2-Hydr­oxy-1-methoxyxanthen-9-one monohydrate

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

doi:10.1107/S1600536809039348

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2798

https://doi.org/10.1107/S1600536809039348

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2-Hydroxy-1-methoxyxanthen-9-one monohydrate

Guangying Chen,^a Jun Zhao,^a Changchun Cen,^a Changri Han ^a ^* and Xinming 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: hchr116@hainnu.edu.cn

(Received 10 September 2009; accepted 28 September 2009; online 23 October 2009)

In the title compound, C₁₄H₁₀O₄·H₂O, isolated from the roots of Calophyllum membranaceum, the xanthene ring system is almost planar (r.m.s. deviation = 0.008 Å). In the crystal structure, intermolecular O—H⋯O and O—H⋯(O,O) hydrogen bonds connect the molecules.

Related literature

For medicinal and botanical background, see: Zou et al. (2005 ); Chen et al. (2008 ).

Experimental

Crystal data

C₁₄H₁₀O₄·H₂O
M_r = 260.24
Monoclinic, P 2₁ /c
a = 8.8008 (6) Å
b = 7.0856 (4) Å
c = 19.4596 (9) Å
β = 102.402 (4)°
V = 1185.16 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 295 K
0.38 × 0.26 × 0.24 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.959, T_max = 0.974
8151 measured reflections
2919 independent reflections
2269 reflections with I > 2σ(I)
R_int = 0.080

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.164
S = 1.04
2919 reflections
181 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 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
O4—H4A⋯O1W	0.82	1.90	2.7126 (16)	174
O1W—H1A⋯O2ⁱ	0.83 (3)	2.03 (3)	2.857 (2)	174 (3)
O1W—H1B⋯O4ⁱⁱ	0.81 (3)	2.34 (3)	2.9540 (19)	134 (2)
O1W—H1B⋯O3ⁱⁱ	0.81 (3)	2.37 (3)	3.1195 (17)	155 (2)
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x, -y, -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/S1600536809039348/hb5095sup1.cif

Structure factors: contains datablock . DOI: https://doi.org/10.1107/S1600536809039348/hb5095Isup2.hkl

checkCIF report

Comment top

Secondary metabolites in the plants of Calophyllum membranaceum are mainly xanthones, coumarins and flavonids (Zou et al., 2005; Chen et al., 2008). The plants in this family were used in folk medicine such as, for rheumatism, arthritis, lumbago and wounds (Zou et al., 2005). The title xanthones was isolated from the 75% EtOH extract of the roots of Calophyllum membranaceum which were collected from Lingshui County, Hainan Province, P. R. China. We have undertaken the X-ray crystal structure analysis of the title xanthone in order to establish its molecular structure and relative stereochemistry.

The xanthene ring system of (I) (C1-C13/O1) is almost planar, with all atoms lying within 0.008 (8)Å of the mean plane.

In the crystal, molecules are linked by intermolecular O–H···O hydrogen bonds into chains (Fig.2). The hydrogen bonds and angles are listed in Table 1.

Related literature top

For medicinal and botanical background, see: Zou et al. (2005); Chen et al. (2008).

Experimental top

Air-dried roots of Calophyllum membranaceum (15.00 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-hexane, successively, yielding a petroleum ether extract, 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 15 fractions (A—N). Fraction C was further separated by column chromatography with a gradient of CHCl₃—CH₃OH to give the title xanthone. The crude product was dissolved in small amount of anhydrous methanol to obtain colourless blocks of (I) by slow evaporation of a methanol solution at 298 K.

Structure description top

The xanthene ring system of (I) (C1-C13/O1) is almost planar, with all atoms lying within 0.008 (8)Å of the mean plane.

In the crystal, molecules are linked by intermolecular O–H···O hydrogen bonds into chains (Fig.2). The hydrogen bonds and angles are listed in Table 1.

For medicinal and botanical background, see: Zou et al. (2005); Chen et al. (2008).

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 (I): displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view of the molecular packing. Dashed lines indicate hydrogen bonds.

2-Hydroxy-1-methoxyxanthen-9-one monohydrate top

Crystal data top

C₁₄H₁₀O₄·H₂O	F(000) = 544
M_r = 260.24	D_x = 1.458 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2919 reflections
a = 8.8008 (6) Å	θ = 2.1–28.2°
b = 7.0856 (4) Å	µ = 0.11 mm⁻¹
c = 19.4596 (9) Å	T = 295 K
β = 102.402 (4)°	Block, colourless
V = 1185.16 (12) Å³	0.38 × 0.26 × 0.24 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	2919 independent reflections
Radiation source: fine-focus sealed tube	2269 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.080
Detector resolution: 0 pixels mm^-1	θ_max = 28.2°, θ_min = 2.1°
ω scans	h = −6→11
Absorption correction: multi-scan (SADABS; Bruker, 1997)	k = −8→9
T_min = 0.959, T_max = 0.974	l = −25→25
8151 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.053	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.164	w = 1/[σ²(F_o²) + (0.0823P)² + 0.2871P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
2919 reflections	Δρ_max = 0.26 e Å⁻³
181 parameters	Δρ_min = −0.36 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.095 (8)

Crystal data top

C₁₄H₁₀O₄·H₂O	V = 1185.16 (12) Å³
M_r = 260.24	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.8008 (6) Å	µ = 0.11 mm⁻¹
b = 7.0856 (4) Å	T = 295 K
c = 19.4596 (9) Å	0.38 × 0.26 × 0.24 mm
β = 102.402 (4)°

Data collection top

Bruker SMART CCD diffractometer	2919 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	2269 reflections with I > 2σ(I)
T_min = 0.959, T_max = 0.974	R_int = 0.080
8151 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.164	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.26 e Å⁻³
2919 reflections	Δρ_min = −0.36 e Å⁻³
181 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	0.65861 (11)	0.14472 (16)	0.26194 (6)	0.0409 (3)
O2	0.24707 (14)	0.1457 (2)	0.33085 (6)	0.0577 (4)
O3	0.09211 (11)	0.10250 (16)	0.19163 (6)	0.0412 (3)
O4	0.11784 (12)	0.12437 (18)	0.05791 (5)	0.0459 (3)
H4A	0.1386	0.1122	0.0190	0.069*
O1W	0.16228 (15)	0.0842 (3)	−0.07501 (6)	0.0581 (4)
H1A	0.181 (3)	0.166 (4)	−0.1024 (17)	0.097 (10)*
H1B	0.080 (3)	0.039 (4)	−0.0954 (14)	0.079 (8)*
C1	0.65891 (18)	0.1459 (2)	0.33241 (8)	0.0377 (3)
C2	0.8053 (2)	0.1522 (2)	0.37783 (9)	0.0491 (4)
H2A	0.8955	0.1548	0.3602	0.059*
C3	0.8131 (2)	0.1546 (3)	0.44946 (10)	0.0577 (5)
H3A	0.9096	0.1575	0.4805	0.069*
C4	0.6771 (3)	0.1527 (3)	0.47583 (9)	0.0593 (5)
H4B	0.6837	0.1550	0.5242	0.071*
C5	0.5341 (2)	0.1475 (2)	0.43070 (9)	0.0497 (4)
H5A	0.4445	0.1464	0.4487	0.060*
C6	0.52170 (18)	0.1439 (2)	0.35728 (7)	0.0367 (3)
C7	0.36878 (17)	0.1408 (2)	0.30878 (7)	0.0360 (3)
C8	0.37350 (15)	0.13504 (18)	0.23329 (7)	0.0299 (3)
C9	0.23858 (15)	0.12734 (19)	0.17825 (7)	0.0316 (3)
C10	0.25162 (16)	0.12938 (19)	0.10794 (7)	0.0343 (3)
C11	0.39927 (17)	0.1332 (2)	0.09150 (7)	0.0374 (3)
H11A	0.4075	0.1331	0.0446	0.045*
C12	0.53188 (17)	0.1372 (2)	0.14382 (8)	0.0372 (3)
H12A	0.6293	0.1385	0.1325	0.045*
C13	0.51916 (16)	0.13944 (19)	0.21397 (7)	0.0318 (3)
C14	0.0097 (2)	0.2739 (3)	0.19948 (11)	0.0578 (5)
H14A	−0.0904	0.2434	0.2086	0.087*
H14B	−0.0035	0.3468	0.1570	0.087*
H14C	0.0681	0.3457	0.2381	0.087*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0304 (5)	0.0548 (7)	0.0354 (6)	−0.0022 (4)	0.0027 (4)	−0.0018 (4)
O2	0.0468 (6)	0.0962 (10)	0.0337 (6)	−0.0072 (6)	0.0163 (5)	−0.0084 (6)
O3	0.0315 (5)	0.0527 (7)	0.0412 (6)	−0.0061 (4)	0.0118 (4)	−0.0017 (4)
O4	0.0377 (6)	0.0689 (8)	0.0284 (5)	−0.0012 (5)	0.0010 (4)	0.0009 (4)
O1W	0.0456 (7)	0.0910 (11)	0.0357 (6)	−0.0150 (7)	0.0044 (5)	0.0005 (6)
C1	0.0426 (7)	0.0330 (7)	0.0337 (7)	−0.0023 (5)	0.0000 (6)	−0.0023 (5)
C2	0.0439 (8)	0.0466 (9)	0.0490 (9)	−0.0025 (7)	−0.0071 (7)	−0.0036 (7)
C3	0.0627 (11)	0.0509 (10)	0.0459 (9)	−0.0027 (8)	−0.0187 (8)	−0.0028 (7)
C4	0.0798 (13)	0.0582 (11)	0.0317 (8)	−0.0053 (9)	−0.0063 (8)	−0.0023 (7)
C5	0.0643 (10)	0.0517 (10)	0.0304 (7)	−0.0039 (7)	0.0042 (7)	−0.0028 (6)
C6	0.0453 (8)	0.0339 (7)	0.0285 (7)	−0.0035 (5)	0.0029 (5)	−0.0022 (5)
C7	0.0400 (7)	0.0387 (7)	0.0296 (7)	−0.0042 (5)	0.0082 (5)	−0.0030 (5)
C8	0.0315 (6)	0.0306 (6)	0.0276 (6)	−0.0029 (5)	0.0062 (5)	−0.0006 (5)
C9	0.0307 (6)	0.0333 (7)	0.0315 (7)	−0.0026 (5)	0.0081 (5)	−0.0002 (5)
C10	0.0347 (7)	0.0370 (7)	0.0298 (6)	−0.0018 (5)	0.0039 (5)	0.0014 (5)
C11	0.0415 (7)	0.0442 (8)	0.0286 (7)	−0.0004 (6)	0.0119 (6)	0.0021 (5)
C12	0.0341 (7)	0.0448 (8)	0.0355 (7)	−0.0009 (6)	0.0138 (5)	0.0008 (6)
C13	0.0302 (6)	0.0325 (7)	0.0324 (7)	−0.0016 (5)	0.0055 (5)	−0.0013 (5)
C14	0.0417 (8)	0.0675 (12)	0.0693 (11)	0.0063 (8)	0.0235 (8)	−0.0022 (9)

Geometric parameters (Å, º) top

O1—C1	1.3708 (18)	C4—H4B	0.9300
O1—C13	1.3737 (16)	C5—C6	1.409 (2)
O2—C7	1.2372 (17)	C5—H5A	0.9300
O3—C9	1.3801 (16)	C6—C7	1.469 (2)
O3—C14	1.439 (2)	C7—C8	1.4790 (18)
O4—C10	1.3576 (17)	C8—C13	1.4116 (18)
O4—H4A	0.8200	C8—C9	1.4191 (18)
O1W—H1A	0.83 (3)	C9—C10	1.3973 (19)
O1W—H1B	0.81 (3)	C10—C11	1.4036 (19)
C1—C6	1.394 (2)	C11—C12	1.375 (2)
C1—C2	1.398 (2)	C11—H11A	0.9300
C2—C3	1.381 (3)	C12—C13	1.3935 (19)
C2—H2A	0.9300	C12—H12A	0.9300
C3—C4	1.400 (3)	C14—H14A	0.9600
C3—H3A	0.9300	C14—H14B	0.9600
C4—C5	1.371 (3)	C14—H14C	0.9600

C1—O1—C13	119.30 (11)	C13—C8—C9	117.41 (12)
C9—O3—C14	115.13 (12)	C13—C8—C7	118.99 (12)
C10—O4—H4A	109.5	C9—C8—C7	123.59 (12)
H1A—O1W—H1B	104 (3)	O3—C9—C10	117.56 (12)
O1—C1—C6	122.10 (13)	O3—C9—C8	121.77 (12)
O1—C1—C2	115.87 (14)	C10—C9—C8	120.48 (12)
C6—C1—C2	122.02 (14)	O4—C10—C9	117.45 (12)
C3—C2—C1	118.55 (17)	O4—C10—C11	122.66 (13)
C3—C2—H2A	120.7	C9—C10—C11	119.88 (12)
C1—C2—H2A	120.7	C12—C11—C10	120.79 (12)
C2—C3—C4	120.59 (16)	C12—C11—H11A	119.6
C2—C3—H3A	119.7	C10—C11—H11A	119.6
C4—C3—H3A	119.7	C11—C12—C13	119.46 (12)
C5—C4—C3	120.29 (16)	C11—C12—H12A	120.3
C5—C4—H4B	119.9	C13—C12—H12A	120.3
C3—C4—H4B	119.9	O1—C13—C12	114.70 (12)
C4—C5—C6	120.70 (17)	O1—C13—C8	123.34 (12)
C4—C5—H5A	119.6	C12—C13—C8	121.95 (13)
C6—C5—H5A	119.6	O3—C14—H14A	109.5
C1—C6—C5	117.85 (14)	O3—C14—H14B	109.5
C1—C6—C7	121.30 (13)	H14A—C14—H14B	109.5
C5—C6—C7	120.84 (14)	O3—C14—H14C	109.5
O2—C7—C6	121.24 (13)	H14A—C14—H14C	109.5
O2—C7—C8	123.82 (13)	H14B—C14—H14C	109.5
C6—C7—C8	114.92 (12)

C13—O1—C1—C6	−0.65 (19)	C14—O3—C9—C10	−93.42 (16)
C13—O1—C1—C2	−179.73 (12)	C14—O3—C9—C8	91.70 (16)
O1—C1—C2—C3	179.71 (14)	C13—C8—C9—O3	173.03 (12)
C6—C1—C2—C3	0.6 (2)	C7—C8—C9—O3	−7.70 (19)
C1—C2—C3—C4	−0.7 (3)	C13—C8—C9—C10	−1.70 (18)
C2—C3—C4—C5	0.3 (3)	C7—C8—C9—C10	177.57 (12)
C3—C4—C5—C6	0.1 (3)	O3—C9—C10—O4	5.96 (18)
O1—C1—C6—C5	−179.30 (13)	C8—C9—C10—O4	−179.09 (12)
C2—C1—C6—C5	−0.3 (2)	O3—C9—C10—C11	−172.99 (12)
O1—C1—C6—C7	−0.2 (2)	C8—C9—C10—C11	1.96 (19)
C2—C1—C6—C7	178.83 (13)	O4—C10—C11—C12	−179.64 (13)
C4—C5—C6—C1	−0.1 (2)	C9—C10—C11—C12	−0.7 (2)
C4—C5—C6—C7	−179.18 (15)	C10—C11—C12—C13	−0.7 (2)
C1—C6—C7—O2	−177.43 (14)	C1—O1—C13—C12	−179.55 (12)
C5—C6—C7—O2	1.6 (2)	C1—O1—C13—C8	−0.03 (18)
C1—C6—C7—C8	1.57 (19)	C11—C12—C13—O1	−179.57 (12)
C5—C6—C7—C8	−179.36 (13)	C11—C12—C13—C8	0.9 (2)
O2—C7—C8—C13	176.82 (14)	C9—C8—C13—O1	−179.21 (12)
C6—C7—C8—C13	−2.15 (17)	C7—C8—C13—O1	1.49 (19)
O2—C7—C8—C9	−2.4 (2)	C9—C8—C13—C12	0.28 (19)
C6—C7—C8—C9	178.59 (12)	C7—C8—C13—C12	−179.03 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O1W	0.82	1.90	2.7126 (16)	174
O1W—H1A···O2ⁱ	0.83 (3)	2.03 (3)	2.857 (2)	174 (3)
O1W—H1B···O4ⁱⁱ	0.81 (3)	2.34 (3)	2.9540 (19)	134 (2)
O1W—H1B···O3ⁱⁱ	0.81 (3)	2.37 (3)	3.1195 (17)	155 (2)

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x, −y, −z.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₀O₄·H₂O
M_r	260.24
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	8.8008 (6), 7.0856 (4), 19.4596 (9)
β (°)	102.402 (4)
V (Å³)	1185.16 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.38 × 0.26 × 0.24

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.959, 0.974
No. of measured, independent and observed [I > 2σ(I)] reflections	8151, 2919, 2269
R_int	0.080
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.164, 1.04
No. of reflections	2919
No. of parameters	181
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.36

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
O4—H4A···O1W	0.82	1.90	2.7126 (16)	174
O1W—H1A···O2ⁱ	0.83 (3)	2.03 (3)	2.857 (2)	174 (3)
O1W—H1B···O4ⁱⁱ	0.81 (3)	2.34 (3)	2.9540 (19)	134 (2)
O1W—H1B···O3ⁱⁱ	0.81 (3)	2.37 (3)	3.1195 (17)	155 (2)

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x, −y, −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 Natural Science Foundation of Hainan Province, China (No. 070207). We thank Bingjing Xin and Tingting Zhang for collecting the crystal data.

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