3-[(E)-2-(2-Meth­oxy­phen­yl)vin­yl]-5,5-di­methyl­cyclo­hex-2-enone

Fatima, Z.; Senthilkumar, G.; Vadivel, A.; Manikandan, H.; Velmurugan, D.

doi:10.1107/S1600536814006527

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 70| Part 5| May 2014| Page o509

doi:10.1107/S1600536814006527

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3-[(E)-2-(2-Methoxyphenyl)vinyl]-5,5-dimethylcyclohex-2-enone

Zeenat Fatima,^a Govindaraj Senthilkumar,^b A. Vadivel,^b Haridoss Manikandan ^b and Devadasan Velmurugan ^a ^*

^aCenter of Advanced Study in Crystallography and Biophysics, University of Madras, Guindy Campus, Chennai 600 025, India, and ^bDepartment of Chemistry, Annamalai University, Annamalainagar 608 002, Tamilnadu, India
^*Correspondence e-mail: shirai2011@gmail.com

(Received 23 March 2014; accepted 24 March 2014; online 2 April 2014)

The title compound, C₁₇H₂₀O₂, has an E conformation about the bridging C=C bond. The cyclohexene ring adopts an envelope conformation with the dimethyl-substituted C atom as the flap. Its mean plane makes a dihedral angle of 7.20 (12)° with the benzene ring. In the crystal, neighbouring molecules are connected via C—H⋯O hydrogen bonds, forming chains running along the a-axis direction.

CCDC reference: 993438

Related literature

For the pharmacological activity of cyclohexanone derivatives, see: Puetz et al. (2003 ); Rajveer et al. (2010 ). For related structures, see: Fatima et al. (2013 ); Hema et al. (2006 ). For ring puckering parametes, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₇H₂₀O₂
M_r = 256.33
Monoclinic, P 2₁ /n
a = 7.208 (4) Å
b = 13.824 (7) Å
c = 15.022 (8) Å
β = 92.13 (2)°
V = 1495.8 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker SMART APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.978, T_max = 0.986
10491 measured reflections
3517 independent reflections
2489 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.085
wR(F²) = 0.283
S = 1.06
3517 reflections
175 parameters
H-atom parameters constrained
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14B⋯O1ⁱ	0.97	2.62	3.554 (4)	161
Symmetry code: (i) x+1, y, z.

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 993438

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814006527/su2717sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814006527/su2717Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814006527/su2717Isup3.cml

checkCIF report

Comment top

Cyclohexanone is an aliphatic cyclic ketone. Cyclohexanone derivatives have potent pharmacological activity in the treatment of a broad spectrum of medical conditions (Puetz et al., 2003). The cyclohexanone moiety constitutes an important structural feature in several anti-inflammatory, analgesic, local anesthetic and antihistaminic drugs (Rajveer et al., 2010). As part of our studies in this area (Fatima et al., 2013; Hema et al., 2006), we have undertaken a single-crystal structure determination of the title compound.

In the title compound, Fig. 1, the cyclohexene ring (C9—C14) adopts an envelope conformation with atom C13 as the flap: puckering parameters (Cremer & Pople, 1975) are Q = 0.464 (3) Å, θ = 52.3 (4) °, and ϕ = 232.2 (4) °. Its mean plane makes a dihedral angle of 7.20 (12)° with the benzene ring (C1—C6).

In the crystal, hydrogen bonded chains running along the a-axis direction are generated by connecting neighbouring molecules via C—H···O hydrogen bonds (Table 1 and Fig. 2).

Related literature top

For the pharmacological activity of cyclohexanone derivatives, see: Puetz et al. (2003); Rajveer et al. (2010). For related structures, see: Fatima et al. (2013); Hema et al. (2006). For ring puckering parametes, see: Cremer & Pople (1975).

Experimental top

A mixture of isophorone (0.01 mol), 2-methoxybezaldehyde (0.01 mol) and sodium hydroxide solution (10 ml, 10%) in ethanol (25 ml) was stirred at room temperature until the starting material disappeared. The resulting mixture was poured into crushed ice and the precipitate was filtered off, dried and recrystallized from ethanol giving p. colourless block-like crystals [Yield = 93%; M.p. = 373-375 K].

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title molecule, with atom labelling. The displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound viewed along the b axis. The hydrogen bonds are shown as dashed lines (see Table 1 for details; H-atoms not involved in hydrogen bonding have been excluded for clarity).

3-[(E)-2-(2-Methoxyphenyl)vinyl]-5,5-dimethylcyclohex-2-enone top

Crystal data top

C₁₇H₂₀O₂	F(000) = 552
M_r = 256.33	D_x = 1.138 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3517 reflections
a = 7.208 (4) Å	θ = 2.0–28.6°
b = 13.824 (7) Å	µ = 0.07 mm⁻¹
c = 15.022 (8) Å	T = 293 K
β = 92.13 (2)°	Block, colourless
V = 1495.8 (14) Å³	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection top

Bruker SMART APEXII area-detector diffractometer	3517 independent reflections
Radiation source: fine-focus sealed tube	2489 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
ω and ϕ scans	θ_max = 28.6°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −9→9
T_min = 0.978, T_max = 0.986	k = −18→17
10491 measured reflections	l = −19→11

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)] = 0.085	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.283	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.1498P)² + 0.8245P] where P = (F_o² + 2F_c²)/3
3517 reflections	(Δ/σ)_max < 0.001
175 parameters	Δρ_max = 0.65 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₇H₂₀O₂	V = 1495.8 (14) Å³
M_r = 256.33	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.208 (4) Å	µ = 0.07 mm⁻¹
b = 13.824 (7) Å	T = 293 K
c = 15.022 (8) Å	0.30 × 0.25 × 0.20 mm
β = 92.13 (2)°

Data collection top

Bruker SMART APEXII area-detector diffractometer	3517 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	2489 reflections with I > 2σ(I)
T_min = 0.978, T_max = 0.986	R_int = 0.054
10491 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.085	0 restraints
wR(F²) = 0.283	H-atom parameters constrained
S = 1.06	Δρ_max = 0.65 e Å⁻³
3517 reflections	Δρ_min = −0.27 e Å⁻³
175 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
C1	1.4696 (5)	0.6141 (2)	0.2237 (2)	0.0617 (8)
H1	1.5376	0.6552	0.1884	0.074*
C2	1.2899 (4)	0.5897 (2)	0.1978 (2)	0.0533 (7)
H2	1.2377	0.6147	0.1451	0.064*
C3	1.1846 (4)	0.52740 (19)	0.25024 (18)	0.0472 (6)
C4	1.2616 (4)	0.49045 (18)	0.33219 (18)	0.0452 (6)
C5	1.4433 (4)	0.51557 (18)	0.35727 (18)	0.0464 (6)
H5	1.4951	0.4915	0.4104	0.056*
C6	1.5515 (4)	0.5767 (2)	0.3041 (2)	0.0617 (8)
H6	1.6732	0.5920	0.3213	0.074*
C7	1.1621 (4)	0.42686 (18)	0.39463 (18)	0.0479 (6)
H7	1.2321	0.4088	0.4452	0.057*
C8	0.9882 (4)	0.39088 (18)	0.39058 (18)	0.0500 (7)
H8	0.9143	0.4049	0.3401	0.060*
C9	0.9055 (3)	0.33023 (16)	0.46110 (16)	0.0411 (6)
C10	0.7259 (4)	0.29964 (19)	0.45218 (19)	0.0496 (7)
H10	0.6585	0.3153	0.4002	0.060*
C11	0.6334 (3)	0.24317 (19)	0.5206 (2)	0.0499 (7)
C12	0.7438 (4)	0.22367 (19)	0.60826 (18)	0.0459 (6)
H12A	0.6987	0.1644	0.6345	0.055*
H12B	0.7219	0.2760	0.6495	0.055*
C13	0.9558 (3)	0.21429 (15)	0.59556 (15)	0.0369 (5)
C14	1.0219 (3)	0.30514 (16)	0.54545 (16)	0.0396 (5)
H14A	1.0200	0.3600	0.5857	0.048*
H14B	1.1495	0.2952	0.5292	0.048*
C15	0.9938 (4)	0.12099 (17)	0.54174 (19)	0.0480 (6)
H15A	0.9532	0.0657	0.5744	0.072*
H15B	1.1244	0.1157	0.5323	0.072*
H15C	0.9272	0.1239	0.4853	0.072*
C16	1.0603 (5)	0.2081 (2)	0.68771 (18)	0.0563 (8)
H16A	1.0354	0.2652	0.7216	0.084*
H16B	1.1913	0.2031	0.6793	0.084*
H16C	1.0187	0.1521	0.7192	0.084*
C17	0.9273 (5)	0.5303 (3)	0.1418 (2)	0.0736 (10)
H17A	0.9271	0.5997	0.1389	0.110*
H17B	0.8023	0.5068	0.1344	0.110*
H17C	1.0008	0.5048	0.0952	0.110*
O1	0.4730 (3)	0.2135 (2)	0.5081 (2)	0.0762 (8)
O2	1.0044 (3)	0.49973 (15)	0.22679 (13)	0.0569 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0701 (18)	0.0601 (16)	0.0560 (17)	−0.0103 (15)	0.0175 (15)	−0.0004 (14)
C2	0.0659 (16)	0.0489 (13)	0.0464 (14)	−0.0038 (12)	0.0184 (13)	−0.0005 (11)
C3	0.0542 (14)	0.0450 (12)	0.0426 (13)	0.0002 (11)	0.0037 (12)	−0.0020 (10)
C4	0.0477 (13)	0.0433 (12)	0.0448 (13)	0.0021 (10)	0.0033 (11)	−0.0035 (10)
C5	0.0477 (13)	0.0468 (12)	0.0445 (13)	0.0005 (10)	−0.0014 (11)	−0.0020 (10)
C6	0.0517 (14)	0.0652 (17)	0.069 (2)	−0.0135 (13)	0.0093 (15)	−0.0085 (15)
C7	0.0576 (14)	0.0416 (12)	0.0446 (13)	0.0017 (11)	0.0024 (12)	0.0073 (10)
C8	0.0646 (16)	0.0446 (12)	0.0404 (13)	0.0084 (12)	−0.0033 (12)	0.0079 (10)
C9	0.0488 (12)	0.0367 (10)	0.0375 (12)	0.0056 (9)	−0.0005 (10)	0.0036 (9)
C10	0.0490 (13)	0.0494 (13)	0.0495 (14)	0.0067 (11)	−0.0090 (12)	0.0045 (11)
C11	0.0390 (12)	0.0479 (13)	0.0627 (17)	0.0036 (10)	0.0002 (12)	−0.0098 (12)
C12	0.0479 (13)	0.0456 (12)	0.0448 (13)	−0.0035 (10)	0.0127 (11)	−0.0038 (10)
C13	0.0432 (11)	0.0346 (10)	0.0327 (11)	−0.0005 (9)	0.0005 (9)	0.0022 (8)
C14	0.0409 (11)	0.0376 (11)	0.0401 (12)	−0.0020 (9)	−0.0014 (10)	0.0062 (9)
C15	0.0581 (14)	0.0363 (11)	0.0497 (14)	0.0092 (10)	0.0051 (12)	−0.0005 (10)
C16	0.0710 (18)	0.0579 (15)	0.0392 (13)	−0.0071 (13)	−0.0096 (13)	0.0101 (11)
C17	0.084 (2)	0.083 (2)	0.0520 (18)	−0.0015 (19)	−0.0171 (17)	0.0147 (16)
O1	0.0395 (10)	0.0955 (18)	0.0935 (19)	−0.0095 (11)	−0.0002 (11)	−0.0084 (14)
O2	0.0559 (11)	0.0680 (12)	0.0461 (11)	−0.0088 (9)	−0.0081 (9)	0.0163 (9)

Geometric parameters (Å, º) top

C1—C2	1.381 (4)	C11—O1	1.234 (3)
C1—C6	1.421 (5)	C11—C12	1.537 (4)
C1—H1	0.9300	C12—C13	1.553 (4)
C2—C3	1.408 (4)	C12—H12A	0.9700
C2—H2	0.9300	C12—H12B	0.9700
C3—O2	1.387 (3)	C13—C14	1.548 (3)
C3—C4	1.426 (4)	C13—C15	1.552 (3)
C4—C5	1.393 (4)	C13—C16	1.553 (3)
C4—C7	1.489 (4)	C14—H14A	0.9700
C5—C6	1.416 (4)	C14—H14B	0.9700
C5—H5	0.9300	C15—H15A	0.9600
C6—H6	0.9300	C15—H15B	0.9600
C7—C8	1.348 (4)	C15—H15C	0.9600
C7—H7	0.9300	C16—H16A	0.9600
C8—C9	1.493 (4)	C16—H16B	0.9600
C8—H8	0.9300	C16—H16C	0.9600
C9—C10	1.364 (4)	C17—O2	1.437 (3)
C9—C14	1.533 (3)	C17—H17A	0.9600
C10—C11	1.470 (4)	C17—H17B	0.9600
C10—H10	0.9300	C17—H17C	0.9600

C2—C1—C6	120.4 (3)	C13—C12—H12A	109.0
C2—C1—H1	119.8	C11—C12—H12B	109.0
C6—C1—H1	119.8	C13—C12—H12B	109.0
C1—C2—C3	120.7 (3)	H12A—C12—H12B	107.8
C1—C2—H2	119.7	C14—C13—C15	111.0 (2)
C3—C2—H2	119.7	C14—C13—C12	108.29 (18)
O2—C3—C2	123.0 (2)	C15—C13—C12	109.07 (19)
O2—C3—C4	116.8 (2)	C14—C13—C16	109.30 (19)
C2—C3—C4	120.1 (3)	C15—C13—C16	109.2 (2)
C5—C4—C3	118.4 (3)	C12—C13—C16	110.0 (2)
C5—C4—C7	116.5 (2)	C9—C14—C13	114.63 (19)
C3—C4—C7	125.0 (2)	C9—C14—H14A	108.6
C4—C5—C6	121.8 (3)	C13—C14—H14A	108.6
C4—C5—H5	119.1	C9—C14—H14B	108.6
C6—C5—H5	119.1	C13—C14—H14B	108.6
C5—C6—C1	118.5 (3)	H14A—C14—H14B	107.6
C5—C6—H6	120.8	C13—C15—H15A	109.5
C1—C6—H6	120.8	C13—C15—H15B	109.5
C8—C7—C4	131.2 (2)	H15A—C15—H15B	109.5
C8—C7—H7	114.4	C13—C15—H15C	109.5
C4—C7—H7	114.4	H15A—C15—H15C	109.5
C7—C8—C9	124.8 (2)	H15B—C15—H15C	109.5
C7—C8—H8	117.6	C13—C16—H16A	109.5
C9—C8—H8	117.6	C13—C16—H16B	109.5
C10—C9—C8	120.5 (2)	H16A—C16—H16B	109.5
C10—C9—C14	119.9 (2)	C13—C16—H16C	109.5
C8—C9—C14	119.5 (2)	H16A—C16—H16C	109.5
C9—C10—C11	123.3 (2)	H16B—C16—H16C	109.5
C9—C10—H10	118.3	O2—C17—H17A	109.5
C11—C10—H10	118.3	O2—C17—H17B	109.5
O1—C11—C10	121.1 (3)	H17A—C17—H17B	109.5
O1—C11—C12	121.6 (3)	O2—C17—H17C	109.5
C10—C11—C12	117.3 (2)	H17A—C17—H17C	109.5
C11—C12—C13	113.0 (2)	H17B—C17—H17C	109.5
C11—C12—H12A	109.0	C3—O2—C17	118.2 (2)

C6—C1—C2—C3	−0.1 (5)	C8—C9—C10—C11	−177.4 (2)
C1—C2—C3—O2	−179.2 (3)	C14—C9—C10—C11	0.6 (4)
C1—C2—C3—C4	1.4 (4)	C9—C10—C11—O1	−176.8 (3)
O2—C3—C4—C5	179.1 (2)	C9—C10—C11—C12	3.7 (4)
C2—C3—C4—C5	−1.6 (4)	O1—C11—C12—C13	148.6 (3)
O2—C3—C4—C7	−1.5 (4)	C10—C11—C12—C13	−31.9 (3)
C2—C3—C4—C7	177.9 (3)	C11—C12—C13—C14	53.3 (3)
C3—C4—C5—C6	0.4 (4)	C11—C12—C13—C15	−67.5 (3)
C7—C4—C5—C6	−179.2 (3)	C11—C12—C13—C16	172.7 (2)
C4—C5—C6—C1	1.0 (4)	C10—C9—C14—C13	24.0 (3)
C2—C1—C6—C5	−1.1 (5)	C8—C9—C14—C13	−158.0 (2)
C5—C4—C7—C8	179.3 (3)	C15—C13—C14—C9	70.0 (3)
C3—C4—C7—C8	−0.2 (5)	C12—C13—C14—C9	−49.6 (3)
C4—C7—C8—C9	−177.6 (3)	C16—C13—C14—C9	−169.5 (2)
C7—C8—C9—C10	177.9 (3)	C2—C3—O2—C17	4.8 (4)
C7—C8—C9—C14	0.0 (4)	C4—C3—O2—C17	−175.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14B···O1ⁱ	0.97	2.62	3.554 (4)	161

Symmetry code: (i) x+1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14B···O1ⁱ	0.97	2.62	3.554 (4)	161.4

Symmetry code: (i) x+1, y, z.

Acknowledgements

The authors thank the TBI X-ray facility, CAS in Crystallography and Biophysics, University of Madras, India, for the data collection and ZF thanks the UGC for a meritorious fellowship.

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