organic compounds
(E)-4-(2-Chloro-1-hydroxy-2,6,6-trimethylcyclohexyl)but-3-en-2-one
aNanjing College of Chemical Technology, No. 625 Geguan Road, Luhe, Nanjing 210048, People's Republic of China
*Correspondence e-mail: dols80@163.com
In the title molecule, C13H21ClO2, there is an intramolecular C—H⋯Cl hydrogen bond. The conformation about the C=C bond is E and the six-membered ring has a chair conformation. In the crystal, molecules are linked by pairs of O—H⋯O hydrogen bonds, forming inversion dimers, which are consolidated by C—H⋯O hydrogen bonds. The dimers are linked via C—H.·O hydrogen bonds, forming chains along [100].
Related literature
For the use of (E)-4-(2-chloro-1-hydroxy-2,6,6-trimethylcyclohexyl)but-3-en-2-one, see: Sakai et al. (1992). For bond-length data, see: Allen et al. (1987).
Experimental
Crystal data
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Refinement
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Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell CAD-4 Software; data reduction: XCAD4 (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: SHELXTL.
Supporting information
10.1107/S1600536812048544/zj2098sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812048544/zj2098Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812048544/zj2098Isup3.cml
(E)-4-(2-Chloro-1-hydroxy-2,6,6-trimethylcyclohexyl)but-3-en-2-one was prepared by the reaction of (E)-4-(2,2,6-trimethyl-7- oxabicyclo[4.1.0]heptan-1-yl)but-3-en-2-one (20.8 g, 0.100 mmol) and 1M hydrochloric acid (30 ml) in ethanol (150 ml) at 273 K for 3 h, and separated by
on silica gel (hexane / ethyl acetate = 8/2, V/V) with a yield of 50%. Single crystals were obtained by dissolving the title compound (0.50 g, 2.04 mmol) in ethyl acetate (30 ml) and evaporating the solvent slowly at 288–293 K for about 1 d.H atoms were positioned geometrically, with O—H = 0.82, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C/O), where x = 1.5 for H.
Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell
CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (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: SHELXTL (Sheldrick, 2008).C13H21ClO2 | F(000) = 528 |
Mr = 244.75 | Dx = 1.216 Mg m−3 |
Monoclinic, P21/n | Melting point = 380–383 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 6.266 (1) Å | Cell parameters from 25 reflections |
b = 8.586 (2) Å | θ = 10–13° |
c = 24.868 (5) Å | µ = 0.27 mm−1 |
β = 92.24 (3)° | T = 298 K |
V = 1336.9 (5) Å3 | Cube, colorless |
Z = 4 | 0.30 × 0.20 × 0.10 mm |
Enraf–Nonius CAD-4 diffractometer | 1611 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.068 |
Graphite monochromator | θmax = 25.4°, θmin = 1.6° |
ω/2θ scans | h = 0→7 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→10 |
Tmin = 0.923, Tmax = 0.973 | l = −29→29 |
2688 measured reflections | 3 standard reflections every 200 reflections |
2450 independent reflections | intensity decay: 1% |
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)] = 0.068 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.179 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.1P)2 + 0.3P] where P = (Fo2 + 2Fc2)/3 |
2450 reflections | (Δ/σ)max < 0.001 |
145 parameters | Δρmax = 0.45 e Å−3 |
1 restraint | Δρmin = −0.29 e Å−3 |
C13H21ClO2 | V = 1336.9 (5) Å3 |
Mr = 244.75 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.266 (1) Å | µ = 0.27 mm−1 |
b = 8.586 (2) Å | T = 298 K |
c = 24.868 (5) Å | 0.30 × 0.20 × 0.10 mm |
β = 92.24 (3)° |
Enraf–Nonius CAD-4 diffractometer | 1611 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.068 |
Tmin = 0.923, Tmax = 0.973 | 3 standard reflections every 200 reflections |
2688 measured reflections | intensity decay: 1% |
2450 independent reflections |
R[F2 > 2σ(F2)] = 0.068 | 1 restraint |
wR(F2) = 0.179 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.45 e Å−3 |
2450 reflections | Δρmin = −0.29 e Å−3 |
145 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 | ||
Cl | 0.73792 (16) | 0.51609 (11) | 0.14841 (4) | 0.0672 (4) | |
O1 | 1.1529 (3) | 0.2036 (2) | 0.09894 (8) | 0.0447 (6) | |
H1A | 1.1530 | 0.1117 | 0.0899 | 0.067* | |
C1 | 0.8845 (5) | 0.1320 (3) | 0.16368 (12) | 0.0425 (7) | |
O2 | 0.6807 (4) | 0.0827 (3) | −0.05952 (10) | 0.0669 (8) | |
C2 | 1.0445 (5) | 0.1541 (4) | 0.21162 (13) | 0.0505 (8) | |
H2A | 1.0002 | 0.0904 | 0.2414 | 0.061* | |
H2B | 1.1839 | 0.1177 | 0.2015 | 0.061* | |
C3 | 1.0635 (6) | 0.3233 (4) | 0.23029 (15) | 0.0622 (10) | |
H3A | 0.9271 | 0.3583 | 0.2430 | 0.075* | |
H3B | 1.1681 | 0.3306 | 0.2600 | 0.075* | |
C4 | 1.1304 (6) | 0.4266 (4) | 0.18449 (15) | 0.0549 (9) | |
H4A | 1.1366 | 0.5335 | 0.1972 | 0.066* | |
H4B | 1.2733 | 0.3972 | 0.1748 | 0.066* | |
C5 | 0.9854 (5) | 0.4199 (3) | 0.13459 (13) | 0.0433 (8) | |
C6 | 0.9465 (5) | 0.2448 (3) | 0.11647 (11) | 0.0365 (7) | |
C7 | 0.8980 (6) | −0.0372 (4) | 0.14485 (15) | 0.0601 (10) | |
H7A | 1.0381 | −0.0573 | 0.1321 | 0.090* | |
H7B | 0.7935 | −0.0550 | 0.1162 | 0.090* | |
H7C | 0.8710 | −0.1056 | 0.1744 | 0.090* | |
C8 | 0.6432 (4) | 0.1588 (3) | 0.18449 (11) | 0.0300 (6) | |
H8A | 0.6166 | 0.0868 | 0.2130 | 0.045* | |
H8B | 0.5415 | 0.1418 | 0.1552 | 0.045* | |
H8C | 0.6298 | 0.2635 | 0.1975 | 0.045* | |
C9 | 1.0807 (6) | 0.5136 (4) | 0.08881 (15) | 0.0615 (10) | |
H9A | 1.2142 | 0.4680 | 0.0795 | 0.092* | |
H9B | 1.1039 | 0.6192 | 0.1003 | 0.092* | |
H9C | 0.9836 | 0.5122 | 0.0580 | 0.092* | |
C10 | 0.7826 (5) | 0.2374 (3) | 0.07141 (12) | 0.0397 (7) | |
H10A | 0.6470 | 0.2752 | 0.0781 | 0.048* | |
C11 | 0.8145 (5) | 0.1811 (4) | 0.02232 (12) | 0.0447 (8) | |
H11A | 0.9515 | 0.1480 | 0.0148 | 0.054* | |
C12 | 0.6479 (5) | 0.1680 (3) | −0.02048 (12) | 0.0447 (8) | |
C13 | 0.4476 (5) | 0.2548 (4) | −0.01817 (13) | 0.0527 (9) | |
H13A | 0.3583 | 0.2309 | −0.0493 | 0.079* | |
H13B | 0.4775 | 0.3645 | −0.0174 | 0.079* | |
H13C | 0.3755 | 0.2260 | 0.0137 | 0.079* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl | 0.0756 (7) | 0.0548 (6) | 0.0719 (7) | 0.0143 (5) | 0.0108 (5) | −0.0036 (4) |
O1 | 0.0380 (11) | 0.0435 (12) | 0.0534 (13) | 0.0036 (9) | 0.0116 (10) | −0.0076 (10) |
C1 | 0.0447 (17) | 0.0388 (16) | 0.0450 (17) | 0.0001 (14) | 0.0132 (14) | 0.0023 (14) |
O2 | 0.0759 (18) | 0.0694 (17) | 0.0551 (14) | 0.0135 (14) | 0.0005 (13) | −0.0249 (13) |
C2 | 0.0510 (19) | 0.0507 (19) | 0.0496 (19) | 0.0063 (16) | −0.0001 (16) | 0.0062 (16) |
C3 | 0.071 (2) | 0.064 (2) | 0.051 (2) | 0.000 (2) | −0.0090 (18) | −0.0096 (18) |
C4 | 0.051 (2) | 0.0417 (18) | 0.071 (2) | −0.0013 (15) | −0.0016 (18) | −0.0108 (17) |
C5 | 0.0494 (19) | 0.0305 (15) | 0.0503 (18) | −0.0027 (14) | 0.0056 (15) | −0.0040 (13) |
C6 | 0.0393 (16) | 0.0359 (15) | 0.0350 (15) | −0.0037 (12) | 0.0098 (13) | −0.0003 (12) |
C7 | 0.078 (3) | 0.0330 (17) | 0.070 (2) | −0.0073 (17) | 0.006 (2) | 0.0025 (16) |
C8 | 0.0208 (12) | 0.0345 (14) | 0.0346 (14) | −0.0033 (11) | 0.0010 (11) | 0.0130 (11) |
C9 | 0.070 (2) | 0.0427 (19) | 0.074 (2) | −0.0124 (17) | 0.023 (2) | 0.0067 (17) |
C10 | 0.0392 (16) | 0.0382 (16) | 0.0423 (16) | 0.0047 (13) | 0.0072 (14) | −0.0021 (13) |
C11 | 0.0503 (18) | 0.0415 (17) | 0.0429 (17) | 0.0026 (14) | 0.0077 (14) | −0.0041 (14) |
C12 | 0.062 (2) | 0.0335 (16) | 0.0393 (16) | −0.0003 (14) | 0.0105 (15) | −0.0040 (13) |
C13 | 0.061 (2) | 0.052 (2) | 0.0450 (18) | 0.0059 (17) | 0.0027 (16) | −0.0053 (16) |
Cl—C5 | 1.802 (3) | C6—C10 | 1.491 (4) |
O1—C6 | 1.425 (3) | C7—H7A | 0.9600 |
O1—H1A | 0.8200 | C7—H7B | 0.9600 |
C1—C7 | 1.530 (4) | C7—H7C | 0.9600 |
C1—C2 | 1.539 (4) | C8—H8A | 0.9600 |
C1—C6 | 1.582 (4) | C8—H8B | 0.9600 |
C1—C8 | 1.633 (4) | C8—H8C | 0.9600 |
O2—C12 | 1.240 (4) | C9—H9A | 0.9600 |
C2—C3 | 1.528 (5) | C9—H9B | 0.9600 |
C2—H2A | 0.9700 | C9—H9C | 0.9600 |
C2—H2B | 0.9700 | C10—C11 | 1.336 (4) |
C3—C4 | 1.516 (5) | C10—H10A | 0.9300 |
C3—H3A | 0.9700 | C11—C12 | 1.466 (4) |
C3—H3B | 0.9700 | C11—H11A | 0.9300 |
C4—C5 | 1.510 (5) | C12—C13 | 1.463 (4) |
C4—H4A | 0.9700 | C13—H13A | 0.9600 |
C4—H4B | 0.9700 | C13—H13B | 0.9600 |
C5—C9 | 1.534 (4) | C13—H13C | 0.9600 |
C5—C6 | 1.586 (4) | ||
C6—O1—H1A | 109.5 | C10—C6—C5 | 110.3 (2) |
C7—C1—C2 | 108.2 (3) | C1—C6—C5 | 114.1 (2) |
C7—C1—C6 | 109.6 (3) | C1—C7—H7A | 109.5 |
C2—C1—C6 | 109.1 (2) | C1—C7—H7B | 109.5 |
C7—C1—C8 | 107.1 (2) | H7A—C7—H7B | 109.5 |
C2—C1—C8 | 108.7 (2) | C1—C7—H7C | 109.5 |
C6—C1—C8 | 114.0 (2) | H7A—C7—H7C | 109.5 |
C3—C2—C1 | 113.1 (3) | H7B—C7—H7C | 109.5 |
C3—C2—H2A | 109.0 | C1—C8—H8A | 109.5 |
C1—C2—H2A | 109.0 | C1—C8—H8B | 109.5 |
C3—C2—H2B | 109.0 | H8A—C8—H8B | 109.5 |
C1—C2—H2B | 109.0 | C1—C8—H8C | 109.5 |
H2A—C2—H2B | 107.8 | H8A—C8—H8C | 109.5 |
C4—C3—C2 | 110.4 (3) | H8B—C8—H8C | 109.5 |
C4—C3—H3A | 109.6 | C5—C9—H9A | 109.5 |
C2—C3—H3A | 109.6 | C5—C9—H9B | 109.5 |
C4—C3—H3B | 109.6 | H9A—C9—H9B | 109.5 |
C2—C3—H3B | 109.6 | C5—C9—H9C | 109.5 |
H3A—C3—H3B | 108.1 | H9A—C9—H9C | 109.5 |
C5—C4—C3 | 114.8 (3) | H9B—C9—H9C | 109.5 |
C5—C4—H4A | 108.6 | C11—C10—C6 | 125.4 (3) |
C3—C4—H4A | 108.6 | C11—C10—H10A | 117.3 |
C5—C4—H4B | 108.6 | C6—C10—H10A | 117.3 |
C3—C4—H4B | 108.6 | C10—C11—C12 | 124.3 (3) |
H4A—C4—H4B | 107.5 | C10—C11—H11A | 117.8 |
C4—C5—C9 | 110.5 (3) | C12—C11—H11A | 117.8 |
C4—C5—C6 | 110.5 (3) | O2—C12—C13 | 120.0 (3) |
C9—C5—C6 | 110.2 (2) | O2—C12—C11 | 118.6 (3) |
C4—C5—Cl | 108.7 (2) | C13—C12—C11 | 121.4 (3) |
C9—C5—Cl | 105.3 (2) | C12—C13—H13A | 109.5 |
C6—C5—Cl | 111.4 (2) | C12—C13—H13B | 109.5 |
O1—C6—C10 | 111.5 (2) | H13A—C13—H13B | 109.5 |
O1—C6—C1 | 109.1 (2) | C12—C13—H13C | 109.5 |
C10—C6—C1 | 110.5 (2) | H13A—C13—H13C | 109.5 |
O1—C6—C5 | 101.0 (2) | H13B—C13—H13C | 109.5 |
C7—C1—C2—C3 | 173.8 (3) | C8—C1—C6—C5 | 72.1 (3) |
C6—C1—C2—C3 | 54.6 (4) | C4—C5—C6—O1 | −69.0 (3) |
C8—C1—C2—C3 | −70.3 (3) | C9—C5—C6—O1 | 53.6 (3) |
C1—C2—C3—C4 | −58.1 (4) | Cl—C5—C6—O1 | 170.10 (19) |
C2—C3—C4—C5 | 56.5 (4) | C4—C5—C6—C10 | 173.0 (2) |
C3—C4—C5—C9 | −173.5 (3) | C9—C5—C6—C10 | −64.5 (3) |
C3—C4—C5—C6 | −51.2 (4) | Cl—C5—C6—C10 | 52.1 (3) |
C3—C4—C5—Cl | 71.4 (3) | C4—C5—C6—C1 | 48.0 (3) |
C7—C1—C6—O1 | −55.7 (3) | C9—C5—C6—C1 | 170.5 (3) |
C2—C1—C6—O1 | 62.6 (3) | Cl—C5—C6—C1 | −73.0 (3) |
C8—C1—C6—O1 | −175.7 (2) | O1—C6—C10—C11 | 8.0 (4) |
C7—C1—C6—C10 | 67.2 (3) | C1—C6—C10—C11 | −113.5 (3) |
C2—C1—C6—C10 | −174.5 (2) | C5—C6—C10—C11 | 119.4 (3) |
C8—C1—C6—C10 | −52.9 (3) | C6—C10—C11—C12 | 176.8 (3) |
C7—C1—C6—C5 | −167.9 (3) | C10—C11—C12—O2 | −163.5 (3) |
C2—C1—C6—C5 | −49.6 (3) | C10—C11—C12—C13 | 17.4 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O2i | 0.82 | 2.12 | 2.858 (3) | 149 |
C7—H7A···O2i | 0.96 | 2.58 | 3.473 (5) | 155 |
C8—H8C···Cl | 0.96 | 2.59 | 3.257 (3) | 127 |
C13—H13C···O1ii | 0.96 | 2.59 | 3.536 (4) | 169 |
Symmetry codes: (i) −x+2, −y, −z; (ii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C13H21ClO2 |
Mr | 244.75 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 6.266 (1), 8.586 (2), 24.868 (5) |
β (°) | 92.24 (3) |
V (Å3) | 1336.9 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.27 |
Crystal size (mm) | 0.30 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.923, 0.973 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2688, 2450, 1611 |
Rint | 0.068 |
(sin θ/λ)max (Å−1) | 0.603 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.068, 0.179, 1.00 |
No. of reflections | 2450 |
No. of parameters | 145 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.45, −0.29 |
Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O2i | 0.8200 | 2.1200 | 2.858 (3) | 149.00 |
C7—H7A···O2i | 0.9600 | 2.5800 | 3.473 (5) | 155.00 |
C8—H8C···Cl | 0.9600 | 2.5900 | 3.257 (3) | 127.00 |
C13—H13C···O1ii | 0.9600 | 2.5900 | 3.536 (4) | 169.00 |
Symmetry codes: (i) −x+2, −y, −z; (ii) x−1, y, z. |
References
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Enraf–Nonius (1985). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sakai, K., Takahashi, K. & Nukano, T. (1992). Tetrahedron, 64, 8229–8238. CrossRef Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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(E)-4-(2-Chloro-1-hydroxy-2,6,6-trimethylcyclohexyl)but-3-en-2-one is an important intermediate used to synthesize abscisic acid (ABA), which has important activities as a plant hormone (Sakai, et al., 1992). We report here the crystal structure of the title compound (Fig. 1).
In the title molecule, bond lengths (Allen et al., 1987) and angles are within normal ranges. In the crystal packing (Fig. 2), mmolecules are linked to form three-dimensional framework by intra- and intermolecular C—H···Cl, C—H···O and O—H···O hydrogen bonds, which may be effective for the stabilization of the crystals (see, Table 1).