1-(2-Hy­dr­oxy-3,5-dimeth­­oxy­phen­yl)ethanone

In title compound, C₁₀H₁₂O₄, all of the non-H atoms lie approximately in a plane with the largest deviation being 0.061 (2) Å. An intra­molecular O—H⋯O hydrogen bond generates an S(6) ring motif. No classical inter­molecular hydrogen bonding occurs, with only van der Waals forces stabilizing the crystal structure.

Related literature

For the biological activity of isoflavones, see: Wang & Murphy (1994); Yoshio et al. (1989). For bond-length data, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995). For the preparation, see: Aalten et al. (1989).

Experimental

Crystal data

• C₁₀H₁₂O₄

• M_r = 196.20

• Monoclinic, P 2₁ /n

• a = 7.733 (4) Å

• b = 8.059 (4) Å

• c = 14.851 (7) Å

• β = 91.416 (10)°

• V = 925.3 (7) ų

• Z = 4

• Mo Kα radiation

• μ = 0.11 mm⁻¹

• T = 113 K

• 0.26 × 0.20 × 0.12 mm

Data collection

• Rigaku Saturn724 CCD diffractometer

• Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2009) T_min = 0.972, T_max = 0.987

• 10288 measured reflections

• 2212 independent reflections

• 1621 reflections with I > 2σ(I)

• R_int = 0.036

Refinement

• R[F² > 2σ(F²)] = 0.035

• wR(F²) = 0.091

• S = 1.04

• 2212 reflections

• 131 parameters

• H-atom parameters constrained

• Δρ_max = 0.27 e Å⁻³

• Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O4	0.84	1.83	2.5666 (14)	145

Data collection: CrystalClear-SM Expert (Rigaku/MSC, 2009); cell refinement: CrystalClear-SM Expert; data reduction: CrystalClear-SM Expert; 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

S1. Comment

Soy isoflavone is secondary metabolite during its growth period. As it could be extracted from plants and have a similar structure of estrogen, people usually call it phytoestrogen. Due to the manifested biological activity, such as antitumor, cardiovascular protection, anti-oxidant, anti-inflammatory, osteoporosis improvement, dual effect on estrogen, isoflavone has been paid more attention in social and academic area (Wang & Murphy, 1994; Yoshio et al., 1989). During the development of our own isoflavone derivatives, the title compound, 1-(2-hydroxy-3,5-dimethoxyphenyl)ethanone, was prepared as an intermediate. The crystallographic analysis of the title compound described herein further confirms the molecular structures of the title compound and isoflavones.

In title compound, C₁₀H₁₂O₄, all bond lengths and angles in the molecule are normal (Allen et al., 1987). All of atoms (C1—C10/O1—O4, except H atoms)lie in a plane with the largest deviation 0.061 (2) Å for C10. The intramolecular O3—H3···O4 hydrogen bonds generate S(6) ring motif (Bernstein et al., 1995). There is no classical intermolecular hydrogen bond found in the structure with only Van der Waals forces stabilizing the crystal.

Related literature

For the biological activity of isoflavone, see: Wang & Murphy (1994); Yoshio et al. (1989). For bond-length data, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995). For the preparation, see: Aalten et al., (1989).

S2. Experimental

Under ice bath, a solution of 2-hydroxyacetophenone(100 g, 0.734 mol) in CH₃OH(1.2L) was added N-bromosuccinimide(392 g, 2.203 mol). Then the reaction mixture was stirred overnight at room temperature. The mixture was added 1L water to form yellow precipitation then filtered. The filtered cake was washed with a little amount of CH₃OH/H₂O=1/1 to yield 80 g light yellow crystals, which is 1-(3,5-dibromo-2-hydroxyphenyl)ethanone. Under ice bath, sodium methoxide(73 g, 1.360 mol) was dissolved in CH₃OH (1L). Then under nitrogen protection, 1-(3,5-dibromo-2-hydroxyphenyl)ethanone (80 g, 0.272 mol) and CuCl(27 g,0.272 mol) was added to the solution quickly followed by DMF(0.5L). The brown suspension was heated to 363 K overnight until LC—MS showed complete. The mixture was neutralized with concentrated HCl to pH5–6, filtered through celite. Then it was extracted with ethyl acetate three times. The combined organic phase was washed with brine, dried over Na₂SO₄ and evaporated in vacuo to obtain crude product. Pure title compound was obtained by column chromatography. Crystals suitable for X-ray diffraction were obtained through slow evaporation of a solution of the pure title compound in ethyl acetate/n-hexane (1/4 by volume)(Aalten et al., 1989).

S3. Refinement

All H atoms were found on difference maps, with C—H = 0.95 or 0.98, O—H = 0.84 Å and included in the final cycles of refinement using a riding model, with U_iso(H) = 1.2U_eq(C) and 1.5U_eq(C, O) for the methyl and hydroxyl H atoms.

Computing details

Data collection: CrystalClear-SM Expert (Rigaku/MSC, 2009); cell refinement: CrystalClear-SM Expert (Rigaku/MSC, 2009); data reduction: CrystalClear-SM Expert (Rigaku/MSC, 2009); 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

Fig. 1. View of the title compound, with displacement ellipsoids drawn at the 40% probability level.

1-(2-Hydroxy-3,5-dimethoxyphenyl)ethanone

Crystal data

C10H12O4	F(000) = 416
Mr = 196.20	Dx = 1.408 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3101 reflections
a = 7.733 (4) Å	θ = 1.4–27.9°
b = 8.059 (4) Å	µ = 0.11 mm^−1
c = 14.851 (7) Å	T = 113 K
β = 91.416 (10)°	Prism, colorless
V = 925.3 (7) Å^3	0.26 × 0.20 × 0.12 mm
Z = 4

Data collection

Rigaku Saturn724 CCD diffractometer	2212 independent reflections
Radiation source: rotating anode	1621 reflections with I > 2σ(I)
Multilayer monochromator	Rint = 0.036
Detector resolution: 14.22 pixels mm^-1	θmax = 27.9°, θmin = 2.7°
ω and ϕ scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2009)	k = −10→10
Tmin = 0.972, Tmax = 0.987	l = −19→19
10288 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.091	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0513P)^2] where P = (Fo^2 + 2Fc^2)/3
2212 reflections	(Δ/σ)max = 0.003
131 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.25 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.91994 (10)	0.94416 (10)	0.30478 (5)	0.0250 (2)
O2	1.34013 (9)	0.60797 (9)	0.45862 (5)	0.0214 (2)
O3	1.15055 (10)	0.58744 (9)	0.60098 (5)	0.0211 (2)
H3	1.0779	0.5817	0.6420	0.032*
O4	0.86931 (10)	0.65890 (10)	0.68062 (5)	0.0244 (2)
C1	0.75834 (15)	1.03005 (14)	0.30265 (8)	0.0231 (3)
H1A	0.6636	0.9496	0.3057	0.035*
H1B	0.7468	1.0937	0.2466	0.035*
H1C	0.7537	1.1058	0.3542	0.035*
C2	0.96176 (14)	0.85633 (13)	0.38174 (7)	0.0183 (2)
C3	1.12493 (14)	0.77847 (12)	0.37976 (7)	0.0189 (2)
H3A	1.1938	0.7880	0.3279	0.023*
C4	1.18437 (14)	0.68864 (13)	0.45298 (7)	0.0175 (2)
C5	1.08271 (13)	0.67472 (12)	0.53088 (7)	0.0169 (2)
C6	0.92014 (13)	0.75150 (12)	0.53199 (7)	0.0171 (2)
C7	0.85964 (14)	0.84275 (13)	0.45606 (7)	0.0185 (2)
H7	0.7492	0.8943	0.4564	0.022*
C8	1.44819 (15)	0.62000 (15)	0.38132 (8)	0.0248 (3)
H8A	1.3885	0.5701	0.3290	0.037*
H8B	1.5571	0.5611	0.3935	0.037*
H8C	1.4724	0.7370	0.3688	0.037*
C9	0.81400 (14)	0.73530 (13)	0.61314 (7)	0.0196 (2)
C10	0.63652 (15)	0.81151 (15)	0.61438 (8)	0.0261 (3)
H10A	0.5841	0.7892	0.6726	0.039*
H10B	0.5642	0.7633	0.5660	0.039*
H10C	0.6456	0.9316	0.6054	0.039*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0233 (4)	0.0318 (4)	0.0201 (4)	0.0054 (3)	0.0026 (3)	0.0080 (3)
O2	0.0161 (4)	0.0290 (4)	0.0192 (4)	0.0037 (3)	0.0035 (3)	0.0023 (3)
O3	0.0202 (4)	0.0268 (4)	0.0163 (4)	0.0024 (3)	0.0012 (3)	0.0028 (3)
O4	0.0248 (4)	0.0308 (5)	0.0177 (4)	0.0009 (3)	0.0024 (3)	0.0011 (3)
C1	0.0231 (6)	0.0236 (6)	0.0223 (6)	0.0024 (5)	−0.0021 (5)	0.0020 (5)
C2	0.0206 (6)	0.0183 (5)	0.0160 (5)	−0.0019 (4)	−0.0008 (4)	0.0005 (4)
C3	0.0192 (6)	0.0207 (5)	0.0170 (5)	−0.0025 (4)	0.0040 (4)	−0.0008 (4)
C4	0.0154 (5)	0.0181 (5)	0.0192 (5)	−0.0006 (4)	0.0010 (4)	−0.0029 (4)
C5	0.0196 (6)	0.0165 (5)	0.0146 (5)	−0.0017 (4)	−0.0013 (4)	−0.0012 (4)
C6	0.0185 (6)	0.0172 (5)	0.0158 (5)	−0.0020 (4)	0.0022 (4)	−0.0027 (4)
C7	0.0165 (5)	0.0186 (5)	0.0204 (6)	0.0000 (4)	−0.0003 (4)	−0.0020 (4)
C8	0.0189 (6)	0.0310 (6)	0.0249 (6)	0.0022 (5)	0.0081 (5)	0.0031 (5)
C9	0.0217 (6)	0.0191 (5)	0.0181 (5)	−0.0024 (4)	0.0012 (4)	−0.0034 (4)
C10	0.0238 (6)	0.0314 (6)	0.0234 (6)	0.0046 (5)	0.0060 (5)	0.0008 (5)

Geometric parameters (Å, º)

O1—C2	1.3762 (14)	C3—H3A	0.9500
O1—C1	1.4283 (14)	C4—C5	1.4192 (15)
O2—C4	1.3695 (13)	C5—C6	1.4016 (15)
O2—C8	1.4398 (14)	C6—C7	1.4161 (16)
O3—C5	1.3516 (13)	C6—C9	1.4806 (16)
O3—H3	0.8400	C7—H7	0.9500
O4—C9	1.2430 (14)	C8—H8A	0.9800
C1—H1A	0.9800	C8—H8B	0.9800
C1—H1B	0.9800	C8—H8C	0.9800
C1—H1C	0.9800	C9—C10	1.5041 (16)
C2—C7	1.3773 (16)	C10—H10A	0.9800
C2—C3	1.4102 (16)	C10—H10B	0.9800
C3—C4	1.3758 (16)	C10—H10C	0.9800
C2—O1—C1	117.07 (9)	C5—C6—C7	119.91 (9)
C4—O2—C8	116.50 (9)	C5—C6—C9	119.08 (10)
C5—O3—H3	109.5	C7—C6—C9	121.00 (10)
O1—C1—H1A	109.5	C2—C7—C6	119.65 (10)
O1—C1—H1B	109.5	C2—C7—H7	120.2
H1A—C1—H1B	109.5	C6—C7—H7	120.2
O1—C1—H1C	109.5	O2—C8—H8A	109.5
H1A—C1—H1C	109.5	O2—C8—H8B	109.5
H1B—C1—H1C	109.5	H8A—C8—H8B	109.5
O1—C2—C7	125.37 (10)	O2—C8—H8C	109.5
O1—C2—C3	113.80 (9)	H8A—C8—H8C	109.5
C7—C2—C3	120.83 (10)	H8B—C8—H8C	109.5
C4—C3—C2	119.95 (10)	O4—C9—C6	120.88 (11)
C4—C3—H3A	120.0	O4—C9—C10	119.23 (10)
C2—C3—H3A	120.0	C6—C9—C10	119.89 (10)
O2—C4—C3	125.05 (9)	C9—C10—H10A	109.5
O2—C4—C5	114.62 (9)	C9—C10—H10B	109.5
C3—C4—C5	120.32 (10)	H10A—C10—H10B	109.5
O3—C5—C6	123.49 (9)	C9—C10—H10C	109.5
O3—C5—C4	117.18 (10)	H10A—C10—H10C	109.5
C6—C5—C4	119.33 (10)	H10B—C10—H10C	109.5
C1—O1—C2—C7	0.96 (15)	O3—C5—C6—C7	179.09 (9)
C1—O1—C2—C3	−178.46 (9)	C4—C5—C6—C7	−0.45 (15)
O1—C2—C3—C4	178.95 (9)	O3—C5—C6—C9	−1.01 (15)
C7—C2—C3—C4	−0.50 (16)	C4—C5—C6—C9	179.46 (9)
C8—O2—C4—C3	0.15 (15)	O1—C2—C7—C6	−178.46 (10)
C8—O2—C4—C5	−179.49 (9)	C3—C2—C7—C6	0.92 (16)
C2—C3—C4—O2	179.97 (9)	C5—C6—C7—C2	−0.44 (16)
C2—C3—C4—C5	−0.41 (16)	C9—C6—C7—C2	179.66 (9)
O2—C4—C5—O3	0.96 (14)	C5—C6—C9—O4	2.04 (15)
C3—C4—C5—O3	−178.69 (9)	C7—C6—C9—O4	−178.05 (10)
O2—C4—C5—C6	−179.47 (9)	C5—C6—C9—C10	−177.77 (10)
C3—C4—C5—C6	0.87 (15)	C7—C6—C9—C10	2.13 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O4	0.84	1.83	2.5666 (14)	145