Ethyl 4-(4-bromo-phen-yl)-6-(4-ethoxy-phen-yl)-2-oxocyclo-hex-3-enecarboxyl-ate.

The title compound, C(23)H(23)BrO(4), is an inter-mediate in the synthesis of fused heterocycles. In the title mol-ecule, the cyclo-hexene ring has a distorted half-chair conformation. The bromo-phenyl ring and the mean plane of the cyclo-hexene ring form a dihedral angle of 13.8 (3)°, whereas the benzene and cyclo-hexene rings are approximately perpendicular [88.44 (17)°]. There are only weak C-H⋯O and C-H⋯π inter-molecular inter-actions.

Related literature

For applications of cyclo­hexenones, see: Eddington et al. (2000 ▶); Li & Strobel (2001 ▶); Luu et al. (2000 ▶); Padmavathi et al. (2000 ▶, 2001 ▶).

Experimental

Crystal data

C23H23BrO4

M = 443.32

Monoclinic,

a = 12.792 (4) Å

b = 14.537 (4) Å

c = 12.114 (4) Å

β = 113.88 (2)°

V = 2059.8 (11) Å3

Z = 4

Mo Kα radiation

μ = 2.02 mm−1

T = 298 (2) K

0.50 × 0.50 × 0.08 mm

Data collection

Bruker P4 diffractometer

Absorption correction: gaussian (XSCANS; Bruker, 1999 ▶) T min = 0.246, T max = 0.941

7765 measured reflections

3630 independent reflections

2088 reflections with I > 2σ(I)

R int = 0.054

3 standard reflections every 97 reflections intensity decay: 6.4%

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.175

S = 1.01

3630 reflections

254 parameters

H-atom parameters constrained

Δρmax = 0.44 e Å−3

Δρmin = −0.41 e Å−3

Data collection: XSCANS (Bruker, 1999 ▶); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL-Plus (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL-Plus; molecular graphics: SHELXTL-Plus and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXTL-Plus.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809003523/gk2184sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809003523/gk2184Isup2.hkl

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

C23H23BrO4	F(000) = 912
Mr = 443.32	Dx = 1.430 Mg m−3
Monoclinic, P21/c	Melting point: 400 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 12.792 (4) Å	Cell parameters from 91 reflections
b = 14.537 (4) Å	θ = 4.6–12.4°
c = 12.114 (4) Å	µ = 2.02 mm−1
β = 113.88 (2)°	T = 298 K
V = 2059.8 (11) Å3	Plate, colourless
Z = 4	0.50 × 0.50 × 0.08 mm

Bruker P4 diffractometer	2088 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.054
graphite	θmax = 25.0°, θmin = 2.2°
ω scans	h = −14→15
Absorption correction: gaussian (XSCANS; Bruker, 1999)	k = −1→17
Tmin = 0.246, Tmax = 0.941	l = −14→14
7765 measured reflections	3 standard reflections every 97 reflections
3630 independent reflections	intensity decay: 6.4%

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)] = 0.059	H-atom parameters constrained
wR(F2) = 0.175	w = 1/[σ2(Fo2) + (0.0744P)2 + 1.4731P] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max < 0.001
3630 reflections	Δρmax = 0.44 e Å−3
254 parameters	Δρmin = −0.41 e Å−3
0 restraints	Extinction correction: SHELXTL-Plus (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0050 (10)

Experimental. Absorption correction based on 6 crystal faces Faces used: 001, 00–1, 20–1, -201, 010, 0–10

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
Br1	0.12714 (6)	0.10565 (5)	1.01969 (7)	0.1061 (4)
O1	0.5590 (3)	0.4373 (2)	0.7177 (4)	0.0864 (11)
O2	0.6752 (4)	0.3470 (3)	0.5468 (4)	0.1049 (13)
O3	0.7863 (4)	0.3351 (3)	0.7398 (4)	0.0901 (11)
O4	0.8559 (3)	−0.0461 (2)	0.5587 (3)	0.0662 (9)
C1	0.2279 (4)	0.1456 (4)	0.9511 (5)	0.0673 (13)
C2	0.2177 (5)	0.2318 (4)	0.9038 (5)	0.0777 (15)
H2A	0.1619	0.2715	0.9068	0.093*
C3	0.2889 (4)	0.2597 (3)	0.8525 (5)	0.0700 (13)
H3A	0.2809	0.3185	0.8200	0.084*
C4	0.3099 (4)	0.0866 (3)	0.9484 (5)	0.0687 (13)
H4A	0.3174	0.0281	0.9818	0.082*
C5	0.3812 (4)	0.1153 (3)	0.8955 (5)	0.0635 (12)
H5A	0.4362	0.0749	0.8922	0.076*
C6	0.3739 (4)	0.2020 (3)	0.8474 (4)	0.0534 (11)
C7	0.4524 (4)	0.2326 (3)	0.7936 (4)	0.0523 (10)
C8	0.5179 (4)	0.1615 (3)	0.7592 (4)	0.0591 (12)
H8A	0.5465	0.1162	0.8234	0.071*
H8B	0.4660	0.1302	0.6871	0.071*
C9	0.6161 (5)	0.1980 (3)	0.7360 (6)	0.0819 (16)
H9A	0.6733	0.2120	0.8171	0.098*
C10	0.4667 (4)	0.3220 (3)	0.7762 (5)	0.0649 (13)
H10A	0.4249	0.3647	0.7988	0.078*
C11	0.5422 (4)	0.3557 (3)	0.7250 (5)	0.0664 (13)
C12	0.5970 (5)	0.2855 (3)	0.6760 (6)	0.0923 (19)
H12A	0.5368	0.2717	0.5965	0.111*
C13	0.6893 (5)	0.3258 (3)	0.6454 (7)	0.0745 (15)
C14	0.8792 (5)	0.3710 (5)	0.7141 (8)	0.122 (3)
H14A	0.9372	0.3963	0.7873	0.147*
H14B	0.8510	0.4203	0.6554	0.147*
C15	0.9299 (8)	0.2991 (7)	0.6667 (11)	0.176 (4)
H15A	0.9915	0.3247	0.6506	0.264*
H15B	0.8728	0.2748	0.5934	0.264*
H15C	0.9587	0.2506	0.7251	0.264*
C16	0.6757 (5)	0.1277 (3)	0.6896 (5)	0.0666 (13)
C17	0.6243 (4)	0.0920 (4)	0.5765 (6)	0.0792 (15)
H17A	0.5488	0.1082	0.5298	0.095*
C18	0.6789 (4)	0.0329 (4)	0.5277 (5)	0.0737 (14)
H18A	0.6411	0.0099	0.4499	0.088*
C19	0.7853 (5)	0.0997 (3)	0.7578 (5)	0.0791 (15)
H19A	0.8221	0.1205	0.8368	0.095*
C20	0.8414 (5)	0.0416 (4)	0.7115 (5)	0.0747 (14)
H20A	0.9160	0.0240	0.7593	0.090*
C21	0.7896 (4)	0.0092 (3)	0.5964 (4)	0.0574 (11)
C22	0.8162 (5)	−0.0624 (4)	0.4328 (5)	0.0775 (14)
H22A	0.7985	−0.0046	0.3891	0.093*
H22B	0.7475	−0.0997	0.4051	0.093*
C23	0.9080 (5)	−0.1110 (4)	0.4114 (6)	0.0858 (17)
H23A	0.8839	−0.1220	0.3265	0.129*
H23B	0.9237	−0.1687	0.4536	0.129*
H23C	0.9759	−0.0739	0.4402	0.129*

	U11	U22	U33	U12	U13	U23
Br1	0.1224 (6)	0.1085 (6)	0.1275 (7)	−0.0075 (4)	0.0918 (5)	−0.0037 (4)
O1	0.107 (3)	0.0405 (19)	0.126 (3)	−0.0019 (18)	0.061 (2)	0.0037 (19)
O2	0.105 (3)	0.111 (3)	0.100 (3)	−0.012 (3)	0.042 (3)	0.002 (3)
O3	0.085 (3)	0.084 (3)	0.100 (3)	−0.009 (2)	0.036 (3)	0.000 (2)
O4	0.068 (2)	0.065 (2)	0.072 (2)	0.0053 (16)	0.0340 (18)	−0.0070 (17)
C1	0.076 (3)	0.067 (3)	0.072 (3)	−0.006 (3)	0.043 (3)	−0.012 (3)
C2	0.085 (4)	0.072 (4)	0.093 (4)	0.016 (3)	0.054 (3)	−0.005 (3)
C3	0.080 (3)	0.054 (3)	0.086 (4)	0.012 (2)	0.044 (3)	0.003 (2)
C4	0.075 (3)	0.051 (3)	0.086 (4)	0.000 (2)	0.039 (3)	0.001 (2)
C5	0.062 (3)	0.051 (3)	0.084 (4)	0.002 (2)	0.037 (3)	−0.005 (2)
C6	0.060 (3)	0.041 (2)	0.061 (3)	0.004 (2)	0.025 (2)	−0.005 (2)
C7	0.057 (3)	0.041 (2)	0.058 (3)	0.0010 (19)	0.022 (2)	−0.003 (2)
C8	0.065 (3)	0.042 (2)	0.078 (3)	−0.005 (2)	0.037 (3)	−0.003 (2)
C9	0.106 (4)	0.048 (3)	0.124 (5)	0.007 (3)	0.080 (4)	0.005 (3)
C10	0.067 (3)	0.050 (3)	0.083 (4)	0.003 (2)	0.036 (3)	−0.004 (2)
C11	0.071 (3)	0.047 (3)	0.079 (4)	0.000 (2)	0.028 (3)	0.000 (2)
C12	0.111 (4)	0.049 (3)	0.153 (6)	−0.006 (3)	0.091 (4)	0.003 (3)
C13	0.081 (4)	0.052 (3)	0.101 (5)	−0.010 (3)	0.048 (4)	−0.006 (3)
C14	0.065 (4)	0.109 (5)	0.189 (8)	−0.015 (4)	0.046 (5)	−0.004 (5)
C15	0.128 (7)	0.185 (9)	0.266 (12)	0.007 (7)	0.133 (8)	0.023 (9)
C16	0.089 (4)	0.047 (3)	0.082 (4)	−0.006 (3)	0.053 (3)	−0.001 (3)
C17	0.057 (3)	0.084 (4)	0.099 (4)	0.010 (3)	0.033 (3)	0.003 (3)
C18	0.061 (3)	0.080 (3)	0.079 (4)	−0.001 (3)	0.027 (3)	−0.014 (3)
C19	0.095 (4)	0.074 (3)	0.072 (4)	0.018 (3)	0.038 (3)	0.002 (3)
C20	0.073 (3)	0.077 (3)	0.068 (4)	0.016 (3)	0.022 (3)	−0.004 (3)
C21	0.068 (3)	0.049 (2)	0.063 (3)	−0.002 (2)	0.034 (3)	0.001 (2)
C22	0.081 (3)	0.081 (3)	0.079 (4)	−0.006 (3)	0.041 (3)	−0.016 (3)
C23	0.094 (4)	0.090 (4)	0.091 (4)	−0.013 (3)	0.056 (3)	−0.027 (3)

Br1—C1	1.886 (5)	C10—H10A	0.9300
O1—C11	1.216 (6)	C11—C12	1.490 (7)
O2—C13	1.176 (7)	C12—C13	1.493 (7)
O3—C13	1.311 (7)	C12—H12A	0.9800
O3—C14	1.442 (7)	C14—C15	1.465 (11)
O4—C21	1.374 (5)	C14—H14A	0.9700
O4—C22	1.419 (6)	C14—H14B	0.9700
C1—C2	1.361 (7)	C15—H15A	0.9600
C1—C4	1.366 (7)	C15—H15B	0.9600
C2—C3	1.357 (7)	C15—H15C	0.9600
C2—H2A	0.9300	C16—C17	1.360 (8)
C3—C6	1.393 (6)	C16—C19	1.370 (7)
C3—H3A	0.9300	C17—C18	1.382 (7)
C4—C5	1.375 (7)	C17—H17A	0.9300
C4—H4A	0.9300	C18—C21	1.365 (7)
C5—C6	1.375 (6)	C18—H18A	0.9300
C5—H5A	0.9300	C19—C20	1.366 (7)
C6—C7	1.470 (6)	C19—H19A	0.9300
C7—C10	1.342 (6)	C20—C21	1.363 (7)
C7—C8	1.492 (6)	C20—H20A	0.9300
C8—C9	1.492 (6)	C22—C23	1.480 (7)
C8—H8A	0.9700	C22—H22A	0.9700
C8—H8B	0.9700	C22—H22B	0.9700
C9—C12	1.436 (7)	C23—H23A	0.9600
C9—C16	1.512 (6)	C23—H23B	0.9600
C9—H9A	0.9800	C23—H23C	0.9600
C10—C11	1.429 (7)
C13—O3—C14	114.9 (5)	C13—C12—H12A	102.8
C21—O4—C22	117.1 (4)	O2—C13—O3	124.1 (5)
C2—C1—C4	120.8 (5)	O2—C13—C12	123.0 (7)
C2—C1—Br1	120.2 (4)	O3—C13—C12	112.9 (6)
C4—C1—Br1	119.1 (4)	O3—C14—C15	111.2 (6)
C3—C2—C1	120.0 (5)	O3—C14—H14A	109.4
C3—C2—H2A	120.0	C15—C14—H14A	109.4
C1—C2—H2A	120.0	O3—C14—H14B	109.4
C2—C3—C6	121.4 (5)	C15—C14—H14B	109.4
C2—C3—H3A	119.3	H14A—C14—H14B	108.0
C6—C3—H3A	119.3	C14—C15—H15A	109.5
C1—C4—C5	118.8 (5)	C14—C15—H15B	109.5
C1—C4—H4A	120.6	H15A—C15—H15B	109.5
C5—C4—H4A	120.6	C14—C15—H15C	109.5
C4—C5—C6	122.1 (4)	H15A—C15—H15C	109.5
C4—C5—H5A	119.0	H15B—C15—H15C	109.5
C6—C5—H5A	119.0	C17—C16—C19	116.9 (5)
C5—C6—C3	117.0 (4)	C17—C16—C9	121.4 (5)
C5—C6—C7	121.5 (4)	C19—C16—C9	121.6 (5)
C3—C6—C7	121.5 (4)	C16—C17—C18	123.1 (5)
C10—C7—C6	121.6 (4)	C16—C17—H17A	118.4
C10—C7—C8	120.0 (4)	C18—C17—H17A	118.4
C6—C7—C8	118.5 (4)	C21—C18—C17	118.4 (5)
C9—C8—C7	114.7 (4)	C21—C18—H18A	120.8
C9—C8—H8A	108.6	C17—C18—H18A	120.8
C7—C8—H8A	108.6	C20—C19—C16	121.1 (5)
C9—C8—H8B	108.6	C20—C19—H19A	119.5
C7—C8—H8B	108.6	C16—C19—H19A	119.5
H8A—C8—H8B	107.6	C21—C20—C19	121.0 (5)
C12—C9—C8	115.2 (4)	C21—C20—H20A	119.5
C12—C9—C16	114.7 (4)	C19—C20—H20A	119.5
C8—C9—C16	114.8 (4)	C20—C21—C18	119.4 (4)
C12—C9—H9A	103.2	C20—C21—O4	115.7 (4)
C8—C9—H9A	103.2	C18—C21—O4	124.9 (4)
C16—C9—H9A	103.2	O4—C22—C23	107.7 (4)
C7—C10—C11	124.0 (4)	O4—C22—H22A	110.2
C7—C10—H10A	118.0	C23—C22—H22A	110.2
C11—C10—H10A	118.0	O4—C22—H22B	110.2
O1—C11—C10	122.4 (5)	C23—C22—H22B	110.2
O1—C11—C12	121.0 (4)	H22A—C22—H22B	108.5
C10—C11—C12	116.6 (4)	C22—C23—H23A	109.5
C9—C12—C11	114.6 (5)	C22—C23—H23B	109.5
C9—C12—C13	118.9 (5)	H23A—C23—H23B	109.5
C11—C12—C13	112.1 (4)	C22—C23—H23C	109.5
C9—C12—H12A	102.8	H23A—C23—H23C	109.5
C11—C12—H12A	102.8	H23B—C23—H23C	109.5
C4—C1—C2—C3	0.5 (9)	C10—C11—C12—C9	−30.2 (8)
Br1—C1—C2—C3	−178.7 (4)	O1—C11—C12—C13	12.5 (8)
C1—C2—C3—C6	−0.4 (9)	C10—C11—C12—C13	−169.7 (5)
C2—C1—C4—C5	−0.9 (8)	C14—O3—C13—O2	−2.3 (8)
Br1—C1—C4—C5	178.3 (4)	C14—O3—C13—C12	178.0 (5)
C1—C4—C5—C6	1.2 (8)	C9—C12—C13—O2	123.8 (7)
C4—C5—C6—C3	−1.2 (7)	C11—C12—C13—O2	−98.6 (7)
C4—C5—C6—C7	178.6 (4)	C9—C12—C13—O3	−56.5 (7)
C2—C3—C6—C5	0.7 (8)	C11—C12—C13—O3	81.1 (6)
C2—C3—C6—C7	−179.0 (5)	C13—O3—C14—C15	−79.5 (8)
C5—C6—C7—C10	−162.0 (5)	C12—C9—C16—C17	−66.9 (7)
C3—C6—C7—C10	17.7 (7)	C8—C9—C16—C17	70.0 (7)
C5—C6—C7—C8	17.5 (6)	C12—C9—C16—C19	110.6 (6)
C3—C6—C7—C8	−162.8 (5)	C8—C9—C16—C19	−112.4 (6)
C10—C7—C8—C9	14.6 (7)	C19—C16—C17—C18	−2.6 (8)
C6—C7—C8—C9	−164.8 (4)	C9—C16—C17—C18	175.1 (5)
C7—C8—C9—C12	−37.7 (7)	C16—C17—C18—C21	0.1 (8)
C7—C8—C9—C16	−174.4 (5)	C17—C16—C19—C20	2.8 (8)
C6—C7—C10—C11	179.6 (4)	C9—C16—C19—C20	−174.8 (5)
C8—C7—C10—C11	0.2 (8)	C16—C19—C20—C21	−0.6 (8)
C7—C10—C11—O1	−175.0 (5)	C19—C20—C21—C18	−2.0 (8)
C7—C10—C11—C12	7.3 (8)	C19—C20—C21—O4	177.9 (4)
C8—C9—C12—C11	45.5 (8)	C17—C18—C21—C20	2.2 (7)
C16—C9—C12—C11	−177.8 (5)	C17—C18—C21—O4	−177.6 (4)
C8—C9—C12—C13	−178.0 (5)	C22—O4—C21—C20	−164.8 (4)
C16—C9—C12—C13	−41.2 (9)	C22—O4—C21—C18	15.0 (6)
O1—C11—C12—C9	152.0 (6)	C21—O4—C22—C23	171.5 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···O1i	0.93	2.42	3.163 (6)	137
C8—H8A···O2ii	0.97	2.59	3.244 (6)	125
C15—H15B···O2	0.96	2.58	3.062 (13)	111
C23—H23A···Cgiii	0.96	2.90	3.741 (6)	147

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5A⋯O1i	0.93	2.42	3.163 (6)	137
C8—H8A⋯O2ii	0.97	2.59	3.244 (6)	125
C15—H15B⋯O2	0.96	2.58	3.062 (13)	111
C23—H23A⋯Cgiii	0.96	2.90	3.741 (6)	147

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