Acta Cryst. (2009). E65, o1559 [ doi:10.1107/S1600536809021291 ]
The molecule of the title compound, C16H28O4, is centrosymmetric. The cyclohexane ring and both six-membered dioxane rings adopt chair conformations. In the crystal, the molecules lie in layers in the (100) planes and the shortest intermolecular contacts are H
H (2.30 Å).
The title compound was obtained by reaction of 1,4-cyclohexanedione (20 mmol), 2,2-dimethyl-1,3-propanediol (40 mmol) and sulfuric acid (0.1 mmol) in hexane (20 ml). The mixture was stirred for 6 h at 333 K. Colourless block-shaped crystals suitable for X-ray diffraction analysis were grown at the bottom of the vessel after 7 days slow evaporation of the solution at room temperature.
H atoms were placed in calculated positions with C—H = 0.99 and 0.98 Å for methylene and methyl H atoms, respectively, and refined as riding with Uiso(H) = 1.2 or 1.5Ueq(C).
Data collection: RAPID-AUTO (Rigaku 2004); cell refinement: RAPID-AUTO (Rigaku 2004); data reduction: RAPID-AUTO (Rigaku 2004); 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: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./bi2376fig1thm.gif)
| Fig. 1. The molecular structure with displacement ellipsoids drawn at the 30% probability level for non-H atoms. Non-labelled atoms are related to labelled atoms by the symmetry operator: 1 - x, 1 - y, 1 - z. |
| C16H28O4 | F(000) = 312 |
| Mr = 284.38 | Dx = 1.223 Mg m−3 |
| Monoclinic, P21/c | Melting point: 430 K |
| Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
| a = 12.639 (8) Å | Cell parameters from 2071 reflections |
| b = 5.838 (4) Å | θ = 3.3–27.5° |
| c = 11.179 (7) Å | µ = 0.09 mm−1 |
| β = 110.611 (8)° | T = 93 K |
| V = 772.1 (9) Å3 | Block, colourless |
| Z = 2 | 0.43 × 0.37 × 0.14 mm |
| Rigaku SPIDER diffractometer | 1243 reflections with I > 2σ(I) |
| Radiation source: Rotating Anode | Rint = 0.048 |
| graphite | θmax = 27.5°, θmin = 3.4° |
| ω scans | h = −16→16 |
| 5721 measured reflections | k = −7→7 |
| 1752 independent reflections | l = −13→14 |
| 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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.095 | H-atom parameters constrained |
| S = 1.00 | w = 1/[σ2(Fo2) + (0.0116P)2 + 0.36P] where P = (Fo2 + 2Fc2)/3 |
| 1752 reflections | (Δ/σ)max < 0.001 |
| 93 parameters | Δρmax = 0.27 e Å−3 |
| 0 restraints | Δρmin = −0.19 e Å−3 |
| C16H28O4 | V = 772.1 (9) Å3 |
| Mr = 284.38 | Z = 2 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 12.639 (8) Å | µ = 0.09 mm−1 |
| b = 5.838 (4) Å | T = 93 K |
| c = 11.179 (7) Å | 0.43 × 0.37 × 0.14 mm |
| β = 110.611 (8)° |
| Rigaku SPIDER diffractometer | Rint = 0.048 |
| 5721 measured reflections | θmax = 27.5° |
| 1752 independent reflections | Standard reflections: 0 |
| 1243 reflections with I > 2σ(I) |
| R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
| wR(F2) = 0.095 | Δρmax = 0.27 e Å−3 |
| S = 1.00 | Δρmin = −0.19 e Å−3 |
| 1752 reflections | Absolute structure: ? |
| 93 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. |
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 | 0.68024 (9) | 0.62454 (18) | 0.57453 (10) | 0.0219 (3) | |
| O2 | 0.66546 (9) | 0.37232 (18) | 0.73088 (10) | 0.0221 (3) | |
| C1 | 0.43232 (13) | 0.7060 (3) | 0.48564 (15) | 0.0224 (4) | |
| H1A | 0.3649 | 0.7851 | 0.4912 | 0.027* | |
| H1B | 0.4768 | 0.8194 | 0.4574 | 0.027* | |
| C2 | 0.50381 (13) | 0.6171 (3) | 0.61780 (15) | 0.0220 (4) | |
| H2A | 0.5299 | 0.7478 | 0.6774 | 0.026* | |
| H2B | 0.4570 | 0.5166 | 0.6505 | 0.026* | |
| C3 | 0.60572 (13) | 0.4836 (3) | 0.61294 (15) | 0.0204 (4) | |
| C4 | 0.74097 (14) | 0.7887 (3) | 0.66956 (15) | 0.0232 (4) | |
| H4A | 0.6868 | 0.8977 | 0.6843 | 0.028* | |
| H4B | 0.7928 | 0.8768 | 0.6380 | 0.028* | |
| C5 | 0.80864 (13) | 0.6730 (3) | 0.79466 (15) | 0.0217 (4) | |
| C6 | 0.72591 (14) | 0.5256 (3) | 0.83191 (15) | 0.0222 (4) | |
| H6A | 0.7677 | 0.4360 | 0.9093 | 0.027* | |
| H6B | 0.6715 | 0.6257 | 0.8526 | 0.027* | |
| C7 | 0.85930 (15) | 0.8559 (3) | 0.89653 (16) | 0.0284 (4) | |
| H7A | 0.9083 | 0.9571 | 0.8691 | 0.034* | |
| H7B | 0.9038 | 0.7820 | 0.9773 | 0.034* | |
| H7C | 0.7983 | 0.9459 | 0.9085 | 0.034* | |
| C8 | 0.90174 (14) | 0.5242 (3) | 0.77798 (16) | 0.0288 (4) | |
| H8A | 0.8680 | 0.4097 | 0.7113 | 0.035* | |
| H8B | 0.9430 | 0.4466 | 0.8587 | 0.035* | |
| H8C | 0.9541 | 0.6206 | 0.7532 | 0.035* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0275 (6) | 0.0188 (6) | 0.0206 (6) | −0.0030 (5) | 0.0099 (5) | −0.0001 (5) |
| O2 | 0.0292 (6) | 0.0154 (6) | 0.0197 (6) | −0.0016 (5) | 0.0060 (5) | 0.0013 (5) |
| C1 | 0.0282 (9) | 0.0151 (8) | 0.0240 (9) | 0.0018 (6) | 0.0093 (7) | −0.0016 (7) |
| C2 | 0.0262 (9) | 0.0184 (8) | 0.0217 (9) | 0.0008 (6) | 0.0087 (7) | −0.0019 (7) |
| C3 | 0.0254 (9) | 0.0167 (8) | 0.0188 (8) | −0.0007 (6) | 0.0074 (7) | 0.0024 (7) |
| C4 | 0.0289 (9) | 0.0160 (8) | 0.0240 (9) | −0.0042 (7) | 0.0083 (7) | 0.0000 (7) |
| C5 | 0.0258 (9) | 0.0182 (8) | 0.0209 (9) | −0.0010 (7) | 0.0083 (7) | 0.0002 (7) |
| C6 | 0.0277 (9) | 0.0207 (8) | 0.0175 (9) | 0.0002 (7) | 0.0073 (7) | 0.0003 (7) |
| C7 | 0.0331 (10) | 0.0254 (9) | 0.0253 (10) | −0.0041 (8) | 0.0084 (8) | −0.0010 (8) |
| C8 | 0.0281 (9) | 0.0291 (10) | 0.0293 (10) | 0.0016 (7) | 0.0105 (8) | 0.0008 (8) |
| O1—C3 | 1.4258 (19) | C4—H4A | 0.990 |
| O1—C4 | 1.4362 (19) | C4—H4B | 0.990 |
| O2—C3 | 1.4248 (19) | C5—C6 | 1.521 (2) |
| O2—C6 | 1.4328 (19) | C5—C8 | 1.526 (2) |
| C1—C3i | 1.516 (2) | C5—C7 | 1.527 (2) |
| C1—C2 | 1.526 (2) | C6—H6A | 0.990 |
| C1—H1A | 0.990 | C6—H6B | 0.990 |
| C1—H1B | 0.990 | C7—H7A | 0.980 |
| C2—C3 | 1.523 (2) | C7—H7B | 0.980 |
| C2—H2A | 0.990 | C7—H7C | 0.980 |
| C2—H2B | 0.990 | C8—H8A | 0.980 |
| C3—C1i | 1.516 (2) | C8—H8B | 0.980 |
| C4—C5 | 1.517 (2) | C8—H8C | 0.980 |
| C3—O1—C4 | 113.58 (12) | H4A—C4—H4B | 108.0 |
| C3—O2—C6 | 113.98 (12) | C4—C5—C6 | 106.59 (13) |
| C3i—C1—C2 | 112.55 (13) | C4—C5—C8 | 110.46 (14) |
| C3i—C1—H1A | 109.1 | C6—C5—C8 | 110.18 (14) |
| C2—C1—H1A | 109.1 | C4—C5—C7 | 109.17 (14) |
| C3i—C1—H1B | 109.1 | C6—C5—C7 | 109.84 (14) |
| C2—C1—H1B | 109.1 | C8—C5—C7 | 110.50 (14) |
| H1A—C1—H1B | 107.8 | O2—C6—C5 | 111.39 (13) |
| C3—C2—C1 | 111.07 (13) | O2—C6—H6A | 109.3 |
| C3—C2—H2A | 109.4 | C5—C6—H6A | 109.3 |
| C1—C2—H2A | 109.4 | O2—C6—H6B | 109.3 |
| C3—C2—H2B | 109.4 | C5—C6—H6B | 109.3 |
| C1—C2—H2B | 109.4 | H6A—C6—H6B | 108.0 |
| H2A—C2—H2B | 108.0 | C5—C7—H7A | 109.5 |
| O2—C3—O1 | 110.54 (12) | C5—C7—H7B | 109.5 |
| O2—C3—C1i | 105.59 (13) | H7A—C7—H7B | 109.5 |
| O1—C3—C1i | 106.05 (13) | C5—C7—H7C | 109.5 |
| O2—C3—C2 | 112.32 (13) | H7A—C7—H7C | 109.5 |
| O1—C3—C2 | 111.86 (13) | H7B—C7—H7C | 109.5 |
| C1i—C3—C2 | 110.12 (13) | C5—C8—H8A | 109.5 |
| O1—C4—C5 | 111.45 (13) | C5—C8—H8B | 109.5 |
| O1—C4—H4A | 109.3 | H8A—C8—H8B | 109.5 |
| C5—C4—H4A | 109.3 | C5—C8—H8C | 109.5 |
| O1—C4—H4B | 109.3 | H8A—C8—H8C | 109.5 |
| C5—C4—H4B | 109.3 | H8B—C8—H8C | 109.5 |
| C3i—C1—C2—C3 | 56.01 (19) | C1—C2—C3—C1i | −54.63 (18) |
| C6—O2—C3—O1 | 54.99 (16) | C3—O1—C4—C5 | 57.12 (17) |
| C6—O2—C3—C1i | 169.25 (12) | O1—C4—C5—C6 | −54.38 (17) |
| C6—O2—C3—C2 | −70.72 (16) | O1—C4—C5—C8 | 65.32 (17) |
| C4—O1—C3—O2 | −55.06 (16) | O1—C4—C5—C7 | −172.97 (13) |
| C4—O1—C3—C1i | −169.04 (12) | C3—O2—C6—C5 | −56.61 (17) |
| C4—O1—C3—C2 | 70.90 (16) | C4—C5—C6—O2 | 54.05 (17) |
| C1—C2—C3—O2 | −172.00 (12) | C8—C5—C6—O2 | −65.83 (17) |
| C1—C2—C3—O1 | 63.02 (16) | C7—C5—C6—O2 | 172.21 (13) |
| Symmetry codes: (i) −x+1, −y+1, −z+1. |
The authors acknowledge financial support from Jiangsu Institute of Nuclear Medicine.
Babler, J. H. & Spina, K. P. (1984). Synth. Commun. 14, 39–44.
Borrett, G. T., Kitteringham, J., Porter, R. A., Shipton, M. R., Vimal, M. & Young, R. C. (1999). US Patent No. 5 962 501.
Luger, P., Plieth, K. & Ruban, G. (1972). Acta Cryst. B28, 706–710.
Rigaku (2004). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
The title compound is useful as an intermediate in the synthesis of Frovatriptan, a 5-HT1-like agonist (Babler & Spina, 1984; Borrett et al., 1999). The molecular structure is shown in Fig. 1. Three six-membered rings exhibit chair conformations, with C—C bond lengths in the range 1.516 (2)–1.527 (2) Å and C—C—C angles in the range 106.59 (13)–112.55 (13)°; these agree well with the values in other cyclohexane derivatives described in the literature (Luger et al., 1972).