volume 66| Part 6| June 2010| Page o1441

https://doi.org/10.1107/S1600536810018374

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1-(5-Hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)ethan-1-one

Bingjing Liu,^a Guangying Chen,^a ^* Changchun Cen,^a Xinming Song ^a and Changri Han ^a

^aKey Laboratory of Tropical Medicinal Plant Chemistry of the Ministry of Education, Hainan Normal University, College of Chemistry & Chemical Engineering, Hainan Normal University, Haikou 571158, People's Republic of China
^*Correspondence e-mail: chgying123@163.com

(Received 28 April 2010; accepted 18 May 2010; online 22 May 2010)

The title chromene, C₁₄H₁₆O₄, was isolated from the stems of Polyalthia plagioneura Diels. The molecular structure is stabilized by an intramolecular O–H⋯O hydrogen bond, which generates an S(6) ring. In the crystal, the molecules are linked by C—H⋯O interactions, generating [010] chains.

Related literature

For medicinal and botanical background to the title compound, see: Allan et al. (1969 ); Manandhar et al. (1985 ); Li et al. (1997 ).

Experimental

Crystal data

C₁₄H₁₆O₄
M_r = 248.28
Triclinic, $[P \overline 1]$
a = 7.3797 (9) Å
b = 8.0066 (10) Å
c = 11.2878 (14) Å
α = 77.948 (1)°
β = 77.411 (1)°
γ = 84.465 (2)°
V = 635.67 (14) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 K
0.45 × 0.40 × 0.39 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.959, T_max = 0.964
3335 measured reflections
2217 independent reflections
1361 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.159
S = 1.08
2217 reflections
167 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O3	0.82	1.75	2.479 (2)	147
C8—H8⋯O3ⁱ	0.93	2.48	3.374 (3)	162
Symmetry code: (i) x, y-1, z.

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); 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

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810018374/hb5429sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810018374/hb5429Isup2.hkl

checkCIF report

Comment top

The title chromene was isolated from plants such as Remirea maritima (Allan et al., 1969), Euodia lunu-ankenda (Manandhar et al., 1985) and Evodia lepta (Li et al., 1997). In our ongoing studies of natural products with biological activity we isolated the chromene from the 75% EtOH extract of the stems of Polyalthia plagioneura, a plant used as a flok medicine which were collected from Bawangling, Hainan Province, P. R. China. We have undertaken the X-ray crystal structure analysis of the title compound in order to establish its molecular structure and relative stereochemistry.

The hydrogen bonds and angles are listed in Table 1.

Related literature top

For medicinal and botanical background to the title compound, see: Allan et al. (1969); Manandhar et al. (1985); Li et al. (1997).

Experimental top

Air-dried stems of Polyalthia plagioneura (20 kg) were ground and percolated (4 × 3 h) with 75% EtOH at 60°C, which was suspended in 5 L water and then partitioned with chloroform, ethyl acetate and n-BuOH, successively, yielding a chloroform extract, an ethyl acetate extract and a n-BuOH extract, respectively. The chloroform extract was subjected to a silica gel CC column using petroleum ether as first eluent and then increasing the polarity with EtOAc, to afford 33 fractions. Fraction 5 was further separated by column chromatography with a gradient of chloroform–ether–EtOAc to give the title compound. The crude product was recrystallised from ethyl acetate to yield colourless blocks of (I).

Structure description top

The hydrogen bonds and angles are listed in Table 1.

For medicinal and botanical background to the title compound, see: Allan et al. (1969); Manandhar et al. (1985); Li et al. (1997).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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. View of the title compound with displacement ellipsoids drawn at the 30% probability level.

1-(5-Hydroxy-7-methoxy-2,2-dimethyl-2H-chromen-6-yl)ethan-1-one top

Crystal data top

C₁₄H₁₆O₄	Z = 2
M_r = 248.28	F(000) = 264
Triclinic, P1	D_x = 1.297 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3797 (9) Å	Cell parameters from 1208 reflections
b = 8.0066 (10) Å	θ = 2.6–24.1°
c = 11.2878 (14) Å	µ = 0.10 mm⁻¹
α = 77.948 (1)°	T = 298 K
β = 77.411 (1)°	Block, colourless
γ = 84.465 (2)°	0.45 × 0.40 × 0.39 mm
V = 635.67 (14) Å³

Data collection top

Bruker SMART CCD diffractometer	2217 independent reflections
Radiation source: fine-focus sealed tube	1361 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −8→8
T_min = 0.959, T_max = 0.964	k = −8→9
3335 measured reflections	l = −13→13

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.159	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0801P)²] where P = (F_o² + 2F_c²)/3
2217 reflections	(Δ/σ)_max < 0.001
167 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₄H₁₆O₄	γ = 84.465 (2)°
M_r = 248.28	V = 635.67 (14) Å³
Triclinic, P1	Z = 2
a = 7.3797 (9) Å	Mo Kα radiation
b = 8.0066 (10) Å	µ = 0.10 mm⁻¹
c = 11.2878 (14) Å	T = 298 K
α = 77.948 (1)°	0.45 × 0.40 × 0.39 mm
β = 77.411 (1)°

Data collection top

Bruker SMART CCD diffractometer	2217 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	1361 reflections with I > 2σ(I)
T_min = 0.959, T_max = 0.964	R_int = 0.019
3335 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.159	H-atom parameters constrained
S = 1.08	Δρ_max = 0.26 e Å⁻³
2217 reflections	Δρ_min = −0.23 e Å⁻³
167 parameters

Special details top

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 > 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	0.1836 (2)	0.20248 (18)	0.25325 (13)	0.0529 (5)
O2	0.2390 (2)	0.76852 (19)	0.29434 (15)	0.0659 (5)
H2	0.2508	0.8241	0.3453	0.099*
O3	0.2742 (3)	0.8220 (2)	0.49648 (17)	0.0720 (6)
O4	0.2615 (2)	0.30717 (19)	0.63521 (13)	0.0604 (5)
C1	0.2377 (3)	0.2453 (3)	0.11859 (19)	0.0534 (7)
C2	0.2004 (4)	0.4317 (3)	0.0732 (2)	0.0584 (7)
H2A	0.1813	0.4684	−0.0072	0.070*
C3	0.1938 (3)	0.5467 (3)	0.1434 (2)	0.0546 (7)
H3	0.1751	0.6624	0.1116	0.066*
C4	0.2160 (3)	0.4900 (3)	0.27044 (19)	0.0431 (6)
C5	0.2349 (3)	0.6020 (3)	0.3466 (2)	0.0451 (6)
C6	0.2498 (3)	0.5431 (3)	0.47159 (19)	0.0419 (5)
C7	0.2432 (3)	0.3632 (3)	0.51639 (19)	0.0429 (6)
C8	0.2232 (3)	0.2528 (3)	0.44272 (19)	0.0433 (5)
H8	0.2184	0.1360	0.4741	0.052*
C9	0.2101 (3)	0.3175 (3)	0.32112 (19)	0.0411 (5)
C10	0.1212 (4)	0.1353 (3)	0.0740 (2)	0.0695 (8)
H10A	0.1443	0.0172	0.1090	0.104*
H10B	0.1534	0.1517	−0.0146	0.104*
H10C	−0.0081	0.1672	0.0992	0.104*
C11	0.4434 (4)	0.1947 (4)	0.0849 (2)	0.0791 (8)
H11A	0.5131	0.2610	0.1191	0.119*
H11B	0.4831	0.2157	−0.0035	0.119*
H11C	0.4640	0.0754	0.1176	0.119*
C12	0.2686 (3)	0.6685 (3)	0.5448 (2)	0.0501 (6)
C13	0.2816 (3)	0.6241 (3)	0.6777 (2)	0.0598 (7)
H13A	0.2903	0.7267	0.7070	0.090*
H13B	0.3900	0.5500	0.6867	0.090*
H13C	0.1727	0.5670	0.7251	0.090*
C14	0.2647 (4)	0.1275 (3)	0.6819 (2)	0.0717 (8)
H14A	0.1481	0.0845	0.6811	0.108*
H14B	0.2846	0.1051	0.7652	0.108*
H14C	0.3635	0.0720	0.6310	0.108*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0793 (12)	0.0426 (10)	0.0413 (9)	−0.0099 (8)	−0.0147 (8)	−0.0124 (7)
O2	0.0982 (14)	0.0346 (10)	0.0677 (11)	−0.0076 (8)	−0.0267 (10)	−0.0039 (8)
O3	0.1000 (15)	0.0432 (11)	0.0818 (13)	−0.0087 (9)	−0.0265 (10)	−0.0213 (9)
O4	0.0955 (14)	0.0452 (10)	0.0444 (9)	−0.0021 (8)	−0.0218 (8)	−0.0104 (8)
C1	0.0680 (18)	0.0559 (16)	0.0383 (12)	−0.0089 (12)	−0.0100 (11)	−0.0119 (11)
C2	0.0750 (18)	0.0597 (17)	0.0403 (13)	−0.0108 (13)	−0.0151 (12)	−0.0023 (12)
C3	0.0694 (17)	0.0430 (14)	0.0500 (14)	−0.0079 (11)	−0.0164 (12)	0.0010 (11)
C4	0.0455 (14)	0.0384 (13)	0.0461 (13)	−0.0026 (10)	−0.0111 (10)	−0.0077 (10)
C5	0.0464 (14)	0.0335 (12)	0.0547 (14)	−0.0029 (9)	−0.0110 (10)	−0.0059 (10)
C6	0.0422 (13)	0.0392 (13)	0.0467 (13)	−0.0003 (10)	−0.0109 (10)	−0.0126 (10)
C7	0.0487 (14)	0.0425 (13)	0.0374 (12)	−0.0004 (10)	−0.0089 (10)	−0.0087 (10)
C8	0.0545 (15)	0.0321 (12)	0.0432 (12)	−0.0029 (10)	−0.0097 (10)	−0.0069 (10)
C9	0.0452 (14)	0.0394 (13)	0.0410 (12)	−0.0041 (10)	−0.0089 (10)	−0.0114 (10)
C10	0.097 (2)	0.0722 (19)	0.0490 (14)	−0.0204 (15)	−0.0228 (14)	−0.0173 (13)
C11	0.076 (2)	0.092 (2)	0.0690 (18)	−0.0014 (15)	−0.0054 (15)	−0.0255 (16)
C12	0.0460 (14)	0.0452 (15)	0.0628 (15)	−0.0024 (11)	−0.0109 (11)	−0.0191 (12)
C13	0.0643 (17)	0.0611 (17)	0.0636 (16)	−0.0029 (12)	−0.0148 (12)	−0.0322 (13)
C14	0.113 (2)	0.0547 (17)	0.0450 (14)	−0.0050 (15)	−0.0215 (14)	0.0016 (12)

Geometric parameters (Å, º) top

O1—C9	1.367 (2)	C6—C12	1.460 (3)
O1—C1	1.460 (2)	C7—C8	1.371 (3)
O2—C5	1.341 (2)	C8—C9	1.383 (3)
O2—H2	0.8200	C8—H8	0.9300
O3—C12	1.237 (3)	C10—H10A	0.9600
O4—C7	1.354 (2)	C10—H10B	0.9600
O4—C14	1.424 (3)	C10—H10C	0.9600
C1—C2	1.493 (3)	C11—H11A	0.9600
C1—C10	1.513 (3)	C11—H11B	0.9600
C1—C11	1.519 (3)	C11—H11C	0.9600
C2—C3	1.326 (3)	C12—C13	1.490 (3)
C2—H2A	0.9300	C13—H13A	0.9600
C3—C4	1.451 (3)	C13—H13B	0.9600
C3—H3	0.9300	C13—H13C	0.9600
C4—C9	1.381 (3)	C14—H14A	0.9600
C4—C5	1.401 (3)	C14—H14B	0.9600
C5—C6	1.415 (3)	C14—H14C	0.9600
C6—C7	1.426 (3)

C9—O1—C1	118.89 (16)	O1—C9—C4	120.78 (18)
C5—O2—H2	109.5	O1—C9—C8	116.67 (18)
C7—O4—C14	118.00 (17)	C4—C9—C8	122.51 (19)
O1—C1—C2	110.59 (18)	C1—C10—H10A	109.5
O1—C1—C10	104.22 (17)	C1—C10—H10B	109.5
C2—C1—C10	112.3 (2)	H10A—C10—H10B	109.5
O1—C1—C11	106.92 (19)	C1—C10—H10C	109.5
C2—C1—C11	111.2 (2)	H10A—C10—H10C	109.5
C10—C1—C11	111.3 (2)	H10B—C10—H10C	109.5
C3—C2—C1	122.2 (2)	C1—C11—H11A	109.5
C3—C2—H2A	118.9	C1—C11—H11B	109.5
C1—C2—H2A	118.9	H11A—C11—H11B	109.5
C2—C3—C4	119.3 (2)	C1—C11—H11C	109.5
C2—C3—H3	120.3	H11A—C11—H11C	109.5
C4—C3—H3	120.3	H11B—C11—H11C	109.5
C9—C4—C5	117.9 (2)	O3—C12—C6	119.8 (2)
C9—C4—C3	118.6 (2)	O3—C12—C13	116.2 (2)
C5—C4—C3	123.4 (2)	C6—C12—C13	124.0 (2)
O2—C5—C4	116.2 (2)	C12—C13—H13A	109.5
O2—C5—C6	121.7 (2)	C12—C13—H13B	109.5
C4—C5—C6	122.1 (2)	H13A—C13—H13B	109.5
C5—C6—C7	116.38 (19)	C12—C13—H13C	109.5
C5—C6—C12	118.6 (2)	H13A—C13—H13C	109.5
C7—C6—C12	125.0 (2)	H13B—C13—H13C	109.5
O4—C7—C8	121.91 (19)	O4—C14—H14A	109.5
O4—C7—C6	116.15 (18)	O4—C14—H14B	109.5
C8—C7—C6	121.93 (19)	H14A—C14—H14B	109.5
C7—C8—C9	119.2 (2)	O4—C14—H14C	109.5
C7—C8—H8	120.4	H14A—C14—H14C	109.5
C9—C8—H8	120.4	H14B—C14—H14C	109.5

C9—O1—C1—C2	−36.1 (3)	C5—C6—C7—O4	178.63 (19)
C9—O1—C1—C10	−157.02 (19)	C12—C6—C7—O4	−2.0 (3)
C9—O1—C1—C11	85.1 (2)	C5—C6—C7—C8	−0.1 (3)
O1—C1—C2—C3	25.1 (3)	C12—C6—C7—C8	179.2 (2)
C10—C1—C2—C3	141.0 (2)	O4—C7—C8—C9	−178.26 (18)
C11—C1—C2—C3	−93.6 (3)	C6—C7—C8—C9	0.4 (3)
C1—C2—C3—C4	−2.5 (4)	C1—O1—C9—C4	25.4 (3)
C2—C3—C4—C9	−11.4 (3)	C1—O1—C9—C8	−157.02 (19)
C2—C3—C4—C5	171.5 (2)	C5—C4—C9—O1	177.07 (19)
C9—C4—C5—O2	−179.63 (18)	C3—C4—C9—O1	−0.1 (3)
C3—C4—C5—O2	−2.6 (3)	C5—C4—C9—C8	−0.4 (3)
C9—C4—C5—C6	0.7 (3)	C3—C4—C9—C8	−177.6 (2)
C3—C4—C5—C6	177.72 (19)	C7—C8—C9—O1	−177.73 (18)
O2—C5—C6—C7	179.90 (18)	C7—C8—C9—C4	−0.2 (3)
C4—C5—C6—C7	−0.4 (3)	C5—C6—C12—O3	−1.2 (3)
O2—C5—C6—C12	0.5 (3)	C7—C6—C12—O3	179.5 (2)
C4—C5—C6—C12	−179.84 (19)	C5—C6—C12—C13	178.7 (2)
C14—O4—C7—C8	1.7 (3)	C7—C6—C12—C13	−0.6 (4)
C14—O4—C7—C6	−177.06 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3	0.82	1.75	2.479 (2)	147
C8—H8···O3ⁱ	0.93	2.48	3.374 (3)	162

Symmetry code: (i) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₆O₄
M_r	248.28
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	7.3797 (9), 8.0066 (10), 11.2878 (14)
α, β, γ (°)	77.948 (1), 77.411 (1), 84.465 (2)
V (Å³)	635.67 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.45 × 0.40 × 0.39

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.959, 0.964
No. of measured, independent and observed [I > 2σ(I)] reflections	3335, 2217, 1361
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.159, 1.08
No. of reflections	2217
No. of parameters	167
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.23

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3	0.82	1.75	2.479 (2)	147
C8—H8···O3ⁱ	0.93	2.48	3.374 (3)	162

Symmetry code: (i) x, y−1, z.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (20862005), the Program for New Century Excellent Talents in Universities (NCET-08-0656) and the University Graduate Student Innovation Science Research Project of Hainan Province (No. Hxwsy2009-10).

References

Allan, R. D., Correll, R. L. & Wells, R. J. (1969). Tetrahedron Lett. 53, 4669–4672. CrossRef Google Scholar
Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Li, G. L., Zeng, J. F., Song, C. Q. & Zhu, D. Y. (1997). Phytochemistry, 44, 1175–1178. CAS Google Scholar
Manandhar, M. D., Hussaini, F. A., Kapil, R. S. & Shoeb, A. (1985). Phytochemistry, 24, 199–200. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar