1-(2-Hydr­oxy-4,5-dimeth­oxyphen­yl)propan-1-one

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

doi:10.1107/S1600536809041798

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2815

https://doi.org/10.1107/S1600536809041798

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1-(2-Hydroxy-4,5-dimethoxyphenyl)propan-1-one

Changchun Cen,^a Guangying Chen,^a ^* Changri Han ^a ^* and Xiaoping Song ^a

^aHainan Provincial Key Laboratory of Tropical Pharmaceutical Herb Chemistry, College of Chemistry & Chemical Engineering, Hainan Normal University, Haikou 571158, People's Republic of China
^*Correspondence e-mail: chgying123@163.com, hchr116@hainnu.edu.cn

(Received 26 September 2009; accepted 13 October 2009; online 23 October 2009)

In the title compound, C₁₁H₁₄O₄, isolated from the stems of Trigonostemon xyphophylloides, an intramolecular O—H⋯O hydrogen bond helps to establish an essentially planar conformation for the molecule (r.m.s. deviation = 0.044 Å).

Related literature

For botanical and biochemical background, see: Tempeam et al. (2005 ); Chen et al. (2009 ). For medicinal applications of this family of compounds, see: Chuakul et al. (1997 ); Tempeam et al. (2002 ).

Experimental

Crystal data

C₁₁H₁₄O₄
M_r = 210.22
Monoclinic, P 2₁ /c
a = 7.1933 (7) Å
b = 9.4874 (12) Å
c = 17.198 (2) Å
β = 113.164 (5)°
V = 1079.1 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.31 × 0.16 × 0.14 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.066, T_max = 0.185
7549 measured reflections
2673 independent reflections
1749 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.094
wR(F²) = 0.295
S = 1.12
2673 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.41 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
O1—H1⋯O2	0.82	1.86	2.577 (4)	146

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/S1600536809041798/hb5121sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809041798/hb5121Isup2.hkl

checkCIF report

Comment top

Secondary metabolites in the plants of Trigonostemon xyphophylloides are mainly daphnane diterpenoids, phenanthrenones, alkaloids and coumarins (Tempeam et al., 2005; Chen et al., 2009). The plants in this family were used in folk medicine such as an emetic for food poisoning, a laxative and an anti-asthmatic, has also been used in the treatment of bloody and mucous sputum or stool. It was applied to reduce abscesses and to alleviate sprains, swelling and bruizes, is particularly effective in treating snake bites especially against snake neurotoxins. (Chuakul et al., 1997; Tempeam et al., 2002). The title compound was isolated from the 75% EtOH extract of the stems of Trigonostemon xyphophylloides which were collected from Jianfengling County, 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 botanical and biochemical background, see: Tempeam et al. (2005); Chen et al. (2009). For medicinal applications of this family of compounds, see: Chuakul et al. (1997); Tempeam et al. (2002).

Experimental top

Air-dried stems of Trigonostemon xyphophylloides (5.9 kg) were ground and percolated (3 × 2.5 h) with 75% EtOH at 333 K, which was suspended in 1.5 l water and then partitioned with petroleum ether, chloroform, ethyl acetate and n-BuOH, successively, yielding a petroleum ether extract, a chloroform extract, an ethyl acetate extract and a n-BuOH extract, respectively. The petroleum ether extract was subjected to a silica gel CC column using petroleum ether as first eluent and then increasing the polarity with EtOAc, to afford 20 fractions (A—T). Fraction D was further separated by column chromatography with a gradient of petroleum ether-EtOAc to give the title compound. The crude product was dissolved in small amount of ethyl acetate to obtain colourless blocks of (I) by slow evaporation of ethyl acetate solution at 298 K.

Structure description top

The hydrogen bonds and angles are listed in Table 1.

For botanical and biochemical background, see: Tempeam et al. (2005); Chen et al. (2009). For medicinal applications of this family of compounds, see: Chuakul et al. (1997); Tempeam et al. (2002).

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: SHELXP-97 (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. View of (I) with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. A view of the molecular packing for (I).

1-(2-Hydroxy-4,5-dimethoxyphenyl)propan-1-one top

Crystal data top

C₁₁H₁₄O₄	F(000) = 448
M_r = 210.22	D_x = 1.294 Mg m⁻³
Monoclinic, P2₁/c	Melting point: not measured K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.1933 (7) Å	Cell parameters from 2673 reflections
b = 9.4874 (12) Å	θ = 2.5–28.4°
c = 17.198 (2) Å	µ = 0.10 mm⁻¹
β = 113.164 (5)°	T = 293 K
V = 1079.1 (2) Å³	Block, colourless
Z = 4	0.31 × 0.16 × 0.14 mm

Data collection top

Bruker SMART CCD diffractometer	2673 independent reflections
Radiation source: fine-focus sealed tube	1749 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ω scans	θ_max = 28.4°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −9→9
T_min = 0.066, T_max = 0.185	k = −12→12
7549 measured reflections	l = −22→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)] = 0.094	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.295	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.1225P)² + 1.1131P] where P = (F_o² + 2F_c²)/3
2673 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₁H₁₄O₄	V = 1079.1 (2) Å³
M_r = 210.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.1933 (7) Å	µ = 0.10 mm⁻¹
b = 9.4874 (12) Å	T = 293 K
c = 17.198 (2) Å	0.31 × 0.16 × 0.14 mm
β = 113.164 (5)°

Data collection top

Bruker SMART CCD diffractometer	2673 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	1749 reflections with I > 2σ(I)
T_min = 0.066, T_max = 0.185	R_int = 0.044
7549 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.094	0 restraints
wR(F²) = 0.295	H-atom parameters constrained
S = 1.12	Δρ_max = 0.41 e Å⁻³
2673 reflections	Δρ_min = −0.28 e Å⁻³
136 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	0.3767 (5)	0.3553 (3)	0.52714 (19)	0.0723 (9)
H1	0.3323	0.3757	0.4768	0.080*
O2	0.1907 (5)	0.3117 (3)	0.36706 (18)	0.0763 (9)
O3	0.2687 (4)	−0.2066 (3)	0.58386 (15)	0.0600 (8)
O4	0.4475 (4)	−0.0386 (3)	0.71051 (14)	0.0581 (7)
C1	0.3465 (5)	0.2161 (4)	0.5358 (2)	0.0497 (8)
C2	0.2485 (5)	0.1275 (3)	0.4653 (2)	0.0435 (7)
C3	0.2245 (5)	−0.0169 (4)	0.48170 (19)	0.0437 (7)
H3	0.1624	−0.0776	0.4364	0.080*
C4	0.2907 (5)	−0.0694 (3)	0.5629 (2)	0.0432 (7)
C5	0.3876 (5)	0.0225 (4)	0.63263 (19)	0.0441 (7)
C6	0.4134 (5)	0.1631 (4)	0.6178 (2)	0.0499 (8)
H6	0.4764	0.2232	0.6633	0.080*
C7	0.1702 (5)	0.1852 (4)	0.3788 (2)	0.0509 (8)
C8	0.0636 (6)	0.0885 (4)	0.3045 (2)	0.0569 (9)
H8A	−0.0529	0.0476	0.3111	0.080*
H8B	0.1545	0.0120	0.3061	0.080*
C9	−0.0065 (8)	0.1589 (5)	0.2186 (3)	0.0801 (14)
H9A	−0.0699	0.0902	0.1752	0.080*
H9B	0.1077	0.1990	0.2110	0.080*
H9C	−0.1017	0.2319	0.2152	0.080*
C10	0.1800 (6)	−0.3028 (4)	0.5156 (2)	0.0600 (10)
H10A	0.1714	−0.3945	0.5376	0.080*
H10B	0.2621	−0.3079	0.4831	0.080*
H10C	0.0469	−0.2709	0.4801	0.080*
C11	0.5335 (7)	0.0537 (5)	0.7830 (2)	0.0699 (12)
H11A	0.5684	−0.0003	0.8340	0.080*
H11B	0.4364	0.1246	0.7809	0.080*
H11C	0.6527	0.0980	0.7821	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.107 (2)	0.0456 (15)	0.0605 (17)	−0.0084 (14)	0.0294 (16)	−0.0016 (13)
O2	0.115 (3)	0.0534 (17)	0.0561 (16)	−0.0070 (16)	0.0287 (17)	0.0092 (13)
O3	0.0858 (18)	0.0402 (13)	0.0372 (12)	−0.0007 (12)	0.0062 (12)	0.0020 (10)
O4	0.0790 (17)	0.0490 (14)	0.0347 (12)	−0.0005 (12)	0.0098 (11)	−0.0045 (10)
C1	0.0556 (19)	0.0434 (18)	0.0509 (18)	0.0009 (15)	0.0219 (15)	−0.0022 (14)
C2	0.0482 (17)	0.0395 (16)	0.0422 (16)	0.0051 (13)	0.0170 (13)	−0.0005 (13)
C3	0.0472 (17)	0.0426 (17)	0.0377 (15)	0.0044 (13)	0.0129 (13)	−0.0046 (13)
C4	0.0444 (16)	0.0399 (16)	0.0413 (16)	0.0072 (13)	0.0125 (13)	−0.0007 (13)
C5	0.0459 (16)	0.0452 (17)	0.0371 (15)	0.0061 (14)	0.0120 (12)	−0.0036 (13)
C6	0.0551 (19)	0.0473 (19)	0.0437 (17)	0.0005 (15)	0.0155 (15)	−0.0091 (14)
C7	0.058 (2)	0.048 (2)	0.0461 (18)	0.0053 (15)	0.0200 (15)	0.0048 (15)
C8	0.069 (2)	0.057 (2)	0.0405 (17)	0.0013 (17)	0.0162 (16)	0.0066 (15)
C9	0.107 (4)	0.073 (3)	0.045 (2)	0.001 (3)	0.013 (2)	0.012 (2)
C10	0.078 (3)	0.0443 (19)	0.0439 (18)	0.0030 (17)	0.0091 (17)	−0.0015 (15)
C11	0.098 (3)	0.065 (3)	0.0358 (17)	−0.002 (2)	0.0149 (19)	−0.0100 (17)

Geometric parameters (Å, º) top

O1—C1	1.355 (4)	C6—H6	0.9300
O1—H1	0.8200	C7—C8	1.513 (5)
O2—C7	1.235 (4)	C8—C9	1.516 (5)
O3—C4	1.376 (4)	C8—H8A	0.9700
O3—C10	1.424 (4)	C8—H8B	0.9700
O4—C5	1.364 (4)	C9—H9A	0.9600
O4—C11	1.448 (4)	C9—H9B	0.9600
C1—C6	1.393 (5)	C9—H9C	0.9600
C1—C2	1.415 (5)	C10—H10A	0.9600
C2—C3	1.423 (5)	C10—H10B	0.9600
C2—C7	1.473 (5)	C10—H10C	0.9600
C3—C4	1.379 (4)	C11—H11A	0.9600
C3—H3	0.9300	C11—H11B	0.9600
C4—C5	1.423 (4)	C11—H11C	0.9600
C5—C6	1.385 (5)

C1—O1—H1	109.5	C7—C8—C9	114.8 (3)
C4—O3—C10	116.8 (3)	C7—C8—H8A	108.6
C5—O4—C11	116.8 (3)	C9—C8—H8A	108.6
O1—C1—C6	117.2 (3)	C7—C8—H8B	108.6
O1—C1—C2	122.2 (3)	C9—C8—H8B	108.6
C6—C1—C2	120.7 (3)	H8A—C8—H8B	107.5
C1—C2—C3	117.4 (3)	C8—C9—H9A	109.5
C1—C2—C7	120.5 (3)	C8—C9—H9B	109.5
C3—C2—C7	122.0 (3)	H9A—C9—H9B	109.5
C4—C3—C2	121.9 (3)	C8—C9—H9C	109.5
C4—C3—H3	119.1	H9A—C9—H9C	109.5
C2—C3—H3	119.1	H9B—C9—H9C	109.5
O3—C4—C3	125.3 (3)	O3—C10—H10A	109.5
O3—C4—C5	115.3 (3)	O3—C10—H10B	109.5
C3—C4—C5	119.4 (3)	H10A—C10—H10B	109.5
O4—C5—C6	125.2 (3)	O3—C10—H10C	109.5
O4—C5—C4	115.3 (3)	H10A—C10—H10C	109.5
C6—C5—C4	119.4 (3)	H10B—C10—H10C	109.5
C5—C6—C1	121.1 (3)	O4—C11—H11A	109.5
C5—C6—H6	119.4	O4—C11—H11B	109.5
C1—C6—H6	119.4	H11A—C11—H11B	109.5
O2—C7—C2	120.2 (3)	O4—C11—H11C	109.5
O2—C7—C8	120.3 (3)	H11A—C11—H11C	109.5
C2—C7—C8	119.5 (3)	H11B—C11—H11C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.82	1.86	2.577 (4)	146

Experimental details

Crystal data
Chemical formula	C₁₁H₁₄O₄
M_r	210.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.1933 (7), 9.4874 (12), 17.198 (2)
β (°)	113.164 (5)
V (Å³)	1079.1 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.31 × 0.16 × 0.14

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.066, 0.185
No. of measured, independent and observed [I > 2σ(I)] reflections	7549, 2673, 1749
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.094, 0.295, 1.12
No. of reflections	2673
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.28

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXP-97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.82	1.86	2.577 (4)	146

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), the Natural Science Foundation of Hainan Province (No. 070207) and the University Graduate Student Innovation Science Research Project of Hainan Province (No. Hxwsy2008–17). We thank Bingjing Xin for collecting the crystal data.

References

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