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organic compounds
| CRYSTALLOGRAPHIC COMMUNICATIONS |
accessrac-2-tert-Butyl-2,4,5,6,6-pentachlorocyclohex-3-en-1-one
aBaku State University, Z. Khalilov St. 23, Baku AZ-1148, Azerbaijan
*Correspondence e-mail: Bahruz_81@mail.ru
The title compound, C10H11Cl5O, is a chiral molecule with two stereogenic centres. However, it crystallizes as a racemate. One of enantiomers reveals the (2S*,5R*). The cyclohexene ring adopts a half-chair conformation.
Related literature
For general background to the synthesis of 2-tert-butyl-2,4,5,6,6-pentachlorocyclohex-3-enone and its derivatives, see: Hartshorn et al. (1992![[Hartshorn, M. P., Roddick, A. D., Steel, P. J. & Wright, G. J. (1992). Aust. J. Chem. 45, 721-730.]](../../../../../../logos/arrows/e_arr.gif "Hartshorn, M. P., Roddick, A. D., Steel, P. J. & Wright, G. J. (1992). Aust. J. Chem. 45, 721-730.")
).
![[Scheme 1]](kp2308scheme1.gif)
Experimental
Crystal data
|
Data collection: APEX2 (Bruker, 2005); cell SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Supporting information
contains datablocks global, I. DOI: 10.1107/S160053681100897X/kp2308sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S160053681100897X/kp2308Isup2.hkl
2,6-di-tert-butylphenol (2.30 mol) and ammonium thiocyanate (4.83 mol) in methanol (1200 mL) was stirred with cooling at 273 K. While the temperature was kept in the range from 273 K to 283 K, chlorine gas was slowly bubbled through the mixture for about 1 h, during which the reaction mixture turned to yellow colour. Ammonia was then bubbled through the mixture for about 1.5 h, keeping the reaction mixture in the temperature range from 273 K to 283 K. The reaction was stirred for one more h at 273 K, poured into 2 L of cold distilled water and refrigerated overnight. The aqueous phase was decanted and the solid was taken up in methanol, precipitated by addition of water, filtered and dried. The resulting gummy yellow solid was recrystallised from methanol and dried in vacuum to yield the product as a white powder. The crystals were dissolved in methanol and recrystallised to yield colourless block-shaped crystals of the title compound.
The other hydrogen atoms were placed in calculated positions with and refined in the riding model with fixed isotropic displacement parameters [Uiso(H) = 1.2Ueq(C)].
Data collection: APEX2 (Bruker, 2005); cell SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./kp2308fig1thm.gif) | Fig. 1. The molecular structure of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. |
| C10H11Cl5O | F(000) = 656 |
| Mr = 324.44 | Dx = 1.626 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 6043 reflections |
| a = 6.9466 (7) Å | θ = 2.6–28.3° |
| b = 15.7237 (15) Å | µ = 1.07 mm−1 |
| c = 12.1785 (13) Å | T = 296 K |
| β = 94.903 (5)° | Prism, colourless |
| V = 1325.3 (2) Å3 | 0.30 × 0.30 × 0.20 mm |
| Z = 4 |
| Bruker APEXII CCD diffractometer | 2880 independent reflections |
| Radiation source: fine-focus sealed tube | 2472 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.024 |
| ϕ and ω scans | θmax = 27.0°, θmin = 2.1° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −8→8 |
| Tmin = 0.740, Tmax = 0.815 | k = −19→20 |
| 11583 measured reflections | l = −13→15 |
| 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)] = 0.031 | Hydrogen site location: difference Fourier map |
| wR(F2) = 0.082 | H-atom parameters constrained |
| S = 1.00 | w = 1/[σ2(Fo2) + (0.0394P)2 + 0.5385P] where P = (Fo2 + 2Fc2)/3 |
| 2880 reflections | (Δ/σ)max = 0.001 |
| 148 parameters | Δρmax = 0.39 e Å−3 |
| 0 restraints | Δρmin = −0.23 e Å−3 |
| C10H11Cl5O | V = 1325.3 (2) Å3 |
| Mr = 324.44 | Z = 4 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 6.9466 (7) Å | µ = 1.07 mm−1 |
| b = 15.7237 (15) Å | T = 296 K |
| c = 12.1785 (13) Å | 0.30 × 0.30 × 0.20 mm |
| β = 94.903 (5)° |
| Bruker APEXII CCD diffractometer | 2880 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2472 reflections with I > 2σ(I) |
| Tmin = 0.740, Tmax = 0.815 | Rint = 0.024 |
| 11583 measured reflections |
| R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
| wR(F2) = 0.082 | H-atom parameters constrained |
| S = 1.00 | Δρmax = 0.39 e Å−3 |
| 2880 reflections | Δρmin = −0.23 e Å−3 |
| 148 parameters |
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 | ||
| Cl1 | 0.71222 (8) | 0.85115 (3) | 0.19948 (5) | 0.05953 (16) | |
| Cl2 | 1.04573 (7) | 0.57732 (3) | 0.09467 (4) | 0.04698 (13) | |
| Cl3 | 1.04201 (9) | 0.55909 (4) | 0.38510 (5) | 0.06249 (17) | |
| Cl4 | 0.60933 (10) | 0.59189 (4) | 0.43935 (5) | 0.0725 (2) | |
| Cl5 | 0.51257 (7) | 0.65020 (4) | 0.21735 (5) | 0.05830 (16) | |
| O1 | 0.7230 (3) | 0.76496 (11) | 0.44023 (14) | 0.0731 (5) | |
| C1 | 0.7672 (3) | 0.73432 (11) | 0.35685 (15) | 0.0392 (4) | |
| C2 | 0.8874 (2) | 0.78139 (10) | 0.27498 (13) | 0.0332 (3) | |
| C3 | 0.9594 (2) | 0.72330 (10) | 0.18964 (13) | 0.0322 (3) | |
| H3 | 1.0140 | 0.7479 | 0.1302 | 0.039* | |
| C4 | 0.9500 (2) | 0.63939 (10) | 0.19366 (13) | 0.0311 (3) | |
| C5 | 0.8610 (3) | 0.58988 (11) | 0.28024 (14) | 0.0382 (4) | |
| H5 | 0.8030 | 0.5383 | 0.2464 | 0.046* | |
| C6 | 0.7021 (3) | 0.64222 (12) | 0.32611 (15) | 0.0412 (4) | |
| C7 | 1.0544 (3) | 0.83642 (11) | 0.33343 (15) | 0.0393 (4) | |
| C8 | 1.1855 (3) | 0.77762 (14) | 0.40573 (18) | 0.0555 (5) | |
| H8A | 1.1150 | 0.7548 | 0.4635 | 0.083* | |
| H8B | 1.2949 | 0.8091 | 0.4374 | 0.083* | |
| H8C | 1.2290 | 0.7319 | 0.3618 | 0.083* | |
| C9 | 1.1720 (4) | 0.87761 (16) | 0.2469 (2) | 0.0649 (6) | |
| H9A | 1.2300 | 0.8341 | 0.2054 | 0.097* | |
| H9B | 1.2713 | 0.9127 | 0.2830 | 0.097* | |
| H9C | 1.0884 | 0.9119 | 0.1981 | 0.097* | |
| C10 | 0.9811 (3) | 0.90805 (13) | 0.40509 (18) | 0.0549 (5) | |
| H10A | 1.0887 | 0.9412 | 0.4357 | 0.082* | |
| H10B | 0.9150 | 0.8838 | 0.4637 | 0.082* | |
| H10C | 0.8939 | 0.9439 | 0.3606 | 0.082* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.0644 (3) | 0.0425 (3) | 0.0680 (3) | 0.0196 (2) | −0.0158 (3) | −0.0037 (2) |
| Cl2 | 0.0602 (3) | 0.0397 (2) | 0.0426 (3) | 0.0075 (2) | 0.0136 (2) | −0.01185 (18) |
| Cl3 | 0.0763 (4) | 0.0583 (3) | 0.0519 (3) | 0.0143 (3) | −0.0003 (3) | 0.0212 (2) |
| Cl4 | 0.0883 (5) | 0.0718 (4) | 0.0632 (4) | −0.0239 (3) | 0.0395 (3) | 0.0014 (3) |
| Cl5 | 0.0372 (2) | 0.0698 (4) | 0.0671 (3) | −0.0054 (2) | −0.0002 (2) | −0.0178 (3) |
| O1 | 0.0907 (12) | 0.0659 (10) | 0.0698 (11) | −0.0203 (9) | 0.0479 (10) | −0.0304 (8) |
| C1 | 0.0370 (9) | 0.0393 (9) | 0.0423 (10) | 0.0002 (7) | 0.0098 (7) | −0.0097 (7) |
| C2 | 0.0370 (9) | 0.0268 (8) | 0.0353 (9) | 0.0040 (6) | 0.0009 (7) | −0.0029 (6) |
| C3 | 0.0372 (9) | 0.0322 (8) | 0.0270 (8) | 0.0004 (7) | 0.0026 (6) | −0.0002 (6) |
| C4 | 0.0335 (8) | 0.0311 (8) | 0.0286 (8) | 0.0034 (6) | 0.0025 (6) | −0.0050 (6) |
| C5 | 0.0482 (10) | 0.0295 (8) | 0.0372 (9) | −0.0016 (7) | 0.0051 (7) | −0.0005 (7) |
| C6 | 0.0421 (10) | 0.0421 (10) | 0.0409 (10) | −0.0075 (8) | 0.0116 (8) | −0.0024 (8) |
| C7 | 0.0442 (10) | 0.0331 (9) | 0.0405 (10) | −0.0044 (7) | 0.0024 (8) | −0.0088 (7) |
| C8 | 0.0505 (12) | 0.0561 (12) | 0.0570 (13) | 0.0041 (10) | −0.0118 (9) | −0.0138 (10) |
| C9 | 0.0754 (16) | 0.0562 (13) | 0.0650 (14) | −0.0310 (12) | 0.0174 (12) | −0.0111 (11) |
| C10 | 0.0675 (14) | 0.0396 (10) | 0.0570 (13) | 0.0000 (10) | 0.0016 (10) | −0.0186 (9) |
| Cl1—C2 | 1.8271 (17) | C5—H5 | 0.9800 |
| Cl2—C4 | 1.7278 (16) | C7—C8 | 1.524 (3) |
| Cl3—C5 | 1.7808 (19) | C7—C9 | 1.531 (3) |
| Cl4—C6 | 1.7593 (18) | C7—C10 | 1.538 (2) |
| Cl5—C6 | 1.790 (2) | C8—H8A | 0.9600 |
| O1—C1 | 1.188 (2) | C8—H8B | 0.9600 |
| C1—C2 | 1.543 (2) | C8—H8C | 0.9600 |
| C1—C6 | 1.553 (2) | C9—H9A | 0.9600 |
| C2—C3 | 1.501 (2) | C9—H9B | 0.9600 |
| C2—C7 | 1.569 (2) | C9—H9C | 0.9600 |
| C3—C4 | 1.322 (2) | C10—H10A | 0.9600 |
| C3—H3 | 0.9300 | C10—H10B | 0.9600 |
| C4—C5 | 1.487 (2) | C10—H10C | 0.9600 |
| C5—C6 | 1.521 (3) | ||
| O1—C1—C2 | 123.48 (16) | Cl4—C6—Cl5 | 108.43 (10) |
| O1—C1—C6 | 119.52 (17) | C8—C7—C9 | 109.08 (18) |
| C2—C1—C6 | 117.00 (14) | C8—C7—C10 | 109.08 (16) |
| C3—C2—C1 | 112.72 (13) | C9—C7—C10 | 107.62 (17) |
| C3—C2—C7 | 111.88 (14) | C8—C7—C2 | 108.04 (14) |
| C1—C2—C7 | 113.04 (14) | C9—C7—C2 | 109.78 (15) |
| C3—C2—Cl1 | 105.30 (11) | C10—C7—C2 | 113.17 (16) |
| C1—C2—Cl1 | 103.84 (11) | C7—C8—H8A | 109.5 |
| C7—C2—Cl1 | 109.40 (11) | C7—C8—H8B | 109.5 |
| C4—C3—C2 | 124.13 (15) | H8A—C8—H8B | 109.5 |
| C4—C3—H3 | 117.9 | C7—C8—H8C | 109.5 |
| C2—C3—H3 | 117.9 | H8A—C8—H8C | 109.5 |
| C3—C4—C5 | 125.00 (15) | H8B—C8—H8C | 109.5 |
| C3—C4—Cl2 | 120.98 (13) | C7—C9—H9A | 109.5 |
| C5—C4—Cl2 | 114.03 (12) | C7—C9—H9B | 109.5 |
| C4—C5—C6 | 109.63 (14) | H9A—C9—H9B | 109.5 |
| C4—C5—Cl3 | 109.88 (12) | C7—C9—H9C | 109.5 |
| C6—C5—Cl3 | 111.96 (13) | H9A—C9—H9C | 109.5 |
| C4—C5—H5 | 108.4 | H9B—C9—H9C | 109.5 |
| C6—C5—H5 | 108.4 | C7—C10—H10A | 109.5 |
| Cl3—C5—H5 | 108.4 | C7—C10—H10B | 109.5 |
| C5—C6—C1 | 112.78 (14) | H10A—C10—H10B | 109.5 |
| C5—C6—Cl4 | 111.74 (13) | C7—C10—H10C | 109.5 |
| C1—C6—Cl4 | 110.43 (13) | H10A—C10—H10C | 109.5 |
| C5—C6—Cl5 | 106.09 (12) | H10B—C10—H10C | 109.5 |
| C1—C6—Cl5 | 107.08 (13) | ||
| O1—C1—C2—C3 | 167.6 (2) | Cl3—C5—C6—Cl4 | −51.23 (16) |
| C6—C1—C2—C3 | −12.6 (2) | C4—C5—C6—Cl5 | 68.58 (15) |
| O1—C1—C2—C7 | 39.5 (3) | Cl3—C5—C6—Cl5 | −169.21 (9) |
| C6—C1—C2—C7 | −140.75 (16) | O1—C1—C6—C5 | −137.5 (2) |
| O1—C1—C2—Cl1 | −79.0 (2) | C2—C1—C6—C5 | 42.7 (2) |
| C6—C1—C2—Cl1 | 100.79 (15) | O1—C1—C6—Cl4 | −11.7 (2) |
| C1—C2—C3—C4 | −10.6 (2) | C2—C1—C6—Cl4 | 168.56 (13) |
| C7—C2—C3—C4 | 118.08 (18) | O1—C1—C6—Cl5 | 106.2 (2) |
| Cl1—C2—C3—C4 | −123.17 (16) | C2—C1—C6—Cl5 | −73.58 (17) |
| C2—C3—C4—C5 | 2.4 (3) | C3—C2—C7—C8 | −69.95 (19) |
| C2—C3—C4—Cl2 | −177.26 (12) | C1—C2—C7—C8 | 58.59 (19) |
| C3—C4—C5—C6 | 28.3 (2) | Cl1—C2—C7—C8 | 173.76 (13) |
| Cl2—C4—C5—C6 | −152.03 (13) | C3—C2—C7—C9 | 48.9 (2) |
| C3—C4—C5—Cl3 | −95.12 (18) | C1—C2—C7—C9 | 177.43 (16) |
| Cl2—C4—C5—Cl3 | 84.53 (13) | Cl1—C2—C7—C9 | −67.40 (18) |
| C4—C5—C6—C1 | −48.3 (2) | C3—C2—C7—C10 | 169.15 (16) |
| Cl3—C5—C6—C1 | 73.88 (17) | C1—C2—C7—C10 | −62.3 (2) |
| C4—C5—C6—Cl4 | −173.43 (12) | Cl1—C2—C7—C10 | 52.87 (18) |
Experimental details
| Crystal data | |
| Chemical formula | C10H11Cl5O |
| Mr | 324.44 |
| Crystal system, space group | Monoclinic, P21/n |
| Temperature (K) | 296 |
| a, b, c (Å) | 6.9466 (7), 15.7237 (15), 12.1785 (13) |
| β (°) | 94.903 (5) |
| V (Å3) | 1325.3 (2) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 1.07 |
| Crystal size (mm) | 0.30 × 0.30 × 0.20 |
| Data collection | |
| Diffractometer | Bruker APEXII CCD diffractometer |
| Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
| Tmin, Tmax | 0.740, 0.815 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 11583, 2880, 2472 |
| Rint | 0.024 |
| (sin θ/λ)max (Å−1) | 0.639 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.082, 1.00 |
| No. of reflections | 2880 |
| No. of parameters | 148 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.39, −0.23 |
Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2001), SHELXTL (Sheldrick, 2008).
Acknowledgements
We thank Atash Kurbanov for fruitful discussions and help in this work.
References
Bruker (2001). SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2005). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Hartshorn, M. P., Roddick, A. D., Steel, P. J. & Wright, G. J. (1992). Aust. J. Chem. 45, 721–730. CrossRef CAS Google Scholar
Sheldrick, G. M. (2003). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
The synthesis of 2-tert-butyl-2,4,5,6,6-pentachlorocyclohex-3-enone and derivatives has been studied (Hartshorn et al., 1992). Here we describe recystallisation and structural characteristics of the target compound. In the title compound, C10H11Cl5O (I), the cyclohexene ring adopts a half-chair conformation (Fig. 1). The tert-butyl group is attached in a pseudo-axial position. Torsion angle between the tert-butyl group and the carbonyl group is O1—C1—C1—C7 is 39.5 (3) °. The molecule (I) possess two stereogenic centres at C2 and C5 carbon atoms. The crystal of (I) is racemate and consists of enantiomeric pairs with the relative configuration 2S*,5R*. The crystal packing is realised by van der Waals interactions.