3-Hy­droxy-1,2-dimeth­oxyxanthone

Xiong, H.-P.; Wu, Z.-J.; Chen, F.-T.; Chen, D.-S.

doi:10.1107/S160053681102160X

organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page o1667

doi:10.1107/S160053681102160X

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3-Hydroxy-1,2-dimethoxyxanthone

Hui-Ping Xiong,^a Zhi-Jun Wu,^b ^* Fa-Tang Chen ^a and Dong-Sheng Chen ^a

^aDepartment of Mathematics and Physics, Shanghai University of Electric Power, Shanghai 200090, People's Republic of China, and ^bDepartment of Pharmacy, Changzheng Hospital, Second Military Medical University, Shanghai 200003, People's Republic of China
^*Correspondence e-mail: wuzhijun999@sina.com

(Received 9 May 2011; accepted 4 June 2011; online 18 June 2011)

The title compound (systematic name: 3-hydroxy-1,2-dimethoxy-9H-xanthen-9-one), C₁₅H₁₂O₅, was isolated from Polygala arillata. The tricyclic unit is essentially planar (r.m.s. deviation = 0.039 Å). In the crystal, the molecules form stacks along the a axis. Intermolecular O—H⋯O hydrogen bonds link the molecules into chains parallel to [010].

Related literature

For general background to the title compound and the plant Polygala arillata, see: Corrêa et al. (1970 ); De Oliveira et al. (1968 ); Dominguez et al. (1990 ); Gottlieb et al. (1970 ); Jiangshu New Medicinal College (1977 ); Li et al. (1999 ); Lin et al. (2005 ); Miao et al. (1996 , 1997 ).

Experimental

Crystal data

C₁₅H₁₂O₅
M_r = 272.25
Triclinic, $[P \overline 1]$
a = 7.338 (2) Å
b = 7.824 (3) Å
c = 11.964 (4) Å
α = 94.634 (4)°
β = 93.561 (4)°
γ = 115.027 (4)°
V = 616.8 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.15 × 0.12 × 0.10 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.984, T_max = 0.989
2562 measured reflections
2126 independent reflections
1697 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.190
S = 1.07
2126 reflections
184 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5⋯O2ⁱ	0.82	1.90	2.713 (3)	169
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 I, a10401a. DOI: 10.1107/S160053681102160X/yk2009sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681102160X/yk2009Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681102160X/yk2009Isup3.cml

checkCIF report

Comment top

Polygala arillata Buch-Ham is mainly distributed in south-west of China. The roots of Polygala arillata has been used in Chinese folk medicine to treat expectorant, hepatitis, pneumonia and rheumatism (Jiangshu New Medicinal College, 1977). Some chemical constituents of this plant have been reported previously (Miao et al., 1996, 1997; Li et al., 1999). Our chemical investigation of this plant for bioactive components resulted in the isolation of the title compound, which was previously obtained from Kielmeyera rupestris (Corrêa et al., 1970), Kielmeyera speciosa (De Oliveira et al., 1968, Gottlieb et al., 1970), Polygala nitida (Dominguez et al., 1990) and Polygala fallax (Lin et al., 2005). Herein we report the crystal structure determination of the title compound.

Related literature top

For general background to the title compound and the plant Polygala arillata, see: Corrêa et al. (1970); De Oliveira et al. (1968); Dominguez et al. (1990); Gottlieb et al. (1970); Jiangshu New Medicinal College (1977); Li et al. (1999); Lin et al. (2005); Miao et al. (1996, 1997).

Experimental top

Three 5 kg portions of dry powdered stem bark of Polygala arillata were refluxed for 1 h with 95% ethanol (50L). After removal of ethanol under reduced pressure, the extract was suspended in water and then partitioned with chloroform, ethyl acetate and n-butanol. The chloroform soluble fraction (50 g) was subjected to silica gel column chromatography using gradient elution (petroleum ether/acetone, 10:1 to 2:1, v/v). 3-hydroxy-1,2-dimethoxyxanthone was obtained from the fraction eluted by 3:1 petroleum ether/acetone ratio. Single crystals suitable for X-ray diffraction analysis were grown by slow evaporation of acetone solution at room temperature.

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. The molecular structure of the title compound, showing the atom-labelling scheme and displacement ellipsoids drawn at the 30% probability level.

3-Hydroxy-1,2-dimethoxy-9H-xanthen-9-one top

Crystal data top

C₁₅H₁₂O₅	Z = 2
M_r = 272.25	F(000) = 284
Triclinic, P1	D_x = 1.466 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.338 (2) Å	Cell parameters from 804 reflections
b = 7.824 (3) Å	θ = 2.9–27.3°
c = 11.964 (4) Å	µ = 0.11 mm⁻¹
α = 94.634 (4)°	T = 293 K
β = 93.561 (4)°	Block, colourless
γ = 115.027 (4)°	0.15 × 0.12 × 0.10 mm
V = 616.8 (3) Å³

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2126 independent reflections
Radiation source: fine-focus sealed tube	1697 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→8
T_min = 0.984, T_max = 0.989	k = −9→5
2562 measured reflections	l = −13→14

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.190	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.1114P)² + 0.1836P] where P = (F_o² + 2F_c²)/3
2126 reflections	(Δ/σ)_max < 0.001
184 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₁₅H₁₂O₅	γ = 115.027 (4)°
M_r = 272.25	V = 616.8 (3) Å³
Triclinic, P1	Z = 2
a = 7.338 (2) Å	Mo Kα radiation
b = 7.824 (3) Å	µ = 0.11 mm⁻¹
c = 11.964 (4) Å	T = 293 K
α = 94.634 (4)°	0.15 × 0.12 × 0.10 mm
β = 93.561 (4)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2126 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1697 reflections with I > 2σ(I)
T_min = 0.984, T_max = 0.989	R_int = 0.037
2562 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	0 restraints
wR(F²) = 0.190	H-atom parameters constrained
S = 1.07	Δρ_max = 0.23 e Å⁻³
2126 reflections	Δρ_min = −0.32 e Å⁻³
184 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 > 2σ(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	0.2867 (3)	0.6977 (2)	0.52398 (13)	0.0473 (5)
O2	0.2172 (3)	0.1946 (2)	0.35370 (16)	0.0603 (6)
O3	0.2629 (2)	0.3673 (2)	0.15973 (14)	0.0498 (5)
O4	0.2920 (3)	0.6826 (2)	0.06394 (14)	0.0544 (5)
O5	0.3176 (3)	0.9927 (2)	0.19396 (15)	0.0592 (6)
H5	0.2921	1.0654	0.2365	0.089*
C1	0.2721 (3)	0.5208 (3)	0.22752 (19)	0.0396 (5)
C2	0.2933 (3)	0.6818 (3)	0.17897 (19)	0.0434 (6)
C3	0.3077 (3)	0.8442 (3)	0.2474 (2)	0.0446 (6)
C4	0.3094 (3)	0.8437 (3)	0.3620 (2)	0.0444 (6)
H4	0.3253	0.9520	0.4077	0.053*
C5	0.2517 (4)	0.5696 (4)	0.6956 (2)	0.0534 (6)
H5A	0.2708	0.6866	0.7317	0.064*
C6	0.2189 (4)	0.4191 (4)	0.7557 (2)	0.0599 (7)
H6	0.2148	0.4343	0.8333	0.072*
C7	0.1919 (4)	0.2451 (4)	0.7025 (2)	0.0599 (7)
H7	0.1689	0.1442	0.7444	0.072*
C8	0.1988 (4)	0.2210 (4)	0.5886 (2)	0.0522 (6)
H8	0.1827	0.1041	0.5537	0.063*
C9	0.2376 (3)	0.3482 (3)	0.4018 (2)	0.0417 (6)
C10	0.2654 (3)	0.5149 (3)	0.34488 (19)	0.0376 (5)
C11	0.2873 (3)	0.6818 (3)	0.4091 (2)	0.0397 (5)
C12	0.2559 (3)	0.5436 (3)	0.5796 (2)	0.0437 (6)
C13	0.2302 (3)	0.3713 (3)	0.5240 (2)	0.0422 (6)
C14	0.0691 (5)	0.2530 (4)	0.0989 (3)	0.0700 (8)
H14A	−0.0279	0.1977	0.1511	0.105*
H14B	0.0770	0.1539	0.0496	0.105*
H14C	0.0278	0.3306	0.0551	0.105*
C15	0.4879 (5)	0.7613 (5)	0.0279 (3)	0.0741 (9)
H15A	0.5620	0.8891	0.0637	0.111*
H15B	0.4772	0.7615	−0.0524	0.111*
H15C	0.5575	0.6865	0.0481	0.111*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0617 (10)	0.0392 (9)	0.0448 (9)	0.0267 (8)	0.0019 (8)	0.0002 (7)
O2	0.0869 (14)	0.0343 (9)	0.0675 (12)	0.0328 (9)	0.0145 (10)	0.0052 (8)
O3	0.0571 (10)	0.0413 (9)	0.0539 (10)	0.0275 (8)	−0.0010 (8)	−0.0093 (7)
O4	0.0648 (11)	0.0587 (11)	0.0442 (10)	0.0317 (9)	−0.0002 (8)	0.0053 (8)
O5	0.0896 (14)	0.0429 (10)	0.0591 (11)	0.0397 (10)	0.0147 (10)	0.0137 (8)
C1	0.0373 (11)	0.0346 (11)	0.0480 (13)	0.0186 (9)	0.0005 (9)	−0.0032 (9)
C2	0.0447 (12)	0.0424 (13)	0.0455 (13)	0.0220 (10)	0.0022 (10)	0.0017 (10)
C3	0.0487 (13)	0.0353 (12)	0.0548 (14)	0.0226 (10)	0.0049 (10)	0.0077 (10)
C4	0.0525 (13)	0.0335 (12)	0.0525 (14)	0.0248 (10)	0.0037 (11)	0.0005 (10)
C5	0.0511 (14)	0.0574 (15)	0.0497 (14)	0.0230 (12)	0.0003 (11)	0.0013 (11)
C6	0.0504 (14)	0.0740 (19)	0.0502 (15)	0.0208 (13)	0.0029 (11)	0.0154 (13)
C7	0.0504 (14)	0.0602 (17)	0.0641 (17)	0.0164 (12)	0.0021 (12)	0.0250 (13)
C8	0.0459 (13)	0.0433 (13)	0.0665 (16)	0.0172 (11)	0.0046 (11)	0.0136 (11)
C9	0.0378 (11)	0.0332 (11)	0.0577 (14)	0.0190 (9)	0.0048 (10)	0.0034 (10)
C10	0.0335 (11)	0.0307 (11)	0.0503 (13)	0.0161 (8)	0.0026 (9)	0.0027 (9)
C11	0.0399 (11)	0.0364 (12)	0.0457 (12)	0.0202 (9)	0.0018 (9)	0.0008 (9)
C12	0.0380 (11)	0.0439 (13)	0.0506 (13)	0.0188 (10)	0.0032 (9)	0.0077 (10)
C13	0.0327 (11)	0.0404 (13)	0.0543 (14)	0.0163 (9)	0.0034 (10)	0.0086 (10)
C14	0.0711 (18)	0.0511 (16)	0.078 (2)	0.0234 (13)	−0.0121 (15)	−0.0171 (14)
C15	0.085 (2)	0.083 (2)	0.0597 (17)	0.0379 (17)	0.0243 (16)	0.0156 (15)

Geometric parameters (Å, º) top

O1—C12	1.366 (3)	C5—H5A	0.9300
O1—C11	1.370 (3)	C6—C7	1.383 (4)
O2—C9	1.234 (3)	C6—H6	0.9300
O3—C1	1.368 (3)	C7—C8	1.367 (4)
O3—C14	1.430 (3)	C7—H7	0.9300
O4—C2	1.376 (3)	C8—C13	1.405 (3)
O4—C15	1.415 (3)	C8—H8	0.9300
O5—C3	1.349 (3)	C9—C10	1.463 (3)
O5—H5	0.8200	C9—C13	1.466 (3)
C1—C2	1.383 (3)	C10—C11	1.402 (3)
C1—C10	1.412 (3)	C12—C13	1.386 (3)
C2—C3	1.415 (3)	C14—H14A	0.9600
C3—C4	1.370 (3)	C14—H14B	0.9600
C4—C11	1.379 (3)	C14—H14C	0.9600
C4—H4	0.9300	C15—H15A	0.9600
C5—C6	1.370 (4)	C15—H15B	0.9600
C5—C12	1.391 (4)	C15—H15C	0.9600

C12—O1—C11	119.52 (18)	O2—C9—C10	124.6 (2)
C1—O3—C14	114.41 (19)	O2—C9—C13	120.0 (2)
C2—O4—C15	113.4 (2)	C10—C9—C13	115.45 (19)
C3—O5—H5	109.5	C11—C10—C1	116.5 (2)
O3—C1—C2	118.6 (2)	C11—C10—C9	119.1 (2)
O3—C1—C10	120.1 (2)	C1—C10—C9	124.3 (2)
C2—C1—C10	121.2 (2)	O1—C11—C4	114.15 (19)
O4—C2—C1	120.4 (2)	O1—C11—C10	123.0 (2)
O4—C2—C3	119.7 (2)	C4—C11—C10	122.9 (2)
C1—C2—C3	119.8 (2)	O1—C12—C13	122.1 (2)
O5—C3—C4	123.5 (2)	O1—C12—C5	116.1 (2)
O5—C3—C2	116.7 (2)	C13—C12—C5	121.8 (2)
C4—C3—C2	119.7 (2)	C12—C13—C8	117.8 (2)
C3—C4—C11	119.7 (2)	C12—C13—C9	120.7 (2)
C3—C4—H4	120.2	C8—C13—C9	121.4 (2)
C11—C4—H4	120.2	O3—C14—H14A	109.5
C6—C5—C12	118.6 (3)	O3—C14—H14B	109.5
C6—C5—H5A	120.7	H14A—C14—H14B	109.5
C12—C5—H5A	120.7	O3—C14—H14C	109.5
C5—C6—C7	120.9 (3)	H14A—C14—H14C	109.5
C5—C6—H6	119.6	H14B—C14—H14C	109.5
C7—C6—H6	119.6	O4—C15—H15A	109.5
C8—C7—C6	120.3 (2)	O4—C15—H15B	109.5
C8—C7—H7	119.9	H15A—C15—H15B	109.5
C6—C7—H7	119.9	O4—C15—H15C	109.5
C7—C8—C13	120.5 (3)	H15A—C15—H15C	109.5
C7—C8—H8	119.7	H15B—C15—H15C	109.5
C13—C8—H8	119.7

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O2ⁱ	0.82	1.90	2.713 (3)	169

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₂O₅
M_r	272.25
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.338 (2), 7.824 (3), 11.964 (4)
α, β, γ (°)	94.634 (4), 93.561 (4), 115.027 (4)
V (Å³)	616.8 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.15 × 0.12 × 0.10

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.984, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	2562, 2126, 1697
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.190, 1.07
No. of reflections	2126
No. of parameters	184
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.32

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
O5—H5···O2ⁱ	0.82	1.90	2.713 (3)	169

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

Acknowledgements

The authors thank Dr Zhen-Xia Chen (Department of Chemistry, Fudan University, Shanghai) for the structure analysis.

References

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