(E)-3-Hy­droxy-5,5-dimethyl-2-(3-phenyl­prop-2-en-1-yl)cyclo­hex-2-en-1-one

Zonouzi, A.; Izakiana, Z.; Ng, S.W.

doi:10.1107/S160053681103220X

organic compounds

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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2337

doi:10.1107/S160053681103220X

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(E)-3-Hydroxy-5,5-dimethyl-2-(3-phenylprop-2-en-1-yl)cyclohex-2-en-1-one

Afsaneh Zonouzi,^a Zakieh Izakiana ^a and Seik Weng Ng ^b,^c ^*

^aDepartment of Chemistry, College of Science, University of Tehran, PO Box 14155-6455 Tehran, Iran, ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^cChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 8 August 2011; accepted 8 August 2011; online 17 August 2011)

Five of the atoms of the six-membered cyclohexene ring of the title compound, C₁₇H₂₀O₂, are essentially coplanar (r.m.s. deviation = 0.006 Å), with the sixth (the dimethylmethyl C atom) deviating from the mean plane of the five atoms by 0.610 (2) Å. This plane is nearly perpendicular to the cinnamyl portion, the two planes being aligned at 85.1 (1)°. Two molecules are linked by an O—H⋯O hydrogen bond about a center of inversion. The cyclohexene ring is disordered over two directly overlapping positions. As a result, the hydroxy group and the keto O atom cannot be distinguished from one another.

Related literature

For the synthesis, see: Gan et al. (2008 ).

Experimental

Crystal data

C₁₇H₂₀O₂
M_r = 256.33
Triclinic, $[P \overline 1]$
a = 5.6480 (2) Å
b = 10.9077 (5) Å
c = 12.4762 (8) Å
α = 70.999 (5)°
β = 89.533 (4)°
γ = 75.783 (4)°
V = 702.31 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 100 K
0.30 × 0.25 × 0.20 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.977, T_max = 0.985
6734 measured reflections
3119 independent reflections
2554 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.120
S = 1.02
3119 reflections
174 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O1ⁱ	0.84	1.76	2.582 (2)	166
O2—H2⋯O2ⁱⁱ	0.84	1.74	2.569 (2)	167
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) -x, -y+2, -z+1.

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681103220X/bt5605sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681103220X/bt5605Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681103220X/bt5605Isup3.cml

checkCIF report

Comment top

Dimedone condenses with aromatic aldehydes. Cinnamaldehyde is the aldehyde in the present study. The compound C₁₇H₂₀O₂ (Scheme I, Fig. 1) possess a hydroxy as well as a ketonic unit; these interact by an O–H···O hydrogen bond to generate a hydrogen-bonded dimer (Table 1). The synthesis illustrates the direct activation of a C–O bond of a cyclic 1,3-dione to yield the C-alkylated product; an earlier report detailed the synthesis that is catalyzed by palladium compounds (Gan et al., 2008). Five of the atoms of the six-membered cyclohexene ring of C₁₇H₂₀O₂ are coplanar, with the sixth (the dimethylmethyl carbon) deviating from the mean-plane of the five. This plane is perpendicular to the cinnamyl portion. Two molecules are linked by an O–H···O hydrogen bond about a center-of-inversion (Table 1).

Related literature top

For the synthesis, see: Gan et al. (2008).

Experimental top

To a stirred solution of dimedone (0.68 g, 5 mmol) and cinnamaldehyde (0.66 g, 5 mmol) in ethanol (10 ml) was added zinc chloride (1 mmol) along with a small amount of a primary amine as catalyst. The mixture was heated for 12 h. The product was purified by column chromatography on silica gel by using an ethyl acetate/n-hexane (1:3) solvent system. The compound was recrystallized from ethyl acetate to give colorless crystals (yield 70%).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₁₇H₂₀O₂ at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

(E)-3-Hydroxy-5,5-dimethyl-2-(3-phenylprop-2-en-1-yl)cyclohex-2-en-1-one top

Crystal data top

C₁₇H₂₀O₂	Z = 2
M_r = 256.33	F(000) = 276
Triclinic, P1	D_x = 1.212 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.6480 (2) Å	Cell parameters from 3442 reflections
b = 10.9077 (5) Å	θ = 2.3–29.3°
c = 12.4762 (8) Å	µ = 0.08 mm⁻¹
α = 70.999 (5)°	T = 100 K
β = 89.533 (4)°	Block, colorless
γ = 75.783 (4)°	0.30 × 0.25 × 0.20 mm
V = 702.31 (6) Å³

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	3119 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2554 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.026
Detector resolution: 10.4041 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −7→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −14→14
T_min = 0.977, T_max = 0.985	l = −11→16
6734 measured reflections

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0515P)² + 0.1884P] where P = (F_o² + 2F_c²)/3
3119 reflections	(Δ/σ)_max = 0.001
174 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₇H₂₀O₂	γ = 75.783 (4)°
M_r = 256.33	V = 702.31 (6) Å³
Triclinic, P1	Z = 2
a = 5.6480 (2) Å	Mo Kα radiation
b = 10.9077 (5) Å	µ = 0.08 mm⁻¹
c = 12.4762 (8) Å	T = 100 K
α = 70.999 (5)°	0.30 × 0.25 × 0.20 mm
β = 89.533 (4)°

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	3119 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	2554 reflections with I > 2σ(I)
T_min = 0.977, T_max = 0.985	R_int = 0.026
6734 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 1.02	Δρ_max = 0.29 e Å⁻³
3119 reflections	Δρ_min = −0.21 e Å⁻³
174 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.86917 (17)	0.62115 (9)	0.45112 (9)	0.0271 (3)
H1	0.9361	0.5411	0.4900	0.041*	0.50
O2	0.19642 (18)	0.96431 (9)	0.45314 (9)	0.0290 (3)
H2	0.0794	0.9797	0.4929	0.044*	0.50
C1	0.6812 (2)	0.66673 (13)	0.50012 (11)	0.0197 (3)
C2	0.6155 (3)	0.57371 (13)	0.60766 (12)	0.0233 (3)
H2A	0.7686	0.5134	0.6523	0.028*
H2B	0.5231	0.5172	0.5873	0.028*
C3	0.4630 (2)	0.64378 (13)	0.68296 (12)	0.0205 (3)
C4	0.2525 (2)	0.75600 (14)	0.60738 (12)	0.0232 (3)
H4A	0.1305	0.7150	0.5857	0.028*
H4B	0.1708	0.8122	0.6521	0.028*
C5	0.3312 (2)	0.84458 (13)	0.50111 (11)	0.0205 (3)
C6	0.5413 (2)	0.79848 (13)	0.45053 (11)	0.0204 (3)
C7	0.3597 (3)	0.54314 (14)	0.77432 (13)	0.0279 (3)
H7A	0.2623	0.5885	0.8223	0.042*
H7B	0.4949	0.4707	0.8213	0.042*
H7C	0.2558	0.5056	0.7380	0.042*
C8	0.6225 (2)	0.70218 (14)	0.74076 (12)	0.0246 (3)
H8A	0.5235	0.7468	0.7888	0.037*
H8B	0.6887	0.7674	0.6828	0.037*
H8C	0.7578	0.6298	0.7878	0.037*
C9	0.6047 (2)	0.88745 (13)	0.34042 (12)	0.0218 (3)
H9A	0.7842	0.8612	0.3361	0.026*
H9B	0.5595	0.9811	0.3404	0.026*
C10	0.4806 (2)	0.88266 (13)	0.23604 (12)	0.0232 (3)
H10	0.5208	0.9356	0.1648	0.028*
C11	0.3217 (2)	0.81262 (13)	0.23315 (12)	0.0223 (3)
H11	0.2803	0.7602	0.3043	0.027*
C12	0.2022 (2)	0.80775 (13)	0.13049 (12)	0.0218 (3)
C13	0.0192 (2)	0.74014 (14)	0.14118 (13)	0.0257 (3)
H13	−0.0262	0.6972	0.2147	0.031*
C14	−0.0978 (3)	0.73432 (15)	0.04654 (14)	0.0303 (4)
H14	−0.2210	0.6869	0.0557	0.036*
C15	−0.0356 (3)	0.79759 (15)	−0.06144 (14)	0.0294 (3)
H15	−0.1168	0.7944	−0.1265	0.035*
C16	0.1453 (3)	0.86525 (14)	−0.07378 (13)	0.0275 (3)
H16	0.1881	0.9093	−0.1476	0.033*
C17	0.2645 (3)	0.86914 (14)	0.02109 (13)	0.0256 (3)
H17	0.3910	0.9144	0.0116	0.031*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0254 (5)	0.0248 (5)	0.0264 (6)	0.0015 (4)	0.0035 (4)	−0.0083 (4)
O2	0.0268 (5)	0.0248 (5)	0.0275 (6)	0.0032 (4)	0.0059 (4)	−0.0055 (4)
C1	0.0183 (6)	0.0232 (6)	0.0187 (7)	−0.0033 (5)	0.0006 (5)	−0.0100 (6)
C2	0.0290 (7)	0.0201 (6)	0.0191 (7)	−0.0029 (6)	0.0011 (5)	−0.0065 (5)
C3	0.0201 (6)	0.0218 (6)	0.0188 (7)	−0.0050 (5)	0.0027 (5)	−0.0059 (5)
C4	0.0189 (6)	0.0276 (7)	0.0210 (8)	−0.0039 (6)	0.0022 (5)	−0.0067 (6)
C5	0.0190 (6)	0.0216 (6)	0.0197 (7)	−0.0021 (5)	−0.0008 (5)	−0.0076 (5)
C6	0.0208 (6)	0.0225 (6)	0.0179 (7)	−0.0045 (5)	0.0004 (5)	−0.0075 (5)
C7	0.0292 (7)	0.0281 (7)	0.0236 (8)	−0.0078 (6)	0.0044 (6)	−0.0047 (6)
C8	0.0226 (7)	0.0296 (7)	0.0226 (8)	−0.0047 (6)	0.0006 (5)	−0.0116 (6)
C9	0.0215 (6)	0.0202 (6)	0.0220 (8)	−0.0041 (5)	0.0030 (5)	−0.0056 (5)
C10	0.0249 (7)	0.0237 (7)	0.0180 (7)	−0.0047 (6)	0.0038 (5)	−0.0040 (5)
C11	0.0228 (6)	0.0225 (6)	0.0174 (7)	−0.0026 (5)	0.0028 (5)	−0.0036 (5)
C12	0.0214 (6)	0.0204 (6)	0.0204 (7)	−0.0008 (5)	0.0016 (5)	−0.0061 (5)
C13	0.0242 (7)	0.0239 (7)	0.0247 (8)	−0.0046 (6)	0.0017 (6)	−0.0035 (6)
C14	0.0257 (7)	0.0306 (7)	0.0354 (9)	−0.0109 (6)	0.0003 (6)	−0.0093 (7)
C15	0.0286 (7)	0.0323 (8)	0.0288 (9)	−0.0058 (6)	−0.0025 (6)	−0.0134 (7)
C16	0.0319 (7)	0.0296 (7)	0.0216 (8)	−0.0076 (6)	0.0054 (6)	−0.0098 (6)
C17	0.0253 (7)	0.0289 (7)	0.0250 (8)	−0.0106 (6)	0.0047 (6)	−0.0095 (6)

Geometric parameters (Å, º) top

O1—C1	1.2946 (16)	C8—H8B	0.9800
O1—H1	0.8400	C8—H8C	0.9800
O2—C5	1.2858 (16)	C9—C10	1.506 (2)
O2—H2	0.8400	C9—H9A	0.9900
C1—C6	1.3941 (18)	C9—H9B	0.9900
C1—C2	1.5026 (19)	C10—C11	1.3212 (19)
C2—C3	1.5296 (19)	C10—H10	0.9500
C2—H2A	0.9900	C11—C12	1.475 (2)
C2—H2B	0.9900	C11—H11	0.9500
C3—C8	1.5260 (19)	C12—C13	1.3922 (19)
C3—C7	1.5276 (19)	C12—C17	1.396 (2)
C3—C4	1.5339 (17)	C13—C14	1.385 (2)
C4—C5	1.5020 (19)	C13—H13	0.9500
C4—H4A	0.9900	C14—C15	1.386 (2)
C4—H4B	0.9900	C14—H14	0.9500
C5—C6	1.4002 (18)	C15—C16	1.381 (2)
C6—C9	1.5005 (19)	C15—H15	0.9500
C7—H7A	0.9800	C16—C17	1.384 (2)
C7—H7B	0.9800	C16—H16	0.9500
C7—H7C	0.9800	C17—H17	0.9500
C8—H8A	0.9800

C1—O1—H1	109.5	C3—C8—H8B	109.5
C5—O2—H2	109.5	H8A—C8—H8B	109.5
O1—C1—C6	119.59 (12)	C3—C8—H8C	109.5
O1—C1—C2	118.58 (11)	H8A—C8—H8C	109.5
C6—C1—C2	121.80 (11)	H8B—C8—H8C	109.5
C1—C2—C3	114.71 (11)	C6—C9—C10	114.36 (11)
C1—C2—H2A	108.6	C6—C9—H9A	108.7
C3—C2—H2A	108.6	C10—C9—H9A	108.7
C1—C2—H2B	108.6	C6—C9—H9B	108.7
C3—C2—H2B	108.6	C10—C9—H9B	108.7
H2A—C2—H2B	107.6	H9A—C9—H9B	107.6
C8—C3—C7	108.85 (12)	C11—C10—C9	126.85 (13)
C8—C3—C2	110.02 (11)	C11—C10—H10	116.6
C7—C3—C2	109.82 (11)	C9—C10—H10	116.6
C8—C3—C4	110.21 (11)	C10—C11—C12	126.52 (13)
C7—C3—C4	109.84 (11)	C10—C11—H11	116.7
C2—C3—C4	108.10 (11)	C12—C11—H11	116.7
C5—C4—C3	114.10 (11)	C13—C12—C17	117.74 (13)
C5—C4—H4A	108.7	C13—C12—C11	119.70 (13)
C3—C4—H4A	108.7	C17—C12—C11	122.56 (12)
C5—C4—H4B	108.7	C14—C13—C12	121.20 (14)
C3—C4—H4B	108.7	C14—C13—H13	119.4
H4A—C4—H4B	107.6	C12—C13—H13	119.4
O2—C5—C6	119.25 (12)	C13—C14—C15	120.14 (14)
O2—C5—C4	118.89 (11)	C13—C14—H14	119.9
C6—C5—C4	121.80 (11)	C15—C14—H14	119.9
C1—C6—C5	119.10 (12)	C16—C15—C14	119.51 (14)
C1—C6—C9	120.71 (12)	C16—C15—H15	120.2
C5—C6—C9	120.07 (11)	C14—C15—H15	120.2
C3—C7—H7A	109.5	C15—C16—C17	120.19 (14)
C3—C7—H7B	109.5	C15—C16—H16	119.9
H7A—C7—H7B	109.5	C17—C16—H16	119.9
C3—C7—H7C	109.5	C16—C17—C12	121.20 (13)
H7A—C7—H7C	109.5	C16—C17—H17	119.4
H7B—C7—H7C	109.5	C12—C17—H17	119.4
C3—C8—H8A	109.5

O1—C1—C2—C3	157.55 (12)	O2—C5—C6—C9	−1.2 (2)
C6—C1—C2—C3	−24.44 (18)	C4—C5—C6—C9	176.16 (12)
C1—C2—C3—C8	−72.89 (14)	C1—C6—C9—C10	90.63 (15)
C1—C2—C3—C7	167.32 (11)	C5—C6—C9—C10	−85.41 (15)
C1—C2—C3—C4	47.50 (15)	C6—C9—C10—C11	2.01 (19)
C8—C3—C4—C5	71.88 (15)	C9—C10—C11—C12	−179.55 (12)
C7—C3—C4—C5	−168.20 (12)	C10—C11—C12—C13	−173.29 (13)
C2—C3—C4—C5	−48.39 (15)	C10—C11—C12—C17	6.5 (2)
C3—C4—C5—O2	−156.07 (12)	C17—C12—C13—C14	−0.2 (2)
C3—C4—C5—C6	26.60 (18)	C11—C12—C13—C14	179.59 (12)
O1—C1—C6—C5	176.74 (12)	C12—C13—C14—C15	−0.7 (2)
C2—C1—C6—C5	−1.3 (2)	C13—C14—C15—C16	0.6 (2)
O1—C1—C6—C9	0.7 (2)	C14—C15—C16—C17	0.4 (2)
C2—C1—C6—C9	−177.34 (12)	C15—C16—C17—C12	−1.3 (2)
O2—C5—C6—C1	−177.27 (12)	C13—C12—C17—C16	1.2 (2)
C4—C5—C6—C1	0.1 (2)	C11—C12—C17—C16	−178.59 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1ⁱ	0.84	1.76	2.582 (2)	166
O2—H2···O2ⁱⁱ	0.84	1.74	2.569 (2)	167

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₇H₂₀O₂
M_r	256.33
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	5.6480 (2), 10.9077 (5), 12.4762 (8)
α, β, γ (°)	70.999 (5), 89.533 (4), 75.783 (4)
V (Å³)	702.31 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.977, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	6734, 3119, 2554
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.120, 1.02
No. of reflections	3119
No. of parameters	174
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.21

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1ⁱ	0.84	1.76	2.582 (2)	166
O2—H2···O2ⁱⁱ	0.84	1.74	2.569 (2)	167

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x, −y+2, −z+1.

Acknowledgements

We thank the Iran National Science Foundation and the University of Malaya for supporting this study.

References

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