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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): o2716–o2717.
Published online 2010 October 2. doi:  10.1107/S1600536810039012
PMCID: PMC3009314

5,7-Dihy­droxy-3,6-dimeth­oxy-2-(4-meth­oxy­phen­yl)-4H-chromen-4-one monohydrate

Abstract

The title compound, C18H16O7·H2O, is a flavonoid isolated from Dodonaea viscosa­. The benzopyran ring system of the flavonoid is essentially planar [maximum deviation = 0.025 (2) Å] and inclined at 5.83 (2)° to the attached benzene ring. The water of hydration is involved in extensive hydrogen bonding, assembling the mol­ecules into a supra­molecular network via classical inter­molecular O—H(...)O hydrogen bonding. The crystal structure is further stabilized by π–π stacking inter­actions [centroid–centroid distance between benzene rings = 3.564 (3) Å].

Related literature

For the anti-oxidant activity of flavonoids, see: Pedrielli et al. (2001 [triangle], for their anti-protozoal activity, see: Calzada et al. (1999 [triangle]) and for their anti-viral activity, see: Lin et al. (1999 [triangle]). For hydrogen-bond motifs, see: Etter et al. (1990 [triangle]). For related structures, see: Arfan et al. (2010 [triangle]); Azhar ul et al. (2004 [triangle]); Ferheen et al. (2005 [triangle]); Hussain et al. (2008 [triangle], 2009 [triangle]); Jan et al. (2009 [triangle]); Khan et al. (2005a [triangle],b [triangle]); Nisar et al. (2010 [triangle]); Riaz et al. (2002 [triangle]); Sharif et al. (2005 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2716-scheme1.jpg

Experimental

Crystal data

  • C18H16O7·H2O
  • M r = 362.32
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2716-efi1.jpg
  • a = 19.869 (4) Å
  • b = 6.8126 (15) Å
  • c = 24.424 (5) Å
  • β = 91.298 (4)°
  • V = 3305.2 (12) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.12 mm−1
  • T = 150 K
  • 0.19 × 0.18 × 0.09 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2008a [triangle]) T min = 0.978, T max = 0.990
  • 14127 measured reflections
  • 3400 independent reflections
  • 2072 reflections with I > 2σ(I)
  • R int = 0.068

Refinement

  • R[F 2 > 2σ(F 2)] = 0.050
  • wR(F 2) = 0.142
  • S = 1.05
  • 3400 reflections
  • 243 parameters
  • 3 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.28 e Å−3
  • Δρmin = −0.28 e Å−3

Data collection: APEX2 (Bruker, 2008 [triangle]); cell refinement: SAINT (Bruker, 2008 [triangle]); data reduction: SAINT; program(s) used to solve structure: SIR2004 (Burla et al., 2005 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008b [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810039012/rk2231sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810039012/rk2231Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the Pakistan Science Foundation for financial support.

supplementary crystallographic information

Comment

Our investigation on natural product chemistry (Arfan et al., (2010); Azhar et al., (2004); Ferheen et al., (2005); Hussain et al., (2008, 2009); Jan et al., 2009) is intended to explore the medicinal aspect of indigenous plants (Khan et al., (2005a); Khan et al., (2005b); Nisar et al., (2010); Riaz et al., (2002); Sharif et al., (2005).) of Pakistan. The plant Dodonaea Viscosa has been screened for the presence of biologically active compounds resulting in the isolation of a Flavonoid (Fig.1). The crystal structure and isolation of the title compound are presented below. Flavonoids, comprising a vast family of polyphenolic secondary metabolites, exhibit a wide range of biological activities, such as anti–oxidant (Pedrielli et al., 2001), anti–viral (Lin et al., 1999), anti–protozoal (Calzada, et al., 1999).

The methoxy groups at C4 and C9 of title compound (Fig. 1) are nearly orthogonal to the benzopyranone moiety, as indicated by the torsion angles 97.5 (3)° and 107.6 (3)° respectively. The methoxy group at C15 is nearly coplanar with the phenyl ring with torsion angle (C17–C15–O7–C16) 0.3 (4)°. Rings A and B (the benzopyrone moiety) are fused at C1 and C7 and almost coplanar, the interplanar angle between the two rings is 1.40 (3)°. Ring C (the phenyl moeity) is attached to benzopyranone system at C11 with an interplanar angle of 5.83 (2)° between the two ring systems.

A combination of intermolecular and intramolecular hydrogen bonding, forming R46(12) and R44(16) patterns (Etter et al., 1990), links the molecules into stepped ribbons perpendicular to b axis (Fig. 2 and Table 1). The ribbons are stacked parallel to the b axis by π–π interactions (Fig. 3); the average interplanar distance is 3.378 (3)Å (under symmetry operation 3/2-x, -1/2+y, 3/2-z) and the distance from the centroid of the phenyl group to the centre of the C1–C7 bond is 3.476 (3)Å.

Experimental

The whole plant of Dodonaea viscosa (50 kg) was powdered and extracted with methanol (100 L × 3) at room temperature and the residue (1 kg) was separated under vacuum. The residue was suspended in water and extracted with n–hexane, chloroform, ethyl acetate and n–butanol respectively. The ethyl acetate fraction (250 g) was subjected repeatedly to column chromatography on silica gel using petroleum ether with a gradient of 25% chloroform to yield the title compound (50 mg). Single crystals suitable for X–ray diffraction analysis were obtained from an ether–chloroform mixture (1:2) by slow evaporation of the solvent at room temperature.

Refinement

H atoms bonded to carbon and the phenol oxygen atoms were placed in geometric positions using a riding model, C—H distances were constrained as 0.95Å, 0.98Å and 0.84Å, for aryl, methyl and phenol groups respectively. Hydrogen atoms on the water molecule were located from difference maps and their coordinates refined under restraints. Thermal parameters were set to Uiso(H) = 1.5Ueq(C, O) for methyl groups and the water molecule and Uiso(H) = 1.2Ueq(C) for all others.

Figures

Fig. 1.
Molecular structure of title compound with atom numbering scheme. Displacement ellipsoids are drawn at 50% probability level. H atoms are presented as a small spheres of arbitrary radius. Several H bonds are drawn by dashed lines.
Fig. 2.
Packing diagram showing the H–bond network (dashed lines).
Fig. 3.
The π–π interactions. Red cirles mark centroids of bonds or rings.

Crystal data

C18H16O7·H2OF(000) = 1520
Mr = 362.32Dx = 1.456 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1391 reflections
a = 19.869 (4) Åθ = 2.6–22.0°
b = 6.8126 (15) ŵ = 0.12 mm1
c = 24.424 (5) ÅT = 150 K
β = 91.298 (4)°Block, yellow
V = 3305.2 (12) Å30.19 × 0.18 × 0.09 mm
Z = 8

Data collection

Bruker APEXII CCD diffractometer3400 independent reflections
Radiation source: fine–focus sealed tube2072 reflections with I > 2σ(I)
graphiteRint = 0.068
[var phi] and ω scansθmax = 26.4°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)h = −24→24
Tmin = 0.978, Tmax = 0.990k = −8→8
14127 measured reflectionsl = −30→30

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.142H atoms treated by a mixture of independent and constrained refinement
S = 1.05w = 1/[σ2(Fo2) + (0.0597P)2 + 1.2286P] where P = (Fo2 + 2Fc2)/3
3400 reflections(Δ/σ)max < 0.001
243 parametersΔρmax = 0.28 e Å3
3 restraintsΔρmin = −0.28 e Å3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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)

xyzUiso*/Ueq
O10.69131 (8)0.1125 (2)0.73867 (6)0.0233 (4)
C10.65171 (12)0.1096 (4)0.69190 (10)0.0229 (6)
C20.58358 (12)0.0898 (4)0.69845 (10)0.0258 (6)
H20.56510.08240.73390.031*
C30.54256 (13)0.0807 (4)0.65176 (10)0.0263 (6)
O20.47576 (9)0.0548 (3)0.65803 (8)0.0367 (5)
H2A0.45730.03290.62740.063 (11)*
C40.56984 (13)0.0955 (4)0.59938 (10)0.0268 (6)
O30.52807 (9)0.0810 (2)0.55366 (7)0.0313 (5)
C50.50843 (15)0.2684 (4)0.53157 (11)0.0381 (7)
H5A0.47890.24880.49930.057*
H5B0.54860.34130.52100.057*
H5C0.48440.34290.55930.057*
C60.63836 (13)0.1158 (4)0.59382 (10)0.0248 (6)
O40.66442 (10)0.1283 (3)0.54307 (7)0.0326 (5)
H4A0.70660.12790.54560.079 (13)*
C70.68135 (12)0.1217 (4)0.64058 (9)0.0223 (5)
C80.75264 (12)0.1433 (4)0.63673 (10)0.0236 (6)
O50.78120 (9)0.1632 (3)0.59130 (7)0.0314 (5)
C90.79061 (12)0.1419 (4)0.68777 (10)0.0230 (6)
O60.85888 (8)0.1730 (3)0.68523 (7)0.0308 (5)
C100.89618 (14)0.0038 (5)0.66731 (12)0.0463 (8)
H10A0.94420.03600.66660.069*
H10B0.8805−0.03410.63050.069*
H10C0.8892−0.10540.69270.069*
C110.75982 (12)0.1256 (4)0.73687 (10)0.0227 (6)
C120.79011 (12)0.1236 (3)0.79246 (10)0.0216 (5)
C130.85991 (12)0.1219 (4)0.80250 (10)0.0264 (6)
H130.88950.12290.77250.032*
C140.88602 (13)0.1188 (4)0.85496 (10)0.0253 (6)
H140.93340.11530.86090.030*
C150.84399 (12)0.1208 (4)0.89942 (10)0.0225 (5)
O70.87539 (8)0.1210 (3)0.94962 (7)0.0300 (4)
C160.83423 (14)0.1220 (5)0.99661 (10)0.0407 (7)
H16A0.86290.12241.02980.061*
H16B0.80570.00470.99630.061*
H16C0.80580.23960.99600.061*
C170.77463 (12)0.1225 (4)0.89071 (10)0.0252 (6)
H170.74530.12390.92090.030*
C180.74882 (12)0.1220 (4)0.83780 (10)0.0232 (6)
H180.70140.12060.83210.028*
O1W0.88745 (11)0.4465 (4)0.57732 (8)0.0492 (6)
H1A0.8602 (15)0.357 (4)0.5866 (12)0.074*
H1B0.8908 (17)0.435 (5)0.5425 (7)0.074*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0190 (9)0.0306 (10)0.0200 (9)−0.0011 (7)−0.0033 (7)−0.0012 (8)
C10.0253 (13)0.0201 (13)0.0230 (13)0.0015 (10)−0.0049 (11)−0.0001 (11)
C20.0245 (14)0.0287 (15)0.0243 (13)0.0006 (11)0.0005 (11)−0.0022 (11)
C30.0240 (14)0.0253 (15)0.0294 (14)−0.0005 (11)−0.0028 (11)−0.0007 (11)
O20.0221 (10)0.0538 (14)0.0340 (11)−0.0035 (9)−0.0051 (8)−0.0030 (9)
C40.0340 (15)0.0214 (14)0.0246 (14)0.0005 (11)−0.0076 (11)−0.0029 (11)
O30.0352 (11)0.0284 (10)0.0297 (10)−0.0006 (8)−0.0143 (8)−0.0011 (8)
C50.0397 (17)0.0334 (17)0.0405 (17)0.0053 (13)−0.0154 (13)0.0020 (13)
C60.0314 (15)0.0206 (13)0.0223 (13)0.0029 (11)−0.0003 (11)−0.0013 (11)
O40.0339 (12)0.0423 (12)0.0217 (10)0.0024 (9)−0.0011 (8)−0.0005 (8)
C70.0260 (13)0.0190 (13)0.0219 (13)0.0025 (11)−0.0018 (10)−0.0010 (10)
C80.0277 (14)0.0206 (13)0.0226 (13)0.0014 (11)0.0029 (11)−0.0005 (10)
O50.0288 (10)0.0439 (12)0.0217 (10)0.0000 (9)0.0026 (8)0.0000 (8)
C90.0191 (13)0.0246 (14)0.0253 (13)−0.0010 (10)0.0012 (10)−0.0005 (11)
O60.0211 (9)0.0428 (12)0.0285 (10)−0.0036 (8)0.0024 (8)0.0014 (8)
C100.0263 (16)0.072 (2)0.0404 (17)0.0160 (15)0.0009 (13)−0.0118 (16)
C110.0189 (13)0.0216 (13)0.0276 (14)0.0014 (10)−0.0004 (11)−0.0009 (11)
C120.0229 (13)0.0181 (13)0.0238 (13)−0.0001 (10)−0.0028 (10)−0.0014 (10)
C130.0236 (13)0.0291 (14)0.0267 (14)−0.0003 (11)0.0013 (11)−0.0012 (12)
C140.0216 (13)0.0264 (14)0.0278 (14)0.0005 (11)−0.0027 (11)0.0016 (11)
C150.0245 (13)0.0189 (13)0.0239 (13)−0.0004 (10)−0.0027 (11)−0.0003 (10)
O70.0262 (10)0.0426 (11)0.0211 (9)0.0009 (8)−0.0041 (7)0.0002 (8)
C160.0323 (16)0.068 (2)0.0211 (14)−0.0006 (15)−0.0012 (12)0.0013 (14)
C170.0249 (14)0.0281 (14)0.0228 (13)0.0010 (11)0.0016 (11)−0.0008 (11)
C180.0207 (13)0.0242 (13)0.0246 (13)−0.0001 (11)−0.0005 (10)−0.0011 (11)
O1W0.0424 (13)0.0714 (17)0.0334 (12)−0.0225 (11)−0.0046 (10)0.0037 (11)

Geometric parameters (Å, °)

O1—C111.366 (3)O6—C101.444 (3)
O1—C11.372 (3)C10—H10A0.9800
C1—C21.373 (3)C10—H10B0.9800
C1—C71.399 (3)C10—H10C0.9800
C2—C31.388 (3)C11—C121.473 (3)
C2—H20.9500C12—C181.393 (3)
C3—O21.351 (3)C12—C131.403 (3)
C3—C41.404 (4)C13—C141.372 (3)
O2—H2A0.8400C13—H130.9500
C4—C61.378 (4)C14—C151.385 (3)
C4—O31.380 (3)C14—H140.9500
O3—C51.436 (3)C15—O71.363 (3)
C5—H5A0.9800C15—C171.390 (3)
C5—H5B0.9800O7—C161.424 (3)
C5—H5C0.9800C16—H16A0.9800
C6—O41.357 (3)C16—H16B0.9800
C6—C71.411 (3)C16—H16C0.9800
O4—H4A0.8400C17—C181.379 (3)
C7—C81.429 (3)C17—H170.9500
C8—O51.265 (3)C18—H180.9500
C8—C91.442 (3)O1W—H1A0.852 (17)
C9—C111.363 (3)O1W—H1B0.859 (17)
C9—O61.376 (3)
C11—O1—C1121.81 (19)O6—C10—H10A109.5
O1—C1—C2116.9 (2)O6—C10—H10B109.5
O1—C1—C7120.0 (2)H10A—C10—H10B109.5
C2—C1—C7123.1 (2)O6—C10—H10C109.5
C1—C2—C3118.1 (2)H10A—C10—H10C109.5
C1—C2—H2121.0H10B—C10—H10C109.5
C3—C2—H2121.0C9—C11—O1120.1 (2)
O2—C3—C2118.2 (2)C9—C11—C12129.0 (2)
O2—C3—C4120.9 (2)O1—C11—C12110.9 (2)
C2—C3—C4120.9 (2)C18—C12—C13117.3 (2)
C3—O2—H2A109.5C18—C12—C11119.8 (2)
C6—C4—O3120.3 (2)C13—C12—C11122.9 (2)
C6—C4—C3120.0 (2)C14—C13—C12121.0 (2)
O3—C4—C3119.7 (2)C14—C13—H13119.5
C4—O3—C5113.20 (19)C12—C13—H13119.5
O3—C5—H5A109.5C13—C14—C15120.7 (2)
O3—C5—H5B109.5C13—C14—H14119.7
H5A—C5—H5B109.5C15—C14—H14119.7
O3—C5—H5C109.5O7—C15—C14115.7 (2)
H5A—C5—H5C109.5O7—C15—C17124.7 (2)
H5B—C5—H5C109.5C14—C15—C17119.6 (2)
O4—C6—C4119.6 (2)C15—O7—C16117.7 (2)
O4—C6—C7120.1 (2)O7—C16—H16A109.5
C4—C6—C7120.3 (2)O7—C16—H16B109.5
C6—O4—H4A109.5H16A—C16—H16B109.5
C1—C7—C6117.6 (2)O7—C16—H16C109.5
C1—C7—C8120.2 (2)H16A—C16—H16C109.5
C6—C7—C8122.2 (2)H16B—C16—H16C109.5
O5—C8—C7122.3 (2)C18—C17—C15119.3 (2)
O5—C8—C9121.5 (2)C18—C17—H17120.3
C7—C8—C9116.2 (2)C15—C17—H17120.3
C11—C9—O6121.0 (2)C17—C18—C12122.1 (2)
C11—C9—C8121.6 (2)C17—C18—H18118.9
O6—C9—C8117.2 (2)C12—C18—H18118.9
C9—O6—C10113.8 (2)H1A—O1W—H1B105 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2A···O1Wi0.841.922.712 (3)157
O2—H2A···O30.842.332.780 (3)114
O4—H4A···O50.841.852.589 (3)146
O1W—H1A···O50.85 (2)2.05 (2)2.886 (3)165 (3)
O1W—H1A···O60.85 (2)2.71 (3)3.288 (3)126 (3)
O1W—H1B···O4ii0.86 (2)2.38 (2)3.135 (3)148 (3)

Symmetry codes: (i) x−1/2, y−1/2, z; (ii) −x+3/2, −y+1/2, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RK2231).

References

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Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography