Acta Cryst. (2008). E64, o498 [ doi:10.1107/S1600536808001785 ]
The asymmetric unit of the title compound, C15H24O4, contains one half-molecule; a twofold rotation axis passes through the central C atom. The non-planar six- and five-membered rings adopt chair and envelope conformations, respectively. In the crystal structure, intermolecular C-H
O hydrogen bonds link the molecules.
The title compound was prepared from a mixture of 2,2-bis-(hydroxymethyl) propane-1,3-diol (0.68 g, 5 mmol), cyclopentanone (10 mmol), freshly activated catalyst TiO2/SO4(2-)(0.6 g, 0.32 mmol) and cyclohexane (80 ml), heated with stirring at refluxing temperature for 2 h, using a Dean-Stark apparatus in a nitrogen atmosphere (Sun et al., 2001). The progress of the reaction was monitored by thin-layer chromatography. After cooling to room temperature, the catalyst was filtered off, the crude product was isolated by distillation and the solid was recrystallized from ethanol. Crystals of (I) were obtained by dissolving the title compound (1.0 g) in toluene (15 ml) and evaporating the solvent slowly at room temperature for about 7 d.
H atoms were positioned geometrically, with C—H = 0.97 Å for methylene H, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).
Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: X-CAD4 (Harms & Wocadlo, 1995); 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: PLATON (Spek, 2003).
![[Figure 1]](./hk2414fig1thm.gif)
| Fig. 1. The molecular structure of the title molecule, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (A) 1 - x, y, 1/2 - z.] |
![[Figure 2]](./hk2414fig2thm.gif)
| Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines. |
| C15H24O4 | F000 = 584 |
| Mr = 268.34 | Dx = 1.206 Mg m−3 |
| Monoclinic, C2/c | Melting point: 401 K |
| Hall symbol: -C 2yc | Mo Kα radiation λ = 0.71073 Å |
| a = 25.605 (5) Å | Cell parameters from 25 reflections |
| b = 5.5820 (11) Å | θ = 10–13º |
| c = 10.337 (2) Å | µ = 0.09 mm−1 |
| β = 90.22 (3)º | T = 294 (2) K |
| V = 1477.4 (5) Å3 | Block, colorless |
| Z = 4 | 0.30 × 0.20 × 0.10 mm |
| Enraf–Nonius CAD-4 diffractometer | Rint = 0.050 |
| Radiation source: fine-focus sealed tube | θmax = 26.0º |
| Monochromator: graphite | θmin = 1.6º |
| T = 294(2) K | h = −31→31 |
| ω/2θ scans | k = 0→6 |
| Absorption correction: ψ scan (North et al., 1968) | l = 0→12 |
| Tmin = 0.965, Tmax = 0.982 | 3 standard reflections |
| 1547 measured reflections | every 120 min |
| 1457 independent reflections | intensity decay: none |
| 864 reflections with I > 2σ(I) |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.067 | H-atom parameters constrained |
| wR(F2) = 0.173 | w = 1/[σ2(Fo2) + (0.06P)2 + 4.5P] where P = (Fo2 + 2Fc2)/3 |
| S = 0.93 | (Δ/σ)max < 0.001 |
| 1457 reflections | Δρmax = 0.26 e Å−3 |
| 87 parameters | Δρmin = −0.21 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C15H24O4 | V = 1477.4 (5) Å3 |
| Mr = 268.34 | Z = 4 |
| Monoclinic, C2/c | Mo Kα |
| a = 25.605 (5) Å | µ = 0.09 mm−1 |
| b = 5.5820 (11) Å | T = 294 (2) K |
| c = 10.337 (2) Å | 0.30 × 0.20 × 0.10 mm |
| β = 90.22 (3)º |
| Enraf–Nonius CAD-4 diffractometer | 864 reflections with I > 2σ(I) |
| Absorption correction: ψ scan (North et al., 1968) | Rint = 0.050 |
| Tmin = 0.965, Tmax = 0.982 | 3 standard reflections |
| 1547 measured reflections | every 120 min |
| 1457 independent reflections | intensity decay: none |
| R[F2 > 2σ(F2)] = 0.067 | 87 parameters |
| wR(F2) = 0.173 | H-atom parameters constrained |
| S = 0.93 | Δρmax = 0.26 e Å−3 |
| 1457 reflections | Δρmin = −0.21 e Å−3 |
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. |
| x | y | z | Uiso*/Ueq | ||
| O1 | 0.43380 (7) | 0.3857 (4) | 0.41870 (16) | 0.0381 (5) | |
| O2 | 0.42692 (7) | 0.0861 (3) | 0.26166 (16) | 0.0324 (5) | |
| C1 | 0.30826 (17) | 0.3438 (9) | 0.3294 (5) | 0.0889 (15) | |
| H1A | 0.2819 | 0.3125 | 0.2638 | 0.107* | |
| H1B | 0.2974 | 0.4816 | 0.3797 | 0.107* | |
| C2 | 0.31481 (15) | 0.1237 (9) | 0.4179 (4) | 0.0803 (13) | |
| H2A | 0.2973 | 0.1514 | 0.4996 | 0.096* | |
| H2B | 0.2993 | −0.0159 | 0.3773 | 0.096* | |
| C3 | 0.36848 (12) | 0.0842 (7) | 0.4393 (3) | 0.0503 (9) | |
| H3A | 0.3768 | −0.0835 | 0.4262 | 0.060* | |
| H3B | 0.3777 | 0.1271 | 0.5274 | 0.060* | |
| C4 | 0.35773 (13) | 0.3897 (7) | 0.2697 (3) | 0.0567 (10) | |
| H4A | 0.3662 | 0.5588 | 0.2750 | 0.068* | |
| H4B | 0.3567 | 0.3436 | 0.1792 | 0.068* | |
| C5 | 0.39900 (11) | 0.2397 (5) | 0.3435 (3) | 0.0336 (7) | |
| C6 | 0.46853 (11) | 0.5234 (5) | 0.3396 (2) | 0.0342 (7) | |
| H6A | 0.4922 | 0.6138 | 0.3945 | 0.041* | |
| H6B | 0.4484 | 0.6366 | 0.2884 | 0.041* | |
| C7 | 0.5000 | 0.3637 (7) | 0.2500 | 0.0278 (8) | |
| C8 | 0.46173 (10) | 0.2072 (5) | 0.1738 (2) | 0.0337 (7) | |
| H8A | 0.4417 | 0.3060 | 0.1145 | 0.040* | |
| H8B | 0.4809 | 0.0901 | 0.1235 | 0.040* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0461 (12) | 0.0405 (12) | 0.0275 (9) | 0.0017 (10) | −0.0016 (8) | −0.0038 (9) |
| O2 | 0.0368 (10) | 0.0236 (10) | 0.0368 (10) | −0.0008 (9) | 0.0005 (8) | −0.0038 (8) |
| C1 | 0.076 (3) | 0.098 (4) | 0.093 (3) | 0.005 (3) | −0.001 (2) | 0.016 (3) |
| C2 | 0.069 (3) | 0.089 (3) | 0.083 (3) | −0.005 (3) | 0.006 (2) | 0.009 (3) |
| C3 | 0.052 (2) | 0.053 (2) | 0.0460 (17) | −0.0121 (17) | 0.0100 (15) | −0.0008 (16) |
| C4 | 0.057 (2) | 0.052 (2) | 0.061 (2) | 0.0252 (18) | −0.0165 (17) | −0.0025 (17) |
| C5 | 0.0338 (14) | 0.0256 (15) | 0.0413 (15) | 0.0057 (12) | −0.0035 (12) | −0.0032 (12) |
| C6 | 0.0469 (16) | 0.0252 (15) | 0.0306 (13) | −0.0021 (13) | −0.0012 (12) | −0.0044 (11) |
| C7 | 0.040 (2) | 0.023 (2) | 0.0204 (16) | 0.000 | −0.0036 (15) | 0.000 |
| C8 | 0.0393 (15) | 0.0322 (16) | 0.0296 (13) | −0.0017 (13) | −0.0019 (12) | −0.0004 (12) |
| O1—C5 | 1.434 (3) | C3—H3B | 0.9700 |
| O1—C6 | 1.434 (3) | C4—C5 | 1.547 (4) |
| O2—C5 | 1.402 (3) | C4—H4A | 0.9700 |
| O2—C8 | 1.443 (3) | C4—H4B | 0.9700 |
| C1—C4 | 1.434 (5) | C6—C7 | 1.519 (3) |
| C1—C2 | 1.540 (6) | C6—H6A | 0.9700 |
| C1—H1A | 0.9700 | C6—H6B | 0.9700 |
| C1—H1B | 0.9700 | C7—C6i | 1.519 (3) |
| C2—C3 | 1.408 (5) | C7—C8 | 1.529 (3) |
| C2—H2A | 0.9700 | C7—C8i | 1.529 (3) |
| C2—H2B | 0.9700 | C8—H8A | 0.9700 |
| C3—C5 | 1.533 (4) | C8—H8B | 0.9700 |
| C3—H3A | 0.9700 | ||
| C5—O1—C6 | 112.37 (19) | H4A—C4—H4B | 108.6 |
| C5—O2—C8 | 114.2 (2) | O2—C5—O1 | 110.9 (2) |
| C4—C1—C2 | 107.7 (4) | O2—C5—C3 | 107.8 (2) |
| C4—C1—H1A | 110.2 | O1—C5—C3 | 106.8 (2) |
| C2—C1—H1A | 110.2 | O2—C5—C4 | 112.5 (2) |
| C4—C1—H1B | 110.2 | O1—C5—C4 | 112.4 (2) |
| C2—C1—H1B | 110.2 | C3—C5—C4 | 106.0 (3) |
| H1A—C1—H1B | 108.5 | O1—C6—C7 | 111.4 (2) |
| C3—C2—C1 | 108.8 (4) | O1—C6—H6A | 109.4 |
| C3—C2—H2A | 109.9 | C7—C6—H6A | 109.4 |
| C1—C2—H2A | 109.9 | O1—C6—H6B | 109.4 |
| C3—C2—H2B | 109.9 | C7—C6—H6B | 109.4 |
| C1—C2—H2B | 109.9 | H6A—C6—H6B | 108.0 |
| H2A—C2—H2B | 108.3 | C6—C7—C6i | 108.1 (3) |
| C2—C3—C5 | 108.0 (3) | C6—C7—C8 | 107.99 (15) |
| C2—C3—H3A | 110.1 | C6i—C7—C8 | 111.22 (14) |
| C5—C3—H3A | 110.1 | C6—C7—C8i | 111.22 (14) |
| C2—C3—H3B | 110.1 | C6i—C7—C8i | 107.99 (15) |
| C5—C3—H3B | 110.1 | C8—C7—C8i | 110.3 (3) |
| H3A—C3—H3B | 108.4 | O2—C8—C7 | 109.86 (18) |
| C1—C4—C5 | 107.1 (3) | O2—C8—H8A | 109.7 |
| C1—C4—H4A | 110.3 | C7—C8—H8A | 109.7 |
| C5—C4—H4A | 110.3 | O2—C8—H8B | 109.7 |
| C1—C4—H4B | 110.3 | C7—C8—H8B | 109.7 |
| C5—C4—H4B | 110.3 | H8A—C8—H8B | 108.2 |
| Symmetry codes: (i) −x+1, y, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C6—H6B···O2ii | 0.97 | 2.58 | 3.413 (4) | 143 |
| Symmetry codes: (ii) x, y+1, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C6—H6B···O2i | 0.97 | 2.58 | 3.413 (4) | 143 |
| Symmetry codes: (i) x, y+1, z. |
The authors thank the Center of Testing and Analysis, Nanjing University, for the support.
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The title compound, (I), is an important intermediate in the synthesis of pesticides (Jermy & Pandurangan, 2005). The crystal structure determination of (I) has been carried out in order to elucidate the molecular conformation.
The asymmetric unit of the title compound, (I), contains one-half molecule (Fig. 1), in which the bond lengths are within normal ranges (Allen et al., 1987).
Ring B (O1/O2/C5—C8) is not planar, having total puckering amplitude, QT, of 0.943 (3) Å. It adopts chair conformation [φ = -32.96 (2)° and θ = 58.52 (3)°] (Cremer & Pople, 1975). Ring A has envelope conformation with atom C1 displaced by -0.222 (3) Å from the plane of the other ring atoms.
In the crystal structure, intermolecular C—H···O hydrogen bonds (Table 1) link the molecules, in which they may be effective in the stabilization of the structure.