Acta Cryst. (2012). E68, o3126 [ doi:10.1107/S1600536812042158 ]
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.
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.
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 Uiso(H) = 1.5Ueq(C), while H atoms attached to sp2 C atoms have C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C).
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).
![[Figure 1]](./im2405fig1thm.gif)
| Fig. 1. Molecular structure of (I) with displacement ellipsoids at the 50% probability level. |
| 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) Å3 | 0.45 × 0.37 × 0.23 mm |
| Z = 4 |
| 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 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(Fo2) + (0.0692P)2 + 0.2297P] where P = (Fo2 + 2Fc2)/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 |
| C12H14O3 | V = 1046.3 (4) Å3 |
| Mr = 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)° |
| Nonius KappaCCD diffractometer | 3784 independent reflections |
| Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor 1997) | 3179 reflections with I > 2σ(I) |
| Tmin = 0.959, Tmax = 0.979 | Rint = 0.018 |
| 6425 measured reflections | θmax = 32.6° |
| R[F2 > 2σ(F2)] = 0.043 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.127 | Δρmax = 0.43 e Å−3 |
| S = 1.04 | Δρmin = −0.22 e Å−3 |
| 3784 reflections | Absolute structure: ? |
| 143 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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. |
| 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) |
| 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) |
| 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) |
| 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) |
| 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) |
The purchase of the diffractometer was made possible by grant No. LEQSF (1999–2000)-ENH-TR-13, administered by the Louisiana Board of Regents.
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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 δr.m.s. = 0.0145 (6) Å. With respect to this molecular plane, the mean plane of the carbonyl group (four atoms, δr.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, δr.m.s. = 0.0018 (4) Å) has dihedral angle 13.27 (7)°.