1-(2-Hy­droxy-5-meth­oxy­phen­yl)-3-methyl­but-2-en-1-one

The title compound, C₁₂H₁₄O₃, is a natural product derived from the medium-sized hawthorn Crataegus persimilis ('prunifolia'). The mean plane of the butene moiety is twisted by 13.27 (7)° with respect to the that of the dioxobenzaldehyde moiety. There is an intra­molecular hydrogen bond between the hydroxyl group and the carbonyl O atom.

Key indicators

• Single-crystal X-ray study
• T = 100 K, P = 0.0 kPa
• Mean [sigma](C-C) = 0.001 Å
• R factor = 0.043
• wR factor = 0.127
• Data-to-parameter ratio = 26.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          2
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          1

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         25

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   2 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

The structure of title compound I can be described in terms of four planar moieties as defined by their constituent non-hydrogen atoms. The phenyl ring and three atoms bonded to it define the main molecular plane, with mean deviation of the defining atoms of δ_r.m.s. = 0.0145 (6) Å. With respect to this molecular plane, the mean plane of the carbonyl group (four atoms, δ_r.m.s. = 0.0044 (4) Å) and the plane of the methoxy group (three atoms) have dihedral angles of 2.50 (6)° and 4.33 (6)° respectively, while the mean plane of the butene moiety (four atoms, δ_r.m.s. = 0.0018 (4) Å) has dihedral angle 13.27 (7)°.

Related literature

For isolation from plant material, see: Castro et al. (1989). For the synthesis, see: Camps et al. (1985). For photolysis to form 4-chromanones, see: Primo et al. (1982). For a related structure, see: Zeller et al. (2010).

S2. Experimental

Compound I was isolated as a natural product (Castro et al., 1989). It has also been synthesized (Camps et al., 1985). Suitable crystals were formed by very slow evaporation of a hexane solution over a period of three years.

S3. Refinement

The positional and isotropic displacement parameters of hydroxyl atom H2A were refined independently. All other H atoms were placed in calculated positions, guided by difference maps, and refined as riding. Torsional parameters for the three methyl groups were refined, with C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C), while H atoms attached to sp² C atoms have C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).

Figures

Fig. 1. Molecular structure of (I) with displacement ellipsoids at the 50% probability level.

1-(2-Hydroxy-5-methoxyphenyl)-3-methylbut-2-en-1-one

Crystal data

C12H14O3	F(000) = 440
Mr = 206.23	Dx = 1.309 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3442 reflections
a = 14.027 (3) Å	θ = 2.5–32.6°
b = 5.816 (1) Å	µ = 0.09 mm^−1
c = 12.829 (3) Å	T = 100 K
β = 91.409 (8)°	Fragment, yellow
V = 1046.3 (4) Å^3	0.45 × 0.37 × 0.23 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	3784 independent reflections
Radiation source: sealed tube	3179 reflections with I > 2σ(I)
Horizonally mounted graphite crystal monochromator	Rint = 0.018
Detector resolution: 9 pixels mm^-1	θmax = 32.6°, θmin = 3.2°
ϕ and ω scans	h = −21→21
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor 1997)	k = −8→7
Tmin = 0.959, Tmax = 0.979	l = −19→19
6425 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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0692P)^2 + 0.2297P] where P = (Fo^2 + 2Fc^2)/3
3784 reflections	(Δ/σ)max = 0.001
143 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.22 e Å^−3
0 constraints

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.38220 (6)	1.03873 (14)	0.88580 (6)	0.01713 (16)
C2	0.31710 (6)	0.89827 (14)	0.93398 (6)	0.01652 (15)
H2	0.3003	0.9281	1.0040	0.020*
C3	0.27530 (6)	0.71019 (14)	0.87973 (6)	0.01641 (15)
C4	0.30238 (6)	0.66752 (15)	0.77617 (6)	0.01796 (16)
C5	0.36779 (6)	0.81313 (15)	0.72851 (6)	0.01992 (17)
H5	0.3853	0.7853	0.6586	0.024*
C6	0.40689 (6)	0.99610 (16)	0.78231 (6)	0.01999 (17)
H6	0.4509	1.0944	0.7491	0.024*
C7	0.20366 (6)	0.55840 (14)	0.92711 (7)	0.01901 (16)
C8	0.17084 (6)	0.60621 (15)	1.03279 (7)	0.01893 (16)
H8	0.1897	0.7485	1.0632	0.023*
C9	0.11620 (6)	0.46622 (15)	1.09083 (7)	0.01933 (16)
C10	0.08404 (7)	0.54666 (17)	1.19537 (7)	0.02467 (19)
H10A	0.1069	0.7037	1.2079	0.037*
H10B	0.1100	0.4446	1.2498	0.037*
H10C	0.0142	0.5442	1.1967	0.037*
C11	0.08255 (7)	0.23100 (16)	1.05970 (8)	0.02593 (19)
H11A	0.0197	0.2424	1.0251	0.039*
H11B	0.0781	0.1342	1.1219	0.039*
H11C	0.1279	0.1625	1.0117	0.039*
C12	0.40983 (6)	1.26466 (15)	1.03865 (7)	0.02072 (17)
H12A	0.3425	1.3041	1.0465	0.031*
H12B	0.4497	1.3925	1.0637	0.031*
H12C	0.4249	1.1263	1.0794	0.031*
O1	0.42786 (5)	1.22263 (11)	0.93148 (5)	0.02247 (15)
O2	0.26717 (5)	0.49087 (12)	0.71825 (5)	0.02388 (15)
H2A	0.2287 (12)	0.416 (3)	0.7580 (14)	0.052 (5)*
O3	0.17042 (5)	0.39337 (13)	0.87547 (6)	0.02755 (16)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0188 (3)	0.0184 (3)	0.0143 (3)	−0.0008 (3)	0.0011 (3)	0.0000 (3)
C2	0.0168 (3)	0.0186 (3)	0.0142 (3)	0.0004 (3)	0.0009 (3)	0.0004 (3)
C3	0.0166 (3)	0.0175 (3)	0.0152 (3)	0.0007 (3)	0.0007 (3)	0.0006 (3)
C4	0.0195 (3)	0.0188 (3)	0.0156 (3)	0.0018 (3)	−0.0008 (3)	−0.0011 (3)
C5	0.0230 (4)	0.0234 (4)	0.0134 (3)	−0.0002 (3)	0.0018 (3)	−0.0006 (3)
C6	0.0226 (4)	0.0235 (4)	0.0140 (3)	−0.0026 (3)	0.0031 (3)	0.0010 (3)
C7	0.0181 (3)	0.0192 (4)	0.0198 (4)	−0.0002 (3)	0.0004 (3)	0.0002 (3)
C8	0.0179 (3)	0.0191 (3)	0.0199 (4)	−0.0006 (3)	0.0027 (3)	0.0002 (3)
C9	0.0157 (3)	0.0199 (4)	0.0224 (4)	0.0013 (3)	0.0007 (3)	0.0035 (3)
C10	0.0241 (4)	0.0267 (4)	0.0236 (4)	−0.0015 (3)	0.0071 (3)	0.0029 (3)
C11	0.0265 (4)	0.0208 (4)	0.0305 (5)	−0.0040 (3)	0.0023 (4)	0.0039 (3)
C12	0.0243 (4)	0.0223 (4)	0.0157 (3)	−0.0029 (3)	0.0026 (3)	−0.0027 (3)
O1	0.0286 (3)	0.0238 (3)	0.0153 (3)	−0.0094 (2)	0.0052 (2)	−0.0030 (2)
O2	0.0301 (3)	0.0225 (3)	0.0190 (3)	−0.0042 (3)	0.0017 (3)	−0.0051 (2)
O3	0.0317 (4)	0.0260 (3)	0.0251 (3)	−0.0101 (3)	0.0034 (3)	−0.0049 (3)

Geometric parameters (Å, º)

C1—O1	1.3708 (10)	C8—H8	0.95
C1—C2	1.3824 (11)	C9—C11	1.4982 (13)
C1—C6	1.4023 (12)	C9—C10	1.5003 (13)
C2—C3	1.4159 (11)	C10—H10A	0.98
C2—H2	0.95	C10—H10B	0.98
C3—C4	1.4127 (12)	C10—H10C	0.98
C3—C7	1.4795 (12)	C11—H11A	0.98
C4—O2	1.3540 (10)	C11—H11B	0.98
C4—C5	1.4002 (12)	C11—H11C	0.98
C5—C6	1.3751 (12)	C12—O1	1.4251 (11)
C5—H5	0.95	C12—H12A	0.98
C6—H6	0.95	C12—H12B	0.98
C7—O3	1.2499 (11)	C12—H12C	0.98
C7—C8	1.4690 (12)	O2—H2A	0.870 (18)
C8—C9	1.3538 (12)
O1—C1—C2	125.22 (7)	C8—C9—C11	125.55 (8)
O1—C1—C6	114.77 (7)	C8—C9—C10	119.40 (8)
C2—C1—C6	120.00 (8)	C11—C9—C10	115.05 (8)
C1—C2—C3	120.46 (7)	C9—C10—H10A	109.5
C1—C2—H2	119.8	C9—C10—H10B	109.5
C3—C2—H2	119.8	H10A—C10—H10B	109.5
C4—C3—C2	118.71 (7)	C9—C10—H10C	109.5
C4—C3—C7	118.86 (7)	H10A—C10—H10C	109.5
C2—C3—C7	122.43 (7)	H10B—C10—H10C	109.5
O2—C4—C5	116.96 (8)	C9—C11—H11A	109.5
O2—C4—C3	123.13 (8)	C9—C11—H11B	109.5
C5—C4—C3	119.91 (8)	H11A—C11—H11B	109.5
C6—C5—C4	120.43 (8)	C9—C11—H11C	109.5
C6—C5—H5	119.8	H11A—C11—H11C	109.5
C4—C5—H5	119.8	H11B—C11—H11C	109.5
C5—C6—C1	120.48 (8)	O1—C12—H12A	109.5
C5—C6—H6	119.8	O1—C12—H12B	109.5
C1—C6—H6	119.8	H12A—C12—H12B	109.5
O3—C7—C8	120.88 (8)	O1—C12—H12C	109.5
O3—C7—C3	119.26 (8)	H12A—C12—H12C	109.5
C8—C7—C3	119.85 (7)	H12B—C12—H12C	109.5
C9—C8—C7	126.04 (8)	C1—O1—C12	117.01 (7)
C9—C8—H8	117	C4—O2—H2A	106.4 (12)
C7—C8—H8	117
O1—C1—C2—C3	−178.95 (8)	C2—C1—C6—C5	−0.92 (13)
C6—C1—C2—C3	0.33 (13)	C4—C3—C7—O3	1.59 (12)
C1—C2—C3—C4	0.82 (12)	C2—C3—C7—O3	−179.06 (8)
C1—C2—C3—C7	−178.54 (8)	C4—C3—C7—C8	−176.96 (7)
C2—C3—C4—O2	179.35 (7)	C2—C3—C7—C8	2.39 (12)
C7—C3—C4—O2	−1.28 (12)	O3—C7—C8—C9	11.11 (14)
C2—C3—C4—C5	−1.39 (12)	C3—C7—C8—C9	−170.37 (8)
C7—C3—C4—C5	177.99 (8)	C7—C8—C9—C11	2.89 (14)
O2—C4—C5—C6	−179.87 (8)	C7—C8—C9—C10	−176.50 (8)
C3—C4—C5—C6	0.82 (13)	C2—C1—O1—C12	3.14 (12)
C4—C5—C6—C1	0.34 (13)	C6—C1—O1—C12	−176.18 (8)
O1—C1—C6—C5	178.43 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O3	0.87 (2)	1.74 (2)	2.523 (1)	149 (2)