3-(4-Chloro-anilino)-2,5-dimethyl-cyclo-hex-2-en-1-one.

In the title compound, C(14)H(16)ClNO, the dihedral angle between the benzene ring and the conjugated part of the cyclo-hexene ring is 61.7 (2)°. Part of the cyclo-hexene ring and one of the attached methyl groups are disordered over two orientations with occupancies of 0.602 (7) and 0.398 (7). In addition, the crystal studied was a racemic twin [Flack parameter = 0.58 (4)]. In the crystal, the mol-ecules are linked into chains in the b-axis direction by inter-molecular N-H⋯O hydrogen bonds. C-H⋯O and C-H⋯Cl inter-actions are also observed.

Related literature

The title compound 3-(4-chloro­phenyl­amino)-2,5-dimethyl­cyclo­hex-2-enone possesses significant anti­convulsant properties. For the anti­convulsant properties of enamino­nes, see: Edafiogho et al. (1992 ▶); Eddington et al. (2003 ▶); Scott et al. (1993 ▶, 1995 ▶). For related structures see: Alexander et al. (2010 ▶, 2011 ▶).

Experimental

Crystal data

C14H16ClNO

M = 249.73

Monoclinic,

a = 6.0775 (5) Å

b = 8.8106 (5) Å

c = 12.5794 (7) Å

β = 99.904 (7)°

V = 663.5 (1) Å3

Z = 2

Cu Kα radiation

μ = 2.41 mm−1

T = 295 K

0.45 × 0.28 × 0.10 mm

Data collection

Oxford Diffraction Xcalibur Ruby Gemini diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T min = 0.679, T max = 1.000

2292 measured reflections

1705 independent reflections

1417 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.054

wR(F 2) = 0.150

S = 1.00

1705 reflections

171 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.22 e Å−3

Δρmin = −0.17 e Å−3

Absolute structure: Flack (1983 ▶), 259 Friedel pairs

Flack parameter: 0.58 (4)

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); 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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811005678/hg2794sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811005678/hg2794Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C14H16ClNO	F(000) = 264
Mr = 249.73	Dx = 1.250 Mg m−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2yb	Cell parameters from 1339 reflections
a = 6.0775 (5) Å	θ = 5.0–73.9°
b = 8.8106 (5) Å	µ = 2.41 mm−1
c = 12.5794 (7) Å	T = 295 K
β = 99.904 (7)°	Chunk, colorless
V = 663.5 (1) Å3	0.45 × 0.28 × 0.10 mm
Z = 2

Oxford Diffraction Xcalibur Ruby Gemini diffractometer	1705 independent reflections
Radiation source: Enhance (Cu) X-ray Source	1417 reflections with I > 2σ(I)
graphite	Rint = 0.029
Detector resolution: 10.5081 pixels mm-1	θmax = 74.1°, θmin = 6.2°
ω scans	h = −7→7
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −10→5
Tmin = 0.679, Tmax = 1.000	l = −13→15
2292 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.054	H-atom parameters constrained
wR(F2) = 0.150	w = 1/[σ2(Fo2) + (0.1145P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max < 0.001
1705 reflections	Δρmax = 0.22 e Å−3
171 parameters	Δρmin = −0.17 e Å−3
1 restraint	Absolute structure: Flack (1983), 259 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.58 (4)

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	Occ. (<1)
Cl1	0.8577 (2)	−0.13354 (18)	0.49024 (9)	0.1059 (5)
O1	0.7909 (4)	0.7372 (4)	−0.0704 (2)	0.0739 (7)
N1	0.6375 (5)	0.3591 (5)	0.1708 (2)	0.0660 (7)
H1	0.5033	0.3524	0.1357	0.079*
C1	0.7018 (5)	0.2490 (4)	0.2532 (2)	0.0577 (8)
C2	0.5554 (6)	0.2139 (6)	0.3223 (3)	0.0706 (10)
H2A	0.4243	0.2693	0.3193	0.085*
C3	0.6030 (7)	0.0966 (6)	0.3961 (3)	0.0775 (11)
H3A	0.5036	0.0717	0.4419	0.093*
C4	0.7978 (7)	0.0183 (5)	0.4006 (3)	0.0716 (10)
C5	0.9464 (6)	0.0537 (5)	0.3342 (3)	0.0685 (9)
H5A	1.0803	0.0009	0.3397	0.082*
C6	0.8969 (6)	0.1680 (5)	0.2591 (3)	0.0630 (8)
H6A	0.9957	0.1904	0.2125	0.076*
C7	0.7639 (6)	0.4728 (4)	0.1416 (3)	0.0576 (8)
C8	0.7074 (6)	0.5456 (4)	0.0452 (3)	0.0576 (7)
C9	0.8352 (5)	0.6705 (5)	0.0176 (3)	0.0614 (8)
C10A	1.051 (3)	0.719 (3)	0.0899 (17)	0.066 (3)	0.602 (7)
H10A	1.0710	0.8274	0.0847	0.080*	0.602 (7)
H10B	1.1773	0.6689	0.0664	0.080*	0.602 (7)
C11A	1.0433 (10)	0.6749 (8)	0.2071 (5)	0.0654 (13)	0.602 (7)
H11A	0.9295	0.7376	0.2324	0.078*	0.602 (7)
C12A	0.977 (3)	0.5058 (16)	0.2158 (13)	0.059 (2)	0.602 (7)
H12A	1.0945	0.4414	0.1976	0.070*	0.602 (7)
H12B	0.9599	0.4834	0.2894	0.070*	0.602 (7)
C14A	1.270 (3)	0.708 (2)	0.279 (2)	0.081 (4)	0.602 (7)
H14A	1.3132	0.8111	0.2684	0.122*	0.602 (7)
H14B	1.3813	0.6404	0.2606	0.122*	0.602 (7)
H14C	1.2575	0.6937	0.3535	0.122*	0.602 (7)
C10B	1.015 (6)	0.732 (5)	0.110 (3)	0.066 (3)	0.398 (7)
H10C	1.1249	0.7883	0.0783	0.080*	0.398 (7)
H10D	0.9443	0.8023	0.1529	0.080*	0.398 (7)
C11B	1.1314 (16)	0.6105 (13)	0.1820 (8)	0.0654 (13)	0.398 (7)
H11B	1.1935	0.5344	0.1386	0.078*	0.398 (7)
C12B	0.950 (5)	0.540 (3)	0.233 (2)	0.059 (2)	0.398 (7)
H12C	0.8849	0.6157	0.2745	0.070*	0.398 (7)
H12D	1.0119	0.4596	0.2822	0.070*	0.398 (7)
C14B	1.321 (6)	0.673 (4)	0.272 (4)	0.081 (4)	0.398 (7)
H14D	1.4200	0.5920	0.3000	0.122*	0.398 (7)
H14E	1.2559	0.7160	0.3298	0.122*	0.398 (7)
H14F	1.4044	0.7502	0.2423	0.122*	0.398 (7)
C13	0.5116 (7)	0.4931 (5)	−0.0383 (3)	0.0716 (10)
H13A	0.5080	0.3842	−0.0402	0.107*
H13B	0.5279	0.5312	−0.1080	0.107*
H13C	0.3749	0.5306	−0.0196	0.107*

	U11	U22	U33	U12	U13	U23
Cl1	0.1398 (11)	0.0944 (8)	0.0775 (6)	0.0012 (8)	0.0015 (6)	0.0320 (6)
O1	0.0719 (15)	0.0806 (17)	0.0706 (14)	0.0063 (14)	0.0158 (11)	0.0202 (13)
N1	0.0611 (14)	0.0737 (18)	0.0575 (14)	−0.0048 (16)	−0.0060 (11)	0.0102 (15)
C1	0.0651 (18)	0.0592 (19)	0.0451 (14)	−0.0076 (16)	−0.0009 (12)	0.0016 (13)
C2	0.0615 (18)	0.085 (3)	0.0630 (18)	−0.0002 (19)	0.0042 (14)	0.0081 (18)
C3	0.074 (2)	0.100 (3)	0.0582 (17)	−0.009 (2)	0.0091 (15)	0.015 (2)
C4	0.087 (3)	0.068 (2)	0.0535 (17)	−0.008 (2)	−0.0037 (15)	0.0098 (16)
C5	0.074 (2)	0.065 (2)	0.0623 (18)	0.003 (2)	−0.0017 (15)	−0.0009 (17)
C6	0.0663 (18)	0.066 (2)	0.0556 (15)	−0.0063 (19)	0.0059 (13)	−0.0038 (16)
C7	0.0562 (16)	0.0566 (19)	0.0579 (16)	−0.0011 (15)	0.0042 (12)	−0.0010 (15)
C8	0.0563 (16)	0.0581 (18)	0.0566 (16)	0.0059 (16)	0.0046 (12)	−0.0017 (15)
C9	0.0585 (16)	0.0611 (19)	0.0660 (18)	0.0088 (17)	0.0144 (14)	0.0059 (17)
C10A	0.057 (7)	0.072 (6)	0.073 (8)	−0.005 (5)	0.021 (4)	0.005 (6)
C11A	0.062 (3)	0.060 (4)	0.070 (3)	0.000 (3)	0.001 (2)	−0.007 (3)
C12A	0.065 (5)	0.051 (7)	0.056 (6)	0.003 (5)	0.000 (3)	−0.006 (4)
C14A	0.070 (10)	0.075 (10)	0.092 (4)	−0.006 (6)	−0.007 (6)	−0.005 (7)
C10B	0.057 (7)	0.072 (6)	0.073 (8)	−0.005 (5)	0.021 (4)	0.005 (6)
C11B	0.062 (3)	0.060 (4)	0.070 (3)	0.000 (3)	0.001 (2)	−0.007 (3)
C12B	0.065 (5)	0.051 (7)	0.056 (6)	0.003 (5)	0.000 (3)	−0.006 (4)
C14B	0.070 (10)	0.075 (10)	0.092 (4)	−0.006 (6)	−0.007 (6)	−0.005 (7)
C13	0.072 (2)	0.075 (2)	0.0617 (19)	0.000 (2)	−0.0045 (16)	0.0077 (18)

Cl1—C4	1.747 (4)	C10A—H10B	0.9700
O1—C9	1.241 (4)	C11A—C14A	1.54 (2)
N1—C7	1.351 (5)	C11A—C12A	1.552 (18)
N1—C1	1.424 (5)	C11A—H11A	0.9800
N1—H1	0.8600	C12A—H12A	0.9700
C1—C6	1.375 (5)	C12A—H12B	0.9700
C1—C2	1.382 (5)	C14A—H14A	0.9600
C2—C3	1.386 (6)	C14A—H14B	0.9600
C2—H2A	0.9300	C14A—H14C	0.9600
C3—C4	1.363 (6)	C10B—C11B	1.50 (4)
C3—H3A	0.9300	C10B—H10C	0.9700
C4—C5	1.367 (5)	C10B—H10D	0.9700
C5—C6	1.378 (6)	C11B—C12B	1.50 (3)
C5—H5A	0.9300	C11B—C14B	1.58 (5)
C6—H6A	0.9300	C11B—H11B	0.9800
C7—C8	1.363 (5)	C12B—H12C	0.9700
C7—C12A	1.489 (19)	C12B—H12D	0.9700
C7—C12B	1.58 (3)	C14B—H14D	0.9600
C8—C9	1.424 (5)	C14B—H14E	0.9600
C8—C13	1.518 (5)	C14B—H14F	0.9600
C9—C10A	1.52 (3)	C13—H13A	0.9600
C9—C10B	1.55 (4)	C13—H13B	0.9600
C10A—C11A	1.53 (2)	C13—H13C	0.9600
C10A—H10A	0.9700
C7—N1—C1	127.3 (3)	C10A—C11A—C14A	110.2 (14)
C7—N1—H1	116.4	C10A—C11A—C12A	111.1 (13)
C1—N1—H1	116.4	C14A—C11A—C12A	110.9 (12)
C6—C1—C2	119.5 (3)	C10A—C11A—H11A	108.2
C6—C1—N1	121.3 (3)	C14A—C11A—H11A	108.2
C2—C1—N1	119.0 (3)	C12A—C11A—H11A	108.2
C1—C2—C3	120.4 (4)	C7—C12A—C11A	110.6 (11)
C1—C2—H2A	119.8	C7—C12A—H12A	109.5
C3—C2—H2A	119.8	C11A—C12A—H12A	109.5
C4—C3—C2	119.0 (4)	C7—C12A—H12B	109.5
C4—C3—H3A	120.5	C11A—C12A—H12B	109.5
C2—C3—H3A	120.5	H12A—C12A—H12B	108.1
C3—C4—C5	121.3 (4)	C11B—C10B—C9	114 (3)
C3—C4—Cl1	119.8 (3)	C11B—C10B—H10C	108.8
C5—C4—Cl1	118.9 (3)	C9—C10B—H10C	108.8
C4—C5—C6	119.8 (4)	C11B—C10B—H10D	108.8
C4—C5—H5A	120.1	C9—C10B—H10D	108.8
C6—C5—H5A	120.1	H10C—C10B—H10D	107.7
C1—C6—C5	120.1 (3)	C10B—C11B—C12B	104.5 (18)
C1—C6—H6A	120.0	C10B—C11B—C14B	113 (2)
C5—C6—H6A	120.0	C12B—C11B—C14B	110 (2)
N1—C7—C8	121.5 (3)	C10B—C11B—H11B	109.7
N1—C7—C12A	116.6 (8)	C12B—C11B—H11B	109.7
C8—C7—C12A	121.7 (8)	C14B—C11B—H11B	109.7
N1—C7—C12B	116.5 (12)	C11B—C12B—C7	109.0 (17)
C8—C7—C12B	120.8 (12)	C11B—C12B—H12C	109.9
C12A—C7—C12B	15.4 (10)	C7—C12B—H12C	109.9
C7—C8—C9	121.1 (3)	C11B—C12B—H12D	109.9
C7—C8—C13	121.3 (3)	C7—C12B—H12D	109.9
C9—C8—C13	117.6 (3)	H12C—C12B—H12D	108.3
O1—C9—C8	122.6 (3)	C11B—C14B—H14D	109.5
O1—C9—C10A	115.7 (10)	C11B—C14B—H14E	109.5
C8—C9—C10A	121.3 (10)	H14D—C14B—H14E	109.5
O1—C9—C10B	121.3 (16)	C11B—C14B—H14F	109.5
C8—C9—C10B	115.6 (15)	H14D—C14B—H14F	109.5
C10A—C9—C10B	14.3 (11)	H14E—C14B—H14F	109.5
C9—C10A—C11A	109.7 (13)	C8—C13—H13A	109.5
C9—C10A—H10A	109.7	C8—C13—H13B	109.5
C11A—C10A—H10A	109.7	H13A—C13—H13B	109.5
C9—C10A—H10B	109.7	C8—C13—H13C	109.5
C11A—C10A—H10B	109.7	H13A—C13—H13C	109.5
H10A—C10A—H10B	108.2	H13B—C13—H13C	109.5
C7—N1—C1—C6	−49.7 (6)	C13—C8—C9—C10A	−172.1 (8)
C7—N1—C1—C2	136.0 (4)	C7—C8—C9—C10B	−9.3 (13)
C6—C1—C2—C3	−1.0 (6)	C13—C8—C9—C10B	173.0 (13)
N1—C1—C2—C3	173.4 (4)	O1—C9—C10A—C11A	159.1 (10)
C1—C2—C3—C4	1.1 (6)	C8—C9—C10A—C11A	−27.6 (17)
C2—C3—C4—C5	0.3 (6)	C10B—C9—C10A—C11A	43 (10)
C2—C3—C4—Cl1	−178.1 (3)	C9—C10A—C11A—C14A	174.3 (12)
C3—C4—C5—C6	−1.7 (6)	C9—C10A—C11A—C12A	50.9 (17)
Cl1—C4—C5—C6	176.7 (3)	N1—C7—C12A—C11A	−152.2 (7)
C2—C1—C6—C5	−0.5 (5)	C8—C7—C12A—C11A	32.7 (10)
N1—C1—C6—C5	−174.8 (3)	C12B—C7—C12A—C11A	−59 (6)
C4—C5—C6—C1	1.9 (6)	C10A—C11A—C12A—C7	−54.1 (13)
C1—N1—C7—C8	162.5 (3)	C14A—C11A—C12A—C7	−177.0 (10)
C1—N1—C7—C12A	−12.5 (7)	O1—C9—C10B—C11B	−149.8 (12)
C1—N1—C7—C12B	−29.8 (10)	C8—C9—C10B—C11B	37.9 (17)
N1—C7—C8—C9	176.7 (3)	C10A—C9—C10B—C11B	−79 (10)
C12A—C7—C8—C9	−8.4 (7)	C9—C10B—C11B—C12B	−63.3 (18)
C12B—C7—C8—C9	9.6 (10)	C9—C10B—C11B—C14B	177.3 (18)
N1—C7—C8—C13	−5.6 (6)	C10B—C11B—C12B—C7	60 (2)
C12A—C7—C8—C13	169.2 (5)	C14B—C11B—C12B—C7	−178.3 (16)
C12B—C7—C8—C13	−172.8 (9)	N1—C7—C12B—C11B	155.6 (11)
C7—C8—C9—O1	178.5 (4)	C8—C7—C12B—C11B	−36.6 (17)
C13—C8—C9—O1	0.7 (5)	C12A—C7—C12B—C11B	61 (6)
C7—C8—C9—C10A	5.6 (9)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1i	0.86	2.10	2.897 (4)	155
C6—H6A···O1ii	0.93	2.42	3.340 (4)	172
C12A—H12A···O1ii	0.97	2.58	3.439 (9)	147
C12B—H12D···Cl1iii	0.97	2.95	3.79 (3)	146

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1i	0.86	2.10	2.897 (4)	155
C6—H6A⋯O1ii	0.93	2.42	3.340 (4)	172
C12A—H12A⋯O1ii	0.97	2.58	3.439 (9)	147
C12B—H12D⋯Cl1iii	0.97	2.95	3.79 (3)	146

Symmetry codes: (i) ; (ii) ; (iii) .