3-[(E)-2-(4-Chloro­phen­yl)ethen­yl]-5,5-di­methyl­cyclo­hex-2-en-1-one

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

doi:10.1107/S1600536813016255

organic compounds

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ISSN: 2056-9890

Volume 69| Part 7| July 2013| Page o1121

https://doi.org/10.1107/S1600536813016255

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3-[(E)-2-(4-Chlorophenyl)ethenyl]-5,5-dimethylcyclohex-2-en-1-one

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

^aCentre 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 1 June 2013; accepted 11 June 2013; online 19 June 2013)

In the title compound, C₁₆H₁₇ClO, the cyclohexene ring adopts a half-chair conformation and the best plane through the six ring atoms makes a dihedral angle of 6.69 (7)° with the chlorophenyl ring. In the crystal, pairs of C—H⋯O hydrogen bonds link the molecules into centrosymmetric R₂²(20) dimers. The dimers are linked into an infinite chains along the b-axis direction by further C—H⋯O hydrogen bonds.

Related literature

For the pharmacological activity of cyclohexanone derivatives, see: Puetz et al.(2003 ); Rajveer et al. (2010 ). For a related structure, see: Hema et al. (2006 ). For conformational analysis, see: Allinger (1977 ); Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₆H₁₇ClO
M_r = 260.75
Monoclinic, P 2₁ /n
a = 13.7630 (4) Å
b = 6.0841 (2) Å
c = 17.5003 (6) Å
β = 105.726 (2)°
V = 1410.54 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.26 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 = 0.927, T_max = 0.951
13158 measured reflections
3552 independent reflections
2611 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.130
S = 1.03
3552 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1ⁱ	0.93	2.41	3.301 (2)	159
C14—H14B⋯O1ⁱⁱ	0.97	2.57	3.4299 (18)	148
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x, y-1, 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

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536813016255/bt6912sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813016255/bt6912Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813016255/bt6912Isup3.cml

checkCIF report

Comment top

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 antiinflammatory, analgesic, local anesthetic and antihistaminic drugs (Rajveer et al., 2010). In view of different applications of this class of compounds, we have undertaken a single-crystal structure determination of the title compound.

Molecules of the title compound, C₁₆H₁₇ClO, (Fig.1) are linked by pairs of intermolecular (C2—H2···O1) hydrogen bonds (Fig. 2) into centrosymmetric R₂²(20) dimers and these dimers are linked into an infinite chains by pairs of (C14—H14B···O1) hydrogen bonds, which propagate in the b axis direction. The cyclohexene ring (C9—C14) adopts a half-chair conformation and makes a dihedral angle of 6.69 (7)° with the phenyl ring (C1—C6).

Related literature top

For the pharmacological activity of cyclohexanone derivatives, see: Puetz et al.(2003); Rajveer et al. (2010). For a related structure, see: Hema et al. (2006). For conformational analysis, see: Allinger (1977); Cremer & Pople (1975).

Experimental top

A mixture of isophorone (0.01 mol), 4-chlorobezaldehyde (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. Yield=90%, Melting point=84–86°C.

Structure description top

For the pharmacological activity of cyclohexanone derivatives, see: Puetz et al.(2003); Rajveer et al. (2010). For a related structure, see: Hema et al. (2006). For conformational analysis, see: Allinger (1977); Cremer & Pople (1975).

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 compound, showing displacement ellipsoids drawn at the 30% probability level. H atoms are presented as small spheres of arbitrary radius.
	Fig. 2. The crystal packing of the title compound viewed down a axis. H-atoms not involved in H-bonds have been excluded for clarity.

3-[(E)-2-(4-Chlorophenyl)ethenyl]-5,5-dimethylcyclohex-2-en-1-one top

Crystal data top

C₁₆H₁₇ClO	F(000) = 552
M_r = 260.75	D_x = 1.228 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.7630 (4) Å	Cell parameters from 3552 reflections
b = 6.0841 (2) Å	θ = 1.7–28.5°
c = 17.5003 (6) Å	µ = 0.26 mm⁻¹
β = 105.726 (2)°	T = 293 K
V = 1410.54 (8) Å³	Block, colourless
Z = 4	0.30 × 0.25 × 0.20 mm

Data collection top

Bruker SMART APEXII area-detector diffractometer	3552 independent reflections
Radiation source: fine-focus sealed tube	2611 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω and φ scans	θ_max = 28.5°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −17→18
T_min = 0.927, T_max = 0.951	k = −8→8
13158 measured reflections	l = −21→23

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.130	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0613P)² + 0.2499P] where P = (F_o² + 2F_c²)/3
3552 reflections	(Δ/σ)_max < 0.001
165 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₁₆H₁₇ClO	V = 1410.54 (8) Å³
M_r = 260.75	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 13.7630 (4) Å	µ = 0.26 mm⁻¹
b = 6.0841 (2) Å	T = 293 K
c = 17.5003 (6) Å	0.30 × 0.25 × 0.20 mm
β = 105.726 (2)°

Data collection top

Bruker SMART APEXII area-detector diffractometer	3552 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	2611 reflections with I > 2σ(I)
T_min = 0.927, T_max = 0.951	R_int = 0.022
13158 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.130	H-atom parameters constrained
S = 1.03	Δρ_max = 0.21 e Å⁻³
3552 reflections	Δρ_min = −0.33 e Å⁻³
165 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	0.25679 (10)	−0.3118 (3)	0.46901 (9)	0.0552 (4)
C2	0.30278 (13)	−0.1202 (3)	0.50163 (9)	0.0631 (4)
H2	0.3008	−0.0766	0.5521	0.076*
C3	0.35172 (13)	0.0062 (3)	0.45851 (9)	0.0600 (4)
H3	0.3831	0.1356	0.4807	0.072*
C4	0.35569 (10)	−0.0537 (2)	0.38278 (8)	0.0490 (3)
C5	0.30813 (11)	−0.2484 (3)	0.35197 (9)	0.0572 (4)
H5	0.3095	−0.2927	0.3014	0.069*
C6	0.25905 (12)	−0.3775 (3)	0.39444 (9)	0.0592 (4)
H6	0.2278	−0.5076	0.3729	0.071*
C7	0.40805 (11)	0.0754 (2)	0.33556 (8)	0.0518 (3)
H7	0.4065	0.0202	0.2857	0.062*
C8	0.45744 (11)	0.2628 (2)	0.35633 (8)	0.0531 (3)
H8	0.4574	0.3211	0.4055	0.064*
C9	0.51163 (10)	0.3859 (2)	0.30951 (8)	0.0471 (3)
C10	0.56090 (11)	0.5706 (2)	0.33930 (8)	0.0529 (3)
H10	0.5568	0.6189	0.3887	0.063*
C11	0.62046 (10)	0.6992 (2)	0.29819 (8)	0.0505 (3)
C12	0.63343 (11)	0.6046 (3)	0.22279 (9)	0.0575 (4)
H12A	0.6915	0.5076	0.2353	0.069*
H12B	0.6472	0.7230	0.1901	0.069*
C13	0.54145 (11)	0.4765 (2)	0.17534 (8)	0.0508 (3)
C14	0.51482 (11)	0.3025 (2)	0.22953 (8)	0.0527 (3)
H14A	0.4494	0.2406	0.2030	0.063*
H14B	0.5640	0.1847	0.2371	0.063*
C15	0.56696 (15)	0.3622 (3)	0.10559 (10)	0.0780 (5)
H15A	0.5103	0.2760	0.0771	0.117*
H15B	0.6244	0.2682	0.1251	0.117*
H15C	0.5823	0.4707	0.0707	0.117*
C16	0.45296 (13)	0.6332 (3)	0.14473 (10)	0.0704 (5)
H16A	0.4715	0.7444	0.1124	0.106*
H16B	0.4358	0.7012	0.1889	0.106*
H16C	0.3958	0.5527	0.1137	0.106*
O1	0.65928 (9)	0.87306 (19)	0.32485 (7)	0.0688 (3)
Cl1	0.19413 (4)	−0.47224 (9)	0.52256 (3)	0.08168 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0494 (7)	0.0594 (9)	0.0550 (8)	−0.0006 (7)	0.0112 (6)	0.0115 (7)
C2	0.0715 (10)	0.0726 (11)	0.0450 (8)	−0.0080 (8)	0.0157 (7)	−0.0013 (7)
C3	0.0696 (9)	0.0585 (9)	0.0504 (8)	−0.0135 (7)	0.0139 (7)	−0.0063 (7)
C4	0.0477 (7)	0.0489 (8)	0.0500 (7)	0.0014 (6)	0.0124 (6)	0.0008 (6)
C5	0.0621 (8)	0.0566 (9)	0.0551 (8)	−0.0045 (7)	0.0192 (7)	−0.0078 (7)
C6	0.0598 (8)	0.0542 (9)	0.0627 (9)	−0.0087 (7)	0.0150 (7)	−0.0033 (7)
C7	0.0558 (8)	0.0525 (8)	0.0481 (7)	0.0004 (6)	0.0155 (6)	−0.0010 (6)
C8	0.0572 (8)	0.0558 (8)	0.0468 (7)	−0.0018 (7)	0.0150 (6)	−0.0011 (6)
C9	0.0470 (7)	0.0471 (7)	0.0458 (7)	0.0024 (6)	0.0100 (5)	0.0007 (6)
C10	0.0564 (8)	0.0568 (8)	0.0448 (7)	−0.0035 (7)	0.0126 (6)	−0.0069 (6)
C11	0.0441 (6)	0.0506 (8)	0.0526 (8)	−0.0005 (6)	0.0059 (6)	−0.0008 (6)
C12	0.0507 (8)	0.0647 (9)	0.0602 (9)	−0.0044 (7)	0.0206 (6)	−0.0052 (7)
C13	0.0545 (7)	0.0525 (8)	0.0464 (7)	0.0003 (6)	0.0155 (6)	−0.0027 (6)
C14	0.0625 (8)	0.0456 (7)	0.0499 (8)	−0.0012 (6)	0.0153 (6)	−0.0048 (6)
C15	0.0945 (13)	0.0874 (13)	0.0605 (10)	−0.0114 (10)	0.0356 (9)	−0.0178 (9)
C16	0.0686 (10)	0.0708 (11)	0.0614 (9)	0.0072 (9)	0.0000 (8)	0.0082 (8)
O1	0.0740 (7)	0.0596 (7)	0.0712 (7)	−0.0183 (6)	0.0170 (6)	−0.0110 (5)
Cl1	0.0819 (3)	0.0909 (4)	0.0745 (3)	−0.0193 (2)	0.0250 (2)	0.0201 (2)

Geometric parameters (Å, º) top

C1—C6	1.373 (2)	C10—C11	1.457 (2)
C1—C2	1.375 (2)	C10—H10	0.9300
C1—Cl1	1.7356 (15)	C11—O1	1.2192 (17)
C2—C3	1.375 (2)	C11—C12	1.494 (2)
C2—H2	0.9300	C12—C13	1.526 (2)
C3—C4	1.390 (2)	C12—H12A	0.9700
C3—H3	0.9300	C12—H12B	0.9700
C4—C5	1.390 (2)	C13—C16	1.525 (2)
C4—C7	1.463 (2)	C13—C15	1.526 (2)
C5—C6	1.378 (2)	C13—C14	1.531 (2)
C5—H5	0.9300	C14—H14A	0.9700
C6—H6	0.9300	C14—H14B	0.9700
C7—C8	1.327 (2)	C15—H15A	0.9600
C7—H7	0.9300	C15—H15B	0.9600
C8—C9	1.4560 (19)	C15—H15C	0.9600
C8—H8	0.9300	C16—H16A	0.9600
C9—C10	1.342 (2)	C16—H16B	0.9600
C9—C14	1.5006 (19)	C16—H16C	0.9600

C6—C1—C2	121.00 (14)	C10—C11—C12	116.55 (12)
C6—C1—Cl1	119.47 (12)	C11—C12—C13	113.41 (12)
C2—C1—Cl1	119.53 (12)	C11—C12—H12A	108.9
C3—C2—C1	119.04 (14)	C13—C12—H12A	108.9
C3—C2—H2	120.5	C11—C12—H12B	108.9
C1—C2—H2	120.5	C13—C12—H12B	108.9
C2—C3—C4	121.89 (14)	H12A—C12—H12B	107.7
C2—C3—H3	119.1	C16—C13—C15	109.80 (14)
C4—C3—H3	119.1	C16—C13—C12	109.72 (13)
C3—C4—C5	117.22 (13)	C15—C13—C12	109.33 (13)
C3—C4—C7	123.38 (13)	C16—C13—C14	110.34 (13)
C5—C4—C7	119.39 (13)	C15—C13—C14	109.04 (13)
C6—C5—C4	121.67 (14)	C12—C13—C14	108.58 (12)
C6—C5—H5	119.2	C9—C14—C13	114.60 (12)
C4—C5—H5	119.2	C9—C14—H14A	108.6
C1—C6—C5	119.18 (14)	C13—C14—H14A	108.6
C1—C6—H6	120.4	C9—C14—H14B	108.6
C5—C6—H6	120.4	C13—C14—H14B	108.6
C8—C7—C4	126.92 (14)	H14A—C14—H14B	107.6
C8—C7—H7	116.5	C13—C15—H15A	109.5
C4—C7—H7	116.5	C13—C15—H15B	109.5
C7—C8—C9	126.19 (14)	H15A—C15—H15B	109.5
C7—C8—H8	116.9	C13—C15—H15C	109.5
C9—C8—H8	116.9	H15A—C15—H15C	109.5
C10—C9—C8	119.59 (13)	H15B—C15—H15C	109.5
C10—C9—C14	120.39 (13)	C13—C16—H16A	109.5
C8—C9—C14	119.99 (12)	C13—C16—H16B	109.5
C9—C10—C11	123.40 (13)	H16A—C16—H16B	109.5
C9—C10—H10	118.3	C13—C16—H16C	109.5
C11—C10—H10	118.3	H16A—C16—H16C	109.5
O1—C11—C10	121.60 (14)	H16B—C16—H16C	109.5
O1—C11—C12	121.83 (14)

C6—C1—C2—C3	−0.1 (2)	C8—C9—C10—C11	177.38 (13)
Cl1—C1—C2—C3	−179.65 (12)	C14—C9—C10—C11	−0.7 (2)
C1—C2—C3—C4	0.3 (3)	C9—C10—C11—O1	175.58 (14)
C2—C3—C4—C5	−0.2 (2)	C9—C10—C11—C12	−5.8 (2)
C2—C3—C4—C7	−179.28 (14)	O1—C11—C12—C13	−147.07 (14)
C3—C4—C5—C6	−0.1 (2)	C10—C11—C12—C13	34.32 (19)
C7—C4—C5—C6	179.07 (13)	C11—C12—C13—C16	66.81 (17)
C2—C1—C6—C5	−0.1 (2)	C11—C12—C13—C15	−172.71 (14)
Cl1—C1—C6—C5	179.41 (11)	C11—C12—C13—C14	−53.85 (17)
C4—C5—C6—C1	0.2 (2)	C10—C9—C14—C13	−21.6 (2)
C3—C4—C7—C8	−0.4 (2)	C8—C9—C14—C13	160.34 (12)
C5—C4—C7—C8	−179.51 (14)	C16—C13—C14—C9	−72.87 (16)
C4—C7—C8—C9	178.10 (13)	C15—C13—C14—C9	166.46 (13)
C7—C8—C9—C10	−178.00 (15)	C12—C13—C14—C9	47.41 (16)
C7—C8—C9—C14	0.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1ⁱ	0.93	2.41	3.301 (2)	159
C14—H14B···O1ⁱⁱ	0.97	2.57	3.4299 (18)	148

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₇ClO
M_r	260.75
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	13.7630 (4), 6.0841 (2), 17.5003 (6)
β (°)	105.726 (2)
V (Å³)	1410.54 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker SMART APEXII area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.927, 0.951
No. of measured, independent and observed [I > 2σ(I)] reflections	13158, 3552, 2611
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.671

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.130, 1.03
No. of reflections	3552
No. of parameters	165
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.33

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1ⁱ	0.93	2.41	3.301 (2)	159
C14—H14B···O1ⁱⁱ	0.97	2.57	3.4299 (18)	148

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

References

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