Acta Cryst. (2008). E64, o1745 [ doi:10.1107/S1600536808025063 ]
In the title compound, C9H14O3, the cyclohexenone ring has an envelope conformation; the flap atom (with the hydroxymethyl groups attached) is displaced by 0.582 (4) Å from the plane of the other five ring atoms. The crystal structure contains an intermolecular O-H
O hydrogen-bonded ring.
A solution of 4,4-bis(hydroxymethyl)-2,6-heptanedione(188 mg, 1 mmol) and sodium methoxide (54 mg, 1 mmol) in methanol (10 ml) was heated at 323 K for 4 h. The reaction mixture was acidified with dilute aqueous HCl, then concentrated and partitioned between water and dichloromethane. The pure product was obtained through silica gel chromatography (eluant petroleum ether/ethyl acetate, 1:1), and diffraction quality crystals were obtained by slow evaporation of a dichloromethane / petroleum ether (1:3) solution at room temperature.
All H atoms were placed in calculated positions, with C—H distances in the range 0.93–0.98Å and included in the final cycles of refinement in the riding-model approximation, with Uiso(H) = 1.2Ueq(C).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004) and Larson (1970); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: CRYSTALS (Watkin et al., 1996); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2004).
![[Figure 1]](./ez2128fig1thm.gif)
| Fig. 1. The unit of (I) with atom labels, showing 50% probability displacement ellipsoids. |
![[Figure 2]](./ez2128fig2thm.gif)
| Fig. 2. A partial packing diagram viewed along the b axis. Hydrogen bonds are drawn as dashed lines. |
| C9H14O3 | Z = 2 |
| Mr = 170.21 | F000 = 184.00 |
| Triclinic, P1 | Dx = 1.241 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation λ = 0.71075 Å |
| a = 5.9791 (3) Å | Cell parameters from 3491 reflections |
| b = 6.22510 (10) Å | θ = 3.7–27.4º |
| c = 13.7493 (8) Å | µ = 0.09 mm−1 |
| α = 90.8104 (17)º | T = 296 (1) K |
| β = 91.3285 (12)º | Chunk, colorless |
| γ = 117.0728 (15)º | 0.43 × 0.40 × 0.20 mm |
| V = 455.38 (4) Å3 |
| Rigaku R-AXIS RAPID diffractometer | 1432 reflections with F2 > 2σ(F2) |
| Detector resolution: 10.00 pixels mm-1 | Rint = 0.018 |
| ω scans | θmax = 27.5º |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −7→7 |
| Tmin = 0.958, Tmax = 0.982 | k = −8→8 |
| 4514 measured reflections | l = −17→17 |
| 2060 independent reflections |
| Refinement on F2 | w = 1/[0.0027Fo2 + 5σ(Fo2) + 1]/(4Fo2) |
| R[F2 > 2σ(F2)] = 0.054 | (Δ/σ)max < 0.001 |
| wR(F2) = 0.195 | Δρmax = 0.29 e Å−3 |
| S = 1.01 | Δρmin = −0.23 e Å−3 |
| 2060 reflections | Extinction correction: Larson (1970) |
| 110 parameters | Extinction coefficient: 107 (30) |
| H-atom parameters constrained |
| C9H14O3 | γ = 117.0728 (15)º |
| Mr = 170.21 | V = 455.38 (4) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 5.9791 (3) Å | Mo Kα |
| b = 6.22510 (10) Å | µ = 0.09 mm−1 |
| c = 13.7493 (8) Å | T = 296 (1) K |
| α = 90.8104 (17)º | 0.43 × 0.40 × 0.20 mm |
| β = 91.3285 (12)º |
| Rigaku R-AXIS RAPID diffractometer | 2060 independent reflections |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 1432 reflections with F2 > 2σ(F2) |
| Tmin = 0.958, Tmax = 0.982 | Rint = 0.018 |
| 4514 measured reflections |
| R[F2 > 2σ(F2)] = 0.054 | ? restraints |
| wR(F2) = 0.195 | H-atom parameters constrained |
| S = 1.01 | Δρmax = 0.29 e Å−3 |
| 2060 reflections | Δρmin = −0.23 e Å−3 |
| 110 parameters |
Refinement. Refinement using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
| x | y | z | Uiso*/Ueq | ||
| O1 | 1.1756 (3) | 1.1069 (3) | 0.16817 (14) | 0.0617 (6) | |
| O2 | 0.8610 (2) | 0.5583 (3) | 0.38179 (12) | 0.0518 (5) | |
| O3 | 0.3183 (3) | 0.5928 (4) | 0.43726 (12) | 0.0625 (6) | |
| C1 | 0.6300 (3) | 0.7646 (4) | 0.31049 (14) | 0.0342 (5) | |
| C2 | 0.4284 (4) | 0.7285 (4) | 0.23242 (14) | 0.0382 (6) | |
| C3 | 0.5141 (4) | 0.7644 (4) | 0.13114 (16) | 0.0395 (6) | |
| C4 | 0.7599 (4) | 0.8911 (4) | 0.11129 (17) | 0.0459 (6) | |
| C5 | 0.9546 (4) | 1.0036 (4) | 0.18614 (18) | 0.0418 (6) | |
| C6 | 0.8686 (4) | 0.9901 (4) | 0.29092 (17) | 0.0435 (6) | |
| C7 | 0.3125 (5) | 0.6558 (5) | 0.05324 (18) | 0.0575 (8) | |
| C8 | 0.6772 (4) | 0.5422 (4) | 0.31014 (16) | 0.0391 (6) | |
| C9 | 0.5370 (4) | 0.7935 (5) | 0.41112 (17) | 0.0497 (7) | |
| H4 | 0.8057 | 0.9066 | 0.0466 | 0.055* | |
| H21 | 0.2949 | 0.5649 | 0.2365 | 0.046* | |
| H22 | 0.3628 | 0.8418 | 0.2467 | 0.046* | |
| H61 | 1.0013 | 0.9953 | 0.3343 | 0.052* | |
| H62 | 0.8404 | 1.1291 | 0.3044 | 0.052* | |
| H71 | 0.3875 | 0.6827 | −0.0093 | 0.069* | |
| H72 | 0.2024 | 0.7294 | 0.0564 | 0.069* | |
| H73 | 0.2183 | 0.4855 | 0.0626 | 0.069* | |
| H81 | 0.5204 | 0.4012 | 0.3225 | 0.047* | |
| H82 | 0.7344 | 0.5243 | 0.2465 | 0.047* | |
| H91 | 0.6684 | 0.8209 | 0.4596 | 0.060* | |
| H92 | 0.5042 | 0.9324 | 0.4103 | 0.060* | |
| H201 | 0.7736 | 0.4867 | 0.4357 | 0.067* | |
| H301 | 0.1888 | 0.6149 | 0.4049 | 0.081* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0437 (10) | 0.0582 (12) | 0.0750 (14) | 0.0149 (8) | 0.0195 (9) | 0.0154 (10) |
| O2 | 0.0403 (9) | 0.0843 (13) | 0.0433 (9) | 0.0383 (9) | 0.0072 (7) | 0.0232 (8) |
| O3 | 0.0444 (9) | 0.1166 (18) | 0.0398 (9) | 0.0471 (11) | 0.0123 (7) | 0.0284 (10) |
| C1 | 0.0325 (10) | 0.0441 (13) | 0.0296 (10) | 0.0205 (9) | 0.0006 (8) | −0.0006 (8) |
| C2 | 0.0357 (10) | 0.0514 (14) | 0.0324 (11) | 0.0239 (10) | 0.0002 (8) | 0.0044 (9) |
| C3 | 0.0480 (12) | 0.0438 (13) | 0.0328 (11) | 0.0263 (11) | −0.0014 (9) | 0.0041 (9) |
| C4 | 0.0556 (14) | 0.0524 (15) | 0.0333 (11) | 0.0272 (12) | 0.0097 (10) | 0.0090 (10) |
| C5 | 0.0422 (12) | 0.0347 (12) | 0.0508 (13) | 0.0190 (10) | 0.0108 (10) | 0.0086 (10) |
| C6 | 0.0423 (12) | 0.0411 (13) | 0.0437 (13) | 0.0163 (10) | −0.0014 (10) | −0.0049 (10) |
| C7 | 0.0663 (17) | 0.0717 (19) | 0.0387 (13) | 0.0360 (15) | −0.0145 (12) | −0.0003 (12) |
| C8 | 0.0371 (11) | 0.0488 (14) | 0.0366 (11) | 0.0238 (10) | −0.0010 (9) | 0.0071 (9) |
| C9 | 0.0473 (13) | 0.0781 (19) | 0.0333 (12) | 0.0367 (13) | 0.0062 (10) | 0.0024 (12) |
| O1—C5 | 1.211 (2) | O3—H301 | 0.948 |
| O2—C8 | 1.426 (3) | C2—H21 | 0.970 |
| O3—C9 | 1.395 (2) | C2—H22 | 0.970 |
| C1—C2 | 1.530 (3) | C4—H4 | 0.930 |
| C1—C6 | 1.512 (2) | C6—H61 | 0.970 |
| C1—C8 | 1.534 (4) | C6—H62 | 0.970 |
| C1—C9 | 1.541 (3) | C7—H71 | 0.960 |
| C2—C3 | 1.480 (3) | C7—H72 | 0.960 |
| C3—C4 | 1.351 (3) | C7—H73 | 0.960 |
| C3—C7 | 1.495 (3) | C8—H81 | 0.970 |
| C4—C5 | 1.445 (3) | C8—H82 | 0.970 |
| C5—C6 | 1.531 (3) | C9—H91 | 0.970 |
| O2—H201 | 0.915 | C9—H92 | 0.970 |
| C2—C1—C6 | 109.76 (18) | C3—C4—H4 | 118.6 |
| C2—C1—C8 | 109.12 (18) | C5—C4—H4 | 118.6 |
| C2—C1—C9 | 109.4 (2) | C1—C6—H61 | 108.4 |
| C6—C1—C8 | 110.8 (2) | C1—C6—H62 | 108.4 |
| C6—C1—C9 | 108.79 (18) | C5—C6—H61 | 108.4 |
| C8—C1—C9 | 109.0 (2) | C5—C6—H62 | 108.4 |
| C1—C2—C3 | 115.5 (2) | H61—C6—H62 | 109.5 |
| C2—C3—C4 | 121.45 (19) | C3—C7—H71 | 109.5 |
| C2—C3—C7 | 115.92 (19) | C3—C7—H72 | 109.5 |
| C4—C3—C7 | 122.6 (2) | C3—C7—H73 | 109.5 |
| C3—C4—C5 | 122.9 (2) | H71—C7—H72 | 109.5 |
| O1—C5—C4 | 122.5 (2) | H71—C7—H73 | 109.5 |
| O1—C5—C6 | 120.8 (2) | H72—C7—H73 | 109.5 |
| C4—C5—C6 | 116.7 (2) | O2—C8—H81 | 108.6 |
| C1—C6—C5 | 113.84 (17) | O2—C8—H82 | 108.6 |
| O2—C8—C1 | 113.12 (18) | C1—C8—H81 | 108.6 |
| O3—C9—C1 | 113.6 (2) | C1—C8—H82 | 108.6 |
| C8—O2—H201 | 105.8 | H81—C8—H82 | 109.5 |
| C9—O3—H301 | 103.4 | O3—C9—H91 | 108.4 |
| C1—C2—H21 | 107.9 | O3—C9—H92 | 108.4 |
| C1—C2—H22 | 107.9 | C1—C9—H91 | 108.4 |
| C3—C2—H21 | 107.9 | C1—C9—H92 | 108.4 |
| C3—C2—H22 | 107.9 | H91—C9—H92 | 109.5 |
| H21—C2—H22 | 109.5 | ||
| C2—C1—C6—C5 | −50.0 (3) | C8—C1—C9—O3 | −58.2 (2) |
| C6—C1—C2—C3 | 44.7 (3) | C9—C1—C8—O2 | −59.9 (2) |
| C2—C1—C8—O2 | −179.24 (16) | C1—C2—C3—C4 | −19.9 (4) |
| C8—C1—C2—C3 | −76.9 (2) | C1—C2—C3—C7 | 161.0 (2) |
| C2—C1—C9—O3 | 61.0 (3) | C2—C3—C4—C5 | −1.2 (4) |
| C9—C1—C2—C3 | 164.0 (2) | C7—C3—C4—C5 | 177.8 (3) |
| C6—C1—C8—O2 | 59.8 (2) | C3—C4—C5—O1 | 176.3 (3) |
| C8—C1—C6—C5 | 70.6 (2) | C3—C4—C5—C6 | −4.6 (4) |
| C6—C1—C9—O3 | −179.1 (2) | O1—C5—C6—C1 | −149.4 (2) |
| C9—C1—C6—C5 | −169.7 (2) | C4—C5—C6—C1 | 31.5 (3) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H201···O3i | 0.92 | 1.85 | 2.738 (2) | 163 |
| O3—H301···O2ii | 0.95 | 1.85 | 2.733 (2) | 155 |
| Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H201···O3i | 0.92 | 1.85 | 2.738 (2) | 163 |
| O3—H301···O2ii | 0.95 | 1.85 | 2.733 (2) | 155 |
| Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y, z. |
This work was partially supported by the Natural Science Foundation of China (20572094, 20672099). Mr Xinju Ma of the College of Pharmaceutical Science of Zhejiang University of Technology is acknowledged for assistance with the crystal-structure analysis.
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Functionalized cyclohex-2-enone derivatives can be used as precursors in the syntheses of some complex compounds, such as vitamin E, amino acids, terpenes etc. (Hu et al., 2003). In addition, cyclohex-2-enone derivatives have been shown to have a wide range of biological activities such as antimicrobial (Li et al., 2001) and anticancer (Aghil et al., 1992) activities, and are involved in the protection of cerebral neurocytes (Luu et al., 2004). We are interested in their further pharmaceutical activity.
In this paper, we present an X-ray crystallographic analysis of the title compound (I) (Fig. 1). The cyclohexenone ring has an envelope conformation, such that the plane which is composed of atoms C1, C2 and C6 (forming the flap) and the C2, C3, C4, C5, C6 plane form a dihedral angle of 41.80 (4)°. Two molecules are linked together through O—H···O interactions. Since each molecule contains a hydrogen-bond donor group (–OH) at one end and an acceptor (–OH) at the other, a ring of four H-bonds is formed between these two molecules and a neighboring pair in the crystal lattice (Fig. 2).