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

Alexander, C.T.; Vargas, D.; Fronczek, F.R.; Watkins, S.F.

doi:10.1107/S1600536812042158

organic compounds

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ISSN: 2056-9890

Volume 68| Part 11| November 2012| Page o3126

doi:10.1107/S1600536812042158

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

Catherine Thomas Alexander,^a David Vargas,^a Frank R. Fronczek ^a ^* and Steven F. Watkins ^a

^aDepartment of Chemistry, Louisiana State University, Baton Rouge LA 70803-1804 USA
^*Correspondence e-mail: ffroncz@lsu.edu

(Received 1 October 2012; accepted 8 October 2012; online 13 October 2012)

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.

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 ).

Experimental

Crystal data

C₁₂H₁₄O₃
M_r = 206.23
Monoclinic, P 2₁ /c
a = 14.027 (3) Å
b = 5.816 (1) Å
c = 12.829 (3) Å
β = 91.409 (8)°
V = 1046.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.45 × 0.37 × 0.23 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor 1997 ) T_min = 0.959, T_max = 0.979
6425 measured reflections
3784 independent reflections
3179 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.127
S = 1.04
3784 reflections
143 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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)

Data collection: COLLECT (Nonius, 2000 ); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812042158/im2405sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812042158/im2405Isup2.hkl

checkCIF report

Comment top

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 top

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).

Experimental top

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.

Computing details top

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 top

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 top

Crystal data top

C₁₂H₁₄O₃	F(000) = 440
M_r = 206.23	D_x = 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) Å³	0.45 × 0.37 × 0.23 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	3784 independent reflections
Radiation source: sealed tube	3179 reflections with I > 2σ(I)
Horizonally mounted graphite crystal monochromator	R_int = 0.018
Detector resolution: 9 pixels mm^-1	θ_max = 32.6°, θ_min = 3.2°
ϕ and ω scans	h = −21→21
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor 1997)	k = −8→7
T_min = 0.959, T_max = 0.979	l = −19→19
6425 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0692P)² + 0.2297P] where P = (F_o² + 2F_c²)/3
3784 reflections	(Δ/σ)_max = 0.001
143 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³
0 constraints

Crystal data top

C₁₂H₁₄O₃	V = 1046.3 (4) Å³
M_r = 206.23	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.027 (3) Å	µ = 0.09 mm⁻¹
b = 5.816 (1) Å	T = 100 K
c = 12.829 (3) Å	0.45 × 0.37 × 0.23 mm
β = 91.409 (8)°

Data collection top

Nonius KappaCCD diffractometer	3784 independent reflections
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor 1997)	3179 reflections with I > 2σ(I)
T_min = 0.959, T_max = 0.979	R_int = 0.018
6425 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.43 e Å⁻³
3784 reflections	Δρ_min = −0.22 e Å⁻³
143 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
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) top

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) top

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)

Experimental details

Crystal data
Chemical formula	C₁₂H₁₄O₃
M_r	206.23
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	14.027 (3), 5.816 (1), 12.829 (3)
β (°)	91.409 (8)
V (Å³)	1046.3 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.45 × 0.37 × 0.23

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (HKL SCALEPACK; Otwinowski & Minor 1997)
T_min, T_max	0.959, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	6425, 3784, 3179
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.758

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.127, 1.04
No. of reflections	3784
No. of parameters	143
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.22

Computer programs: COLLECT (Nonius, 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR2002 (Burla et al., 2003), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX publication routines (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

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)

Footnotes

†CAS Registry 84346–78–1.

Acknowledgements

The purchase of the diffractometer was made possible by grant No. LEQSF (1999–2000)-ENH-TR-13, administered by the Louisiana Board of Regents.

References

Burla, M. C., Camalli, M., Carrozzini, B., Cascarano, G. L., Giacovazzo, C., Polidori, G. & Spagna, R. (2003). J. Appl. Cryst. 36, 1103. CrossRef IUCr Journals Google Scholar
Camps, F., Coll, J., Colomina, O. & Messeguer, A. (1985). J. Heterocycl. Chem. 22, 363–368. CrossRef CAS Google Scholar
Castro, V., Tamayo-Castillo, G. & Jakupovic, J. (1989). Phytochemistry, 28, 2415–2418. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Nonius (2000). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Primo, J., Tormo, R. & Miranda, M. A. (1982). Heterocycles, 19, 1819–1822. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zeller, M., Sridharan, M., Rajendra Prasad, K. J. & Ngendahimana, A. (2010). Acta Cryst. E66, o297–o298. Web of Science CSD CrossRef IUCr Journals Google Scholar