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Acta Crystallogr Sect E Struct Rep Online. 2010 May 1; 66(Pt 5): o1120–o1121.
Published online 2010 April 21. doi:  10.1107/S1600536810013590
PMCID: PMC2979227

1-(2,6-Dihydr­oxy-4-methoxy­phen­yl)-3-phenyl­propan-1-one1

Abstract

The title compound, C16H16O4, a dihydro­chalcone, was isolated from the rhizomes of Etlingera littoralis. The mol­ecule is twisted with a dihedral angle of 71.69 (6)° between the two aromatic rings. The propanone unit makes dihedral angles of 4.07 (6) and 73.56 (7)°, respectively, with the 2,6-dihydroxy-4-methoxyphenyl and phenyl rings. The meth­oxy group is approximately coplanar with the attached benzene ring with a dihedral angle of 1.74 (10)°. An intra­molecular O—H(...)O hydrogen bond generates an S(6) ring motif. In the crystal, inter­molecular O—H(...)O hydrogen bonds link the mol­ecules into chains along [201]. A π–π inter­action with a centroid–centroid distance of 3.5185 (6) Å is also observed.

Related literature

For details of hydrogen-bond motifs, see: Bernstein et al. (1995 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]). For background to dihydro­chalcones and their activities, see: Nilsson (1961 [triangle]); Nowakowska (2007 [triangle]); Portet et al. (2007 [triangle]). For Zingiberaceae plants, see: Chuakul & Boonpleng (2003 [triangle]); Reanmongkol et al. (2006 [triangle]); Sirirugsa (1999 [triangle]); Tewtrakul, Subhadhirasakul & Kummee (2003 [triangle]); Tewtrakul, Subhadhirasakul, Puripattanavong & Panphadung (2003 [triangle]). For a related structure, see: Ng et al. (2005 [triangle]). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1120-scheme1.jpg

Experimental

Crystal data

  • C16H16O4
  • M r = 272.29
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1120-efi1.jpg
  • a = 7.2142 (6) Å
  • b = 30.522 (2) Å
  • c = 6.5587 (5) Å
  • β = 107.267 (2)°
  • V = 1379.09 (18) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 100 K
  • 0.46 × 0.34 × 0.18 mm

Data collection

  • Bruker APEX DUO CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2009 [triangle]) T min = 0.958, T max = 0.983
  • 17744 measured reflections
  • 3044 independent reflections
  • 2940 reflections with I > 2σ(I)
  • R int = 0.025

Refinement

  • R[F 2 > 2σ(F 2)] = 0.034
  • wR(F 2) = 0.097
  • S = 1.08
  • 3044 reflections
  • 186 parameters
  • 2 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.34 e Å−3
  • Δρmin = −0.40 e Å−3

Data collection: APEX2 (Bruker, 2009 [triangle]); cell refinement: SAINT (Bruker, 2009 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810013590/is2537sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810013590/is2537Isup2.hkl

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

Acknowledgments

JJ and TK thank the Center of Excellence for Innovation in Chemistry (PERCH-CIC) and the Faculty of Science and Technology, Suratthani Rajabhat University, for financial support. The Natural Products Research Laboratory, School of Science, Mae Fah Luang University, is gratefully acknowledged for laboratory facilities. SC thanks the Prince of Songkla University for financial support. Mr Nawong Boonnak is acknowledged for providing useful information. The authors also thank the Malaysian Government and Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

supplementary crystallographic information

Comment

Zingiberaceae plants are the ground plants of tropical forests. Many of them are used for food, spices, medicines, dyes, perfume and aesthetics (Sirirugsa, 1999). Secondary metabolites from Zingiberaceae plants have found to be anti-inflammatory (Reanmongkol et al., 2006), HIV-1 protease inhibitory (Tewtrakul, Subhadhirasakul & Kummee, 2003; Tewtrakul, Subhadhirasakul, Puripattanavong & Panphadung, 2003). Etlingera littoralis is one of the Zingiberaceae plants and its decoction of the rhizomes has been used for the treatment of stomachache, carminative and heart tonic (Chuakul & Boonpleng, 2003). As part of our study of chemical constituents and bioactive compounds from the rhizomes of Etlingera littoralis which were collected from Surat Thani province in the southern of Thailand, the title dihydrochalcone, (I), was isolated. Herein we report its crystal structure. The title compound was found to possess antibacterial (Nowakowska, 2007) and antiplasmodial activities (Portet et al., 2007).

The molecule of the title dihydrochalcone (Fig. 1), C16H16O4, is twisted as the dihedral angle between the 2,6-dihydroxy-4-methoxyphenyl and phenyl rings is 71.69 (6)°. Whereas the 1-propanone unit (C7–C9/O1) makes the dihedral angles of 4.07 (6) and 73.56 (7)° with the C1–C6 benzene and C10–C15 phenyl rings, respectively. The two hydroxy and a methoxy groups are co-planar with the attached benzene ring with the r.m.s. of 0.0078 (1) Å for the ten non H atoms and the torsion angle C16–O3–C3–C2 = -1.66 (15)°. An intramolecular O2—H1O2···O1 hydrogen bond generates an S(6) ring motif (Bernstein et al., 1995) (Fig. 1 and Table 1). The bond distances are of normal values (Allen et al., 1987) and are comparable with the closely related structure (Ng et al., 2005).

In the crystal packing (Fig. 2) , O—H···O hydrogen bonds (Table 1) formed between the two hydroxy groups link the molecules into chains along the [201] direction in which the adjacent chains are in anti-parallel manner. A π–π interaction with Cg1···Cg1 distance of 3.5185 (6) Å was observed (symmetry code x, -y, -1/2+z); Cg1 is the centroid of the C1–C6 benzene ring.

Experimental

The fresh rhizomes of E. littoralis (3.89 kg) were chopped and extracted with 50% CH2Cl2-MeOH, over the period of 3 days at room temperature. The extraction was filtered and evaporated to dryness under reduced pressure to give crude extract which was further partitioned with water and CH2Cl2 to afford the dichloromethane extract (22.88 g). The portion of dichloromethane extract (11.80 g) was subjected to quick column chromatography (QCC) on silica gel eluting with a gradient of EtOAc–hexane to give thirteen fractions. Fraction F8 (322.4 mg) was washed with 20% CH2Cl2-hexane yielding solid which was further separated by column chromatography on silica gel with 70% CH2Cl2-hexane to give compound (I) (50.1 mg). Yellow block-shaped single crystals of the compound (I) suitable for X-ray structure determination were obtained from ethyl acetate by slow evaporation at room temperature after a few days, Mp 443 K. The NMR spectral data were consistent with the X-ray structure.

Refinement

Hydroxy H atoms attached to O4 was located from a difference map and isotropically refined. The remaining H atoms were placed in calculated positions, with d(O—H) = 0.82 Å and d(C—H) = 0.93 Å for aromatic, 0.97 for CH2 and 0.96 Å for CH3 atoms. The Uiso(H) values were constrained to be 1.5Ueq of the carrier atom for hydroxy and methyl H atoms and 1.2Ueq for the remaining H atoms. A rotating group model was used for the methyl groups. The highest residual electron densitypeak is located at 0.69 Å from C1 and the deepest hole is located at 0.84 Å from C7. A total of 2607 Friedel pairs were merged before final refinement as there is no large anomalous dispersion for the determination of the absolute configuration.

Figures

Fig. 1.
The molecular structure of the title compound, with 50% probability displacement ellipsoids and the atom-numbering scheme.
Fig. 2.
The crystal packing of the title compound viewed down the b axis, showing chains running along the [201] direction. Hydrogen bonds are shown as dashed lines.

Crystal data

C16H16O4F(000) = 576
Mr = 272.29Dx = 1.311 Mg m3
Monoclinic, CcMelting point: 443 K
Hall symbol: C -2ycMo Kα radiation, λ = 0.71073 Å
a = 7.2142 (6) ÅCell parameters from 3044 reflections
b = 30.522 (2) Åθ = 2.7–35.0°
c = 6.5587 (5) ŵ = 0.09 mm1
β = 107.267 (2)°T = 100 K
V = 1379.09 (18) Å3Block, yellow
Z = 40.46 × 0.34 × 0.18 mm

Data collection

Bruker APEX DUO CCD area-detector diffractometer3044 independent reflections
Radiation source: sealed tube2940 reflections with I > 2σ(I)
graphiteRint = 0.025
[var phi] and ω scansθmax = 35.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)h = −11→11
Tmin = 0.958, Tmax = 0.983k = −49→48
17744 measured reflectionsl = −10→10

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)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097H atoms treated by a mixture of independent and constrained refinement
S = 1.08w = 1/[σ2(Fo2) + (0.0648P)2 + 0.1812P] where P = (Fo2 + 2Fc2)/3
3044 reflections(Δ/σ)max = 0.001
186 parametersΔρmax = 0.34 e Å3
2 restraintsΔρmin = −0.40 e Å3

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.
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 > 2sigma(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
O10.57929 (10)0.09273 (3)0.16110 (12)0.01772 (14)
O20.40256 (10)0.02283 (2)0.09183 (12)0.01659 (14)
H1O20.42120.04940.09970.025*
O30.76008 (12)−0.11076 (2)0.22402 (13)0.01827 (13)
O41.09458 (10)0.02313 (2)0.35682 (12)0.01540 (13)
H1O41.186 (4)0.0088 (8)0.419 (4)0.043 (6)*
C10.57479 (11)0.00170 (3)0.15654 (13)0.01230 (14)
C20.56979 (13)−0.04392 (3)0.15433 (14)0.01400 (15)
H2A0.4524−0.05890.11020.017*
C30.74533 (14)−0.06642 (3)0.21997 (15)0.01307 (13)
C40.92225 (13)−0.04409 (3)0.28721 (14)0.01272 (14)
H4A1.0381−0.05970.32980.015*
C50.92521 (11)0.00137 (3)0.29051 (12)0.01140 (13)
C60.75073 (14)0.02604 (3)0.22318 (15)0.01112 (13)
C70.74075 (13)0.07385 (3)0.21838 (14)0.01271 (13)
C80.91965 (13)0.10221 (3)0.27702 (14)0.01421 (14)
H8A1.00230.09360.19110.017*
H8B0.99110.09710.42550.017*
C90.87479 (16)0.15107 (3)0.24454 (17)0.01880 (16)
H9A0.78930.15590.10130.023*
H9B0.80810.16080.34480.023*
C101.05757 (16)0.17743 (3)0.27659 (18)0.01983 (18)
C111.1302 (2)0.20381 (4)0.4562 (2)0.0303 (2)
H11A1.06620.20490.56010.036*
C121.2988 (3)0.22868 (4)0.4815 (3)0.0440 (4)
H12A1.34550.24630.60130.053*
C131.3961 (2)0.22708 (5)0.3287 (3)0.0453 (4)
H13A1.50740.24380.34550.054*
C141.3276 (2)0.20066 (5)0.1517 (3)0.0396 (3)
H14A1.39380.19920.04990.048*
C151.15876 (19)0.17616 (4)0.1255 (2)0.0273 (2)
H15A1.11280.15870.00490.033*
C160.58350 (17)−0.13568 (3)0.16199 (18)0.0230 (2)
H16A0.6136−0.16640.17750.034*
H16B0.5142−0.12940.01570.034*
H16C0.5046−0.12790.25130.034*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0124 (3)0.0166 (3)0.0227 (3)0.0027 (2)0.0030 (2)0.0000 (3)
O20.0085 (3)0.0182 (3)0.0212 (3)0.0004 (2)0.0016 (2)−0.0017 (2)
O30.0201 (3)0.0120 (3)0.0216 (3)−0.0026 (2)0.0044 (2)−0.0005 (2)
O40.0072 (2)0.0147 (3)0.0221 (3)−0.0008 (2)0.0010 (2)0.0007 (2)
C10.0087 (3)0.0161 (3)0.0118 (3)−0.0003 (3)0.0025 (2)−0.0004 (3)
C20.0119 (3)0.0157 (3)0.0139 (3)−0.0030 (3)0.0030 (3)−0.0011 (3)
C30.0144 (3)0.0129 (3)0.0116 (3)−0.0014 (3)0.0034 (2)−0.0004 (3)
C40.0111 (3)0.0132 (3)0.0134 (3)0.0002 (3)0.0029 (2)0.0002 (3)
C50.0089 (3)0.0135 (3)0.0114 (3)−0.0005 (3)0.0025 (2)0.0002 (3)
C60.0087 (3)0.0128 (3)0.0114 (3)−0.0007 (3)0.0022 (2)−0.0004 (3)
C70.0117 (3)0.0137 (3)0.0124 (3)0.0003 (3)0.0032 (2)−0.0002 (3)
C80.0130 (3)0.0125 (3)0.0161 (3)−0.0013 (3)0.0028 (3)−0.0007 (3)
C90.0179 (4)0.0126 (3)0.0242 (4)0.0011 (3)0.0036 (3)−0.0009 (3)
C100.0203 (4)0.0112 (3)0.0232 (4)−0.0016 (3)−0.0010 (3)0.0012 (3)
C110.0361 (6)0.0168 (4)0.0293 (5)−0.0027 (4)−0.0035 (4)−0.0040 (4)
C120.0459 (8)0.0190 (5)0.0472 (8)−0.0115 (5)−0.0170 (6)0.0002 (5)
C130.0297 (6)0.0271 (6)0.0637 (10)−0.0136 (5)−0.0098 (6)0.0190 (6)
C140.0266 (5)0.0360 (7)0.0532 (8)−0.0074 (5)0.0073 (6)0.0202 (6)
C150.0251 (5)0.0238 (5)0.0308 (5)−0.0043 (4)0.0052 (4)0.0054 (4)
C160.0263 (5)0.0178 (4)0.0227 (4)−0.0090 (4)0.0040 (4)−0.0014 (3)

Geometric parameters (Å, °)

O1—C71.2531 (11)C8—H8B0.9700
O2—C11.3516 (11)C9—C101.5052 (14)
O2—H1O20.8200C9—H9A0.9700
O3—C31.3574 (11)C9—H9B0.9700
O3—C161.4349 (13)C10—C111.3943 (15)
O4—C51.3445 (10)C10—C151.3951 (17)
O4—H1O40.79 (3)C11—C121.401 (2)
C1—C21.3928 (13)C11—H11A0.9300
C1—C61.4230 (12)C12—C131.384 (3)
C2—C31.3917 (14)C12—H12A0.9300
C2—H2A0.9300C13—C141.379 (3)
C3—C41.3978 (13)C13—H13A0.9300
C4—C51.3877 (12)C14—C151.3956 (18)
C4—H4A0.9300C14—H14A0.9300
C5—C61.4201 (12)C15—H15A0.9300
C6—C71.4607 (11)C16—H16A0.9600
C7—C81.5061 (13)C16—H16B0.9600
C8—C91.5276 (13)C16—H16C0.9600
C8—H8A0.9700
C1—O2—H1O2109.5C10—C9—C8111.21 (8)
C3—O3—C16117.72 (9)C10—C9—H9A109.4
C5—O4—H1O4115.4 (18)C8—C9—H9A109.4
O2—C1—C2117.08 (8)C10—C9—H9B109.4
O2—C1—C6120.02 (8)C8—C9—H9B109.4
C2—C1—C6122.90 (8)H9A—C9—H9B108.0
C3—C2—C1118.14 (8)C11—C10—C15118.14 (11)
C3—C2—H2A120.9C11—C10—C9121.36 (11)
C1—C2—H2A120.9C15—C10—C9120.50 (9)
O3—C3—C2123.84 (9)C10—C11—C12120.52 (15)
O3—C3—C4114.90 (9)C10—C11—H11A119.7
C2—C3—C4121.26 (7)C12—C11—H11A119.7
C5—C4—C3120.05 (8)C13—C12—C11120.27 (14)
C5—C4—H4A120.0C13—C12—H12A119.9
C3—C4—H4A120.0C11—C12—H12A119.9
O4—C5—C4120.48 (8)C14—C13—C12119.88 (13)
O4—C5—C6118.37 (7)C14—C13—H13A120.1
C4—C5—C6121.15 (8)C12—C13—H13A120.1
C5—C6—C1116.50 (7)C13—C14—C15119.88 (16)
C5—C6—C7124.74 (8)C13—C14—H14A120.1
C1—C6—C7118.76 (8)C15—C14—H14A120.1
O1—C7—C6120.09 (8)C10—C15—C14121.29 (13)
O1—C7—C8117.52 (7)C10—C15—H15A119.4
C6—C7—C8122.38 (8)C14—C15—H15A119.4
C7—C8—C9113.30 (7)O3—C16—H16A109.5
C7—C8—H8A108.9O3—C16—H16B109.5
C9—C8—H8A108.9H16A—C16—H16B109.5
C7—C8—H8B108.9O3—C16—H16C109.5
C9—C8—H8B108.9H16A—C16—H16C109.5
H8A—C8—H8B107.7H16B—C16—H16C109.5
O2—C1—C2—C3179.91 (8)C5—C6—C7—O1−178.29 (8)
C6—C1—C2—C3−0.16 (14)C1—C6—C7—O11.64 (14)
C16—O3—C3—C2−1.66 (15)C5—C6—C7—C82.74 (15)
C16—O3—C3—C4178.47 (8)C1—C6—C7—C8−177.33 (8)
C1—C2—C3—O3−179.62 (8)O1—C7—C8—C9−3.30 (12)
C1—C2—C3—C40.24 (14)C6—C7—C8—C9175.70 (8)
O3—C3—C4—C5−179.79 (8)C7—C8—C9—C10−172.32 (8)
C2—C3—C4—C50.34 (14)C8—C9—C10—C11−108.05 (11)
C3—C4—C5—O4179.38 (7)C8—C9—C10—C1572.21 (12)
C3—C4—C5—C6−1.01 (14)C15—C10—C11—C120.83 (17)
O4—C5—C6—C1−179.33 (7)C9—C10—C11—C12−178.92 (11)
C4—C5—C6—C11.05 (13)C10—C11—C12—C13−0.5 (2)
O4—C5—C6—C70.60 (14)C11—C12—C13—C14−0.4 (2)
C4—C5—C6—C7−179.02 (8)C12—C13—C14—C151.0 (2)
O2—C1—C6—C5179.46 (8)C11—C10—C15—C14−0.27 (17)
C2—C1—C6—C5−0.46 (14)C9—C10—C15—C14179.47 (11)
O2—C1—C6—C7−0.47 (13)C13—C14—C15—C10−0.6 (2)
C2—C1—C6—C7179.60 (8)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H1O2···O10.821.712.4576 (11)150
O4—H1O4···O2i0.80 (3)1.90 (3)2.6920 (10)175 (3)

Symmetry codes: (i) x+1, −y, z+1/2.

Footnotes

1This paper is dedicated to Her Royal Highness Princess Maha Chakri Sirindhorn of Thailand on the occasion of her 55th Birthday Anniversary which fell on April 2nd, 2010.

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IS2537).

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