(E)-4-(2-Chloro-1-hy­droxy-2,6,6-tri­methyl­cyclo­hex­yl)but-3-en-2-one

Liu, S.; Yang, X.-Y.; Zhang, Y.-L.

doi:10.1107/S1600536812048544

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page o3485

doi:10.1107/S1600536812048544

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(E)-4-(2-Chloro-1-hydroxy-2,6,6-trimethylcyclohexyl)but-3-en-2-one

Shan Liu,^a ^* Xiao-Yan Yang ^a and Yu-Ling Zhang ^a

^aNanjing College of Chemical Technology, No. 625 Geguan Road, Luhe, Nanjing 210048, People's Republic of China
^*Correspondence e-mail: dols80@163.com

(Received 6 November 2012; accepted 26 November 2012; online 30 November 2012)

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

C₁₃H₂₁ClO₂
M_r = 244.75
Monoclinic, P 2₁ /n
a = 6.266 (1) Å
b = 8.586 (2) Å
c = 24.868 (5) Å
β = 92.24 (3)°
V = 1336.9 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 298 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.923, T_max = 0.973
2688 measured reflections
2450 independent reflections
1611 reflections with I > 2σ(I)
R_int = 0.068
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.068
wR(F²) = 0.179
S = 1.00
2450 reflections
145 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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.

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812048544/zj2098sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812048544/zj2098Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812048544/zj2098Isup3.cml

checkCIF report

Comment top

(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).

Related literature top

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 top

(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 column chromatography 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.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: 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).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 40% probability level. H atoms are presented as small spheres of arbitrary radius.
	Fig. 2. A view of the C—H···Cl, C—H···O and O—H···O hydrogen bonds (dotted lines) in the crystal structure of the title compound. [Symmter codes: (i) 2 - x,-y,-z; (ii) 2 - x,-y,-z; (iii) -1 + x,y,z.]

(E)-4-(2-Chloro-1-hydroxy-2,6,6-trimethylcyclohexyl)but-3-en-2-one top

Crystal data top

C₁₃H₂₁ClO₂	F(000) = 528
M_r = 244.75	D_x = 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

Data collection top

Enraf–Nonius CAD-4 diffractometer	1611 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.068
Graphite monochromator	θ_max = 25.4°, θ_min = 1.6°
ω/2θ scans	h = 0→7
Absorption correction: ψ scan (North et al., 1968)	k = 0→10
T_min = 0.923, T_max = 0.973	l = −29→29
2688 measured reflections	3 standard reflections every 200 reflections
2450 independent reflections	intensity decay: 1%

Refinement top

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(F_o²) + (0.1P)² + 0.3P] where P = (F_o² + 2F_c²)/3
2450 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.45 e Å⁻³
1 restraint	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₃H₂₁ClO₂	V = 1336.9 (5) Å³
M_r = 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)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1611 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.068
T_min = 0.923, T_max = 0.973	3 standard reflections every 200 reflections
2688 measured reflections	intensity decay: 1%
2450 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.068	1 restraint
wR(F²) = 0.179	H-atom parameters constrained
S = 1.00	Δρ_max = 0.45 e Å⁻³
2450 reflections	Δρ_min = −0.29 e Å⁻³
145 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.923, 0.973
No. of measured, independent and observed [I > 2σ(I)] reflections	2688, 2450, 1611
R_int	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
Δρ_max, Δρ_min (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).

Hydrogen-bond geometry (Å, º) top

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

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Volume 68| Part 12| December 2012| Page o3485

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