tert-Butyl 4-(4-chloro-anilino)-6-methyl-2-oxocyclo-hex-3-ene-carboxyl-ate.

In the title compound, C(18)H(22)ClNO(3), the dihedral angle between the benzene ring and the conjugated part of the enaminone ring is 55.19 (9)°. The ester substituent makes a dihedral angle of 81.0 (2)° with this latter moiety. The crystal structure features N-H⋯O and weak C-H⋯O inter-molecular inter-actions.

Related literature

Our research on enamino­nes has led to several compounds possessing anti­convulsant properties, see: Edafiogho et al. (1992 ▶); Eddington et al. (2003 ▶); Scott et al. (1993 ▶, 1995 ▶).

Experimental

Crystal data

C18H22ClNO3

M = 335.82

Orthorhombic,

a = 11.0801 (3) Å

b = 10.9095 (3) Å

c = 29.2474 (7) Å

V = 3535.39 (16) Å3

Z = 8

Mo Kα radiation

μ = 0.23 mm−1

T = 295 K

0.45 × 0.38 × 0.08 mm

Data collection

Oxford Diffraction Xcalibur Ruby Gemini diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007 ▶) T min = 0.93, T max = 0.98

9798 measured reflections

3708 independent reflections

2925 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.055

wR(F 2) = 0.172

S = 1.09

3708 reflections

212 parameters

H-atom parameters constrained

Δρmax = 0.39 e Å−3

Δρmin = −0.25 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 ▶); 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: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810051743/om2378sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810051743/om2378Isup2.hkl

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

C18H22ClNO3	Dx = 1.262 Mg m−3
Mr = 335.82	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 5335 reflections
a = 11.0801 (3) Å	θ = 4.5–77.5°
b = 10.9095 (3) Å	µ = 0.23 mm−1
c = 29.2474 (7) Å	T = 295 K
V = 3535.39 (16) Å3	Plate, colorless
Z = 8	0.45 × 0.38 × 0.08 mm
F(000) = 1424

Oxford Diffraction Xcalibur Ruby Gemini diffractometer	3708 independent reflections
Radiation source: Enhance (Cu) X-ray Source	2925 reflections with I > 2σ(I)
graphite	Rint = 0.030
Detector resolution: 10.5081 pixels mm-1	θmax = 26.8°, θmin = 2.3°
ω scans	h = −13→14
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007)	k = −13→7
Tmin = 0.93, Tmax = 0.98	l = −22→36
9798 measured reflections

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.172	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.1062P)2 + 0.3243P] where P = (Fo2 + 2Fc2)/3
3708 reflections	(Δ/σ)max < 0.001
212 parameters	Δρmax = 0.39 e Å−3
0 restraints	Δρmin = −0.25 e Å−3

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
Cl1	0.91865 (8)	0.65446 (7)	0.66441 (3)	0.0944 (3)
O1	0.91038 (13)	0.17651 (17)	0.43476 (6)	0.0689 (4)
O2	0.7403 (2)	0.01470 (14)	0.37719 (6)	0.0785 (5)
O3	0.78836 (13)	0.16309 (12)	0.32703 (4)	0.0545 (3)
N1	0.63017 (13)	0.40873 (17)	0.52106 (5)	0.0539 (4)
H1	0.5536	0.4180	0.5243	0.065*
C1	0.70410 (16)	0.46315 (18)	0.55484 (6)	0.0492 (4)
C2	0.8068 (2)	0.5287 (2)	0.54365 (7)	0.0628 (5)
H2	0.8314	0.5333	0.5133	0.075*
C3	0.8732 (2)	0.5875 (2)	0.57713 (8)	0.0682 (6)
H3	0.9429	0.6305	0.5695	0.082*
C4	0.8349 (2)	0.5817 (2)	0.62193 (7)	0.0621 (5)
C5	0.7323 (2)	0.5180 (2)	0.63334 (7)	0.0659 (5)
H5	0.7068	0.5154	0.6636	0.079*
C6	0.66736 (17)	0.4583 (2)	0.60016 (6)	0.0584 (5)
H6	0.5985	0.4144	0.6081	0.070*
C7	0.66666 (15)	0.34364 (17)	0.48417 (5)	0.0447 (4)
C8	0.56893 (15)	0.32234 (19)	0.44950 (6)	0.0507 (4)
H8A	0.5601	0.3956	0.4310	0.061*
H8B	0.4933	0.3091	0.4654	0.061*
C9	0.59232 (15)	0.21420 (18)	0.41826 (6)	0.0489 (4)
H9	0.5873	0.1391	0.4365	0.059*
C10	0.72128 (15)	0.22487 (16)	0.39930 (6)	0.0447 (4)
H10A	0.7270	0.3016	0.3820	0.054*
C11	0.81263 (14)	0.23012 (17)	0.43840 (6)	0.0472 (4)
C12	0.78047 (15)	0.29974 (18)	0.47760 (6)	0.0485 (4)
H12	0.8391	0.3159	0.4995	0.058*
C13	0.49731 (19)	0.2070 (2)	0.38044 (7)	0.0635 (5)
H13A	0.4184	0.2022	0.3939	0.095*
H13B	0.5115	0.1355	0.3621	0.095*
H13C	0.5024	0.2789	0.3616	0.095*
C14	0.75164 (18)	0.12016 (16)	0.36732 (6)	0.0507 (4)
C15	0.8185 (2)	0.0796 (2)	0.28902 (6)	0.0586 (5)
C16	0.9248 (3)	0.0025 (4)	0.30166 (10)	0.1008 (11)
H16C	0.9005	−0.0585	0.3234	0.151*
H16D	0.9863	0.0534	0.3149	0.151*
H16A	0.9560	−0.0368	0.2748	0.151*
C17	0.8512 (4)	0.1665 (3)	0.25068 (9)	0.0955 (10)
H17A	0.9144	0.2205	0.2607	0.143*
H17B	0.7816	0.2139	0.2423	0.143*
H17C	0.8783	0.1204	0.2247	0.143*
C18	0.7086 (3)	0.0050 (4)	0.27656 (11)	0.1025 (11)
H18A	0.6868	−0.0465	0.3019	0.154*
H18B	0.7264	−0.0450	0.2504	0.154*
H18C	0.6428	0.0590	0.2695	0.154*

	U11	U22	U33	U12	U13	U23
Cl1	0.1084 (6)	0.0928 (5)	0.0821 (4)	−0.0154 (4)	−0.0342 (4)	−0.0178 (4)
O1	0.0460 (7)	0.0958 (11)	0.0648 (9)	0.0202 (7)	−0.0022 (6)	−0.0154 (8)
O2	0.1255 (15)	0.0446 (8)	0.0653 (9)	0.0057 (8)	0.0129 (9)	0.0027 (7)
O3	0.0694 (8)	0.0495 (7)	0.0446 (6)	0.0010 (6)	0.0015 (6)	−0.0036 (5)
N1	0.0414 (7)	0.0721 (10)	0.0481 (8)	0.0038 (7)	0.0036 (6)	−0.0087 (7)
C1	0.0474 (8)	0.0557 (10)	0.0443 (8)	0.0047 (7)	0.0002 (6)	−0.0028 (7)
C2	0.0743 (13)	0.0642 (12)	0.0499 (10)	−0.0136 (10)	0.0051 (9)	0.0020 (9)
C3	0.0743 (13)	0.0604 (12)	0.0700 (12)	−0.0195 (11)	−0.0015 (10)	0.0011 (10)
C4	0.0714 (12)	0.0577 (11)	0.0571 (10)	0.0041 (9)	−0.0161 (9)	−0.0065 (9)
C5	0.0642 (11)	0.0887 (15)	0.0447 (9)	0.0067 (11)	−0.0011 (8)	−0.0058 (10)
C6	0.0470 (9)	0.0802 (13)	0.0479 (9)	0.0015 (9)	0.0032 (7)	−0.0037 (9)
C7	0.0413 (8)	0.0528 (9)	0.0399 (7)	−0.0010 (7)	0.0017 (6)	0.0020 (7)
C8	0.0364 (7)	0.0677 (11)	0.0480 (8)	0.0020 (7)	−0.0013 (6)	−0.0027 (8)
C9	0.0441 (8)	0.0538 (10)	0.0489 (9)	−0.0056 (7)	−0.0048 (7)	0.0038 (7)
C10	0.0476 (8)	0.0448 (8)	0.0418 (8)	−0.0005 (6)	−0.0001 (6)	0.0007 (7)
C11	0.0383 (7)	0.0561 (9)	0.0471 (8)	0.0006 (7)	0.0020 (6)	0.0001 (7)
C12	0.0378 (7)	0.0630 (10)	0.0445 (8)	0.0029 (7)	−0.0034 (6)	−0.0022 (7)
C13	0.0538 (10)	0.0735 (13)	0.0633 (11)	−0.0086 (9)	−0.0151 (9)	−0.0045 (10)
C14	0.0575 (9)	0.0469 (9)	0.0478 (9)	0.0033 (8)	−0.0038 (7)	−0.0005 (7)
C15	0.0693 (11)	0.0613 (11)	0.0451 (9)	0.0034 (9)	−0.0008 (8)	−0.0103 (8)
C16	0.102 (2)	0.126 (3)	0.0742 (16)	0.051 (2)	0.0111 (15)	−0.0059 (17)
C17	0.147 (3)	0.0849 (17)	0.0544 (13)	−0.0033 (19)	0.0192 (16)	−0.0025 (12)
C18	0.102 (2)	0.125 (3)	0.0800 (17)	−0.0311 (19)	0.0000 (15)	−0.0427 (18)

Cl1—C4	1.742 (2)	C9—C13	1.529 (2)
O1—C11	1.235 (2)	C9—C10	1.537 (2)
O2—C14	1.193 (3)	C9—H9	0.9800
O3—C14	1.332 (2)	C10—C14	1.514 (2)
O3—C15	1.475 (2)	C10—C11	1.528 (2)
N1—C7	1.353 (2)	C10—H10A	0.9800
N1—C1	1.414 (2)	C11—C12	1.421 (2)
N1—H1	0.8600	C12—H12	0.9300
C1—C2	1.383 (3)	C13—H13A	0.9600
C1—C6	1.388 (3)	C13—H13B	0.9600
C2—C3	1.383 (3)	C13—H13C	0.9600
C2—H2	0.9300	C15—C16	1.494 (3)
C3—C4	1.379 (3)	C15—C18	1.509 (3)
C3—H3	0.9300	C15—C17	1.512 (3)
C4—C5	1.373 (3)	C16—H16C	0.9600
C5—C6	1.373 (3)	C16—H16D	0.9600
C5—H5	0.9300	C16—H16A	0.9600
C6—H6	0.9300	C17—H17A	0.9600
C7—C12	1.363 (2)	C17—H17B	0.9600
C7—C8	1.502 (2)	C17—H17C	0.9600
C8—C9	1.515 (3)	C18—H18A	0.9600
C8—H8A	0.9700	C18—H18B	0.9600
C8—H8B	0.9700	C18—H18C	0.9600
C14—O3—C15	121.26 (15)	C11—C10—H10	108.1
C7—N1—C1	127.17 (15)	C9—C10—H10	108.1
C7—N1—H1	116.4	O1—C11—C12	122.87 (17)
C1—N1—H1	116.4	O1—C11—C10	119.88 (16)
C2—C1—C6	119.15 (18)	C12—C11—C10	117.24 (15)
C2—C1—N1	121.90 (17)	C7—C12—C11	122.28 (16)
C6—C1—N1	118.77 (17)	C7—C12—H12	118.9
C3—C2—C1	120.67 (19)	C11—C12—H12	118.9
C3—C2—H2	119.7	C9—C13—H13A	109.5
C1—C2—H2	119.7	C9—C13—H13B	109.5
C4—C3—C2	119.2 (2)	H13A—C13—H13B	109.5
C4—C3—H3	120.4	C9—C13—H13C	109.5
C2—C3—H3	120.4	H13A—C13—H13C	109.5
C5—C4—C3	120.60 (19)	H13B—C13—H13C	109.5
C5—C4—Cl1	119.86 (17)	O2—C14—O3	125.85 (18)
C3—C4—Cl1	119.54 (19)	O2—C14—C10	123.68 (18)
C6—C5—C4	120.15 (19)	O3—C14—C10	110.43 (15)
C6—C5—H5	119.9	O3—C15—C16	109.85 (18)
C4—C5—H5	119.9	O3—C15—C18	109.42 (19)
C5—C6—C1	120.22 (19)	C16—C15—C18	113.1 (3)
C5—C6—H6	119.9	O3—C15—C17	103.07 (18)
C1—C6—H6	119.9	C16—C15—C17	110.3 (2)
N1—C7—C12	124.99 (16)	C18—C15—C17	110.6 (2)
N1—C7—C8	113.84 (15)	C15—C16—H16C	109.5
C12—C7—C8	121.18 (15)	C15—C16—H16D	109.5
C7—C8—C9	113.86 (15)	H16C—C16—H16D	109.5
C7—C8—H8A	108.8	C15—C16—H16A	109.5
C9—C8—H8A	108.8	H16C—C16—H16A	109.5
C7—C8—H8B	108.8	H16D—C16—H16A	109.5
C9—C8—H8B	108.8	C15—C17—H17A	109.5
H8A—C8—H8B	107.7	C15—C17—H17B	109.5
C8—C9—C13	111.01 (16)	H17A—C17—H17B	109.5
C8—C9—C10	108.52 (14)	C15—C17—H17C	109.5
C13—C9—C10	112.52 (16)	H17A—C17—H17C	109.5
C8—C9—H9	108.2	H17B—C17—H17C	109.5
C13—C9—H9	108.2	C15—C18—H18A	109.5
C10—C9—H9	108.2	C15—C18—H18B	109.5
C14—C10—C11	110.08 (14)	H18A—C18—H18B	109.5
C14—C10—C9	111.85 (15)	C15—C18—H18C	109.5
C11—C10—C9	110.40 (14)	H18A—C18—H18C	109.5
C14—C10—H10	108.1	H18B—C18—H18C	109.5
C7—N1—C1—C2	44.5 (3)	C8—C9—C10—C11	57.46 (19)
C7—N1—C1—C6	−140.4 (2)	C13—C9—C10—C11	−179.30 (17)
C6—C1—C2—C3	0.8 (3)	C14—C10—C11—O1	17.6 (2)
N1—C1—C2—C3	175.9 (2)	C9—C10—C11—O1	141.56 (18)
C1—C2—C3—C4	−1.0 (4)	C14—C10—C11—C12	−163.43 (16)
C2—C3—C4—C5	0.2 (4)	C9—C10—C11—C12	−39.5 (2)
C2—C3—C4—Cl1	179.48 (19)	N1—C7—C12—C11	178.91 (18)
C3—C4—C5—C6	0.7 (4)	C8—C7—C12—C11	−1.1 (3)
Cl1—C4—C5—C6	−178.60 (18)	O1—C11—C12—C7	−170.34 (19)
C4—C5—C6—C1	−0.8 (3)	C10—C11—C12—C7	10.7 (3)
C2—C1—C6—C5	0.1 (3)	C15—O3—C14—O2	0.7 (3)
N1—C1—C6—C5	−175.1 (2)	C15—O3—C14—C10	−177.35 (16)
C1—N1—C7—C12	12.9 (3)	C11—C10—C14—O2	70.1 (3)
C1—N1—C7—C8	−167.05 (18)	C9—C10—C14—O2	−53.0 (3)
N1—C7—C8—C9	−158.30 (16)	C11—C10—C14—O3	−111.80 (17)
C12—C7—C8—C9	21.7 (3)	C9—C10—C14—O3	125.08 (17)
C7—C8—C9—C13	−173.31 (16)	C14—O3—C15—C16	−64.0 (3)
C7—C8—C9—C10	−49.2 (2)	C14—O3—C15—C18	60.7 (3)
C8—C9—C10—C14	−179.60 (14)	C14—O3—C15—C17	178.4 (2)
C13—C9—C10—C14	−56.4 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1i	0.86	2.24	2.909 (2)	135.
C6—H6···O1i	0.93	2.63	3.363 (2)	137.
C10—H10···O2ii	0.98	2.36	3.255 (2)	152.0

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1i	0.86	2.24	2.909 (2)	135
C6—H6⋯O1i	0.93	2.63	3.363 (2)	137
C10—H10⋯O2ii	0.98	2.36	3.255 (2)	152

Symmetry codes: (i) ; (ii) .