Ethyl 4-(4-bromo-phen-yl)-6-r-phenyl-2-oxocyclo-hex-3-ene-1-t-carboxyl-ate.

In the title compound, C(21)H(19)BrO(3), the cyclo-hexene ring adopts an envelope conformation, with all substituents equatorial. The plane through its five coplanar atoms makes dihedral angles of 28.88 (10) and 71.94 (10)° with the bromo-benzene and phenyl rings, respectively. The dihedral angle between the latter two rings is 51.49 (15)°. Inter-molecular C-H⋯O hydrogen bonds are found in the crystal structure; a C-H⋯π inter-action is also present.

Related literature

For the synthesis of cyclo­hexenone derivatives, see: Chong et al. (1997 ▶); Inokuchi et al. (2001 ▶). For their applications and for related structures, see: Anuradha et al. (2009 ▶); Fun et al. (2010 ▶).

Experimental

Crystal data

C21H19BrO3

M = 399.26

Monoclinic,

a = 11.0138 (2) Å

b = 13.8197 (4) Å

c = 12.1477 (3) Å

β = 95.180 (2)°

V = 1841.42 (8) Å3

Z = 4

Cu Kα radiation

μ = 3.17 mm−1

T = 295 K

0.44 × 0.36 × 0.12 mm

Data collection

Oxford Diffraction Xcalibur Ruby Gemini diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T min = 0.444, T max = 1.000

8385 measured reflections

3851 independent reflections

3210 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.150

S = 1.08

3851 reflections

227 parameters

H-atom parameters constrained

Δρmax = 0.32 e Å−3

Δρmin = −0.61 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810025353/tk2685sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810025353/tk2685Isup2.hkl

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

C21H19BrO3	F(000) = 816
Mr = 399.26	Dx = 1.440 Mg m−3
Monoclinic, P21/c	Melting point: 359 K
Hall symbol: -P 2ybc	Cu Kα radiation, λ = 1.54184 Å
a = 11.0138 (2) Å	Cell parameters from 4868 reflections
b = 13.8197 (4) Å	θ = 4.9–77.3°
c = 12.1477 (3) Å	µ = 3.17 mm−1
β = 95.180 (2)°	T = 295 K
V = 1841.42 (8) Å3	Prism, colourless
Z = 4	0.44 × 0.36 × 0.12 mm

Oxford Diffraction Xcalibur Ruby Gemini diffractometer	3851 independent reflections
Radiation source: Enhance (Cu) X-ray Source	3210 reflections with I > 2σ(I)
graphite	Rint = 0.021
Detector resolution: 10.5081 pixels mm-1	θmax = 77.5°, θmin = 4.9°
ω scans	h = −13→13
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −17→12
Tmin = 0.444, Tmax = 1.000	l = −14→15
8385 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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.150	H-atom parameters constrained
S = 1.08	w = 1/[σ2(Fo2) + (0.0892P)2 + 0.401P] where P = (Fo2 + 2Fc2)/3
3851 reflections	(Δ/σ)max = 0.001
227 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.61 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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 > 2σ(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
Br4	−0.27481 (3)	0.39721 (4)	−0.28199 (3)	0.1008 (2)
O2	0.0731 (2)	−0.01378 (13)	0.24548 (16)	0.0754 (7)
O11	0.2865 (2)	0.06999 (16)	0.46249 (16)	0.0814 (7)
O12	0.3423 (2)	0.03049 (16)	0.29591 (17)	0.0801 (8)
C1	0.1736 (2)	0.13392 (17)	0.30076 (18)	0.0551 (7)
C2	0.0916 (3)	0.07028 (17)	0.22341 (19)	0.0585 (7)
C3	0.0292 (2)	0.11697 (16)	0.12766 (19)	0.0557 (7)
C4	0.0424 (2)	0.21111 (16)	0.10325 (16)	0.0493 (6)
C5	0.1310 (2)	0.27481 (16)	0.17181 (18)	0.0547 (7)
C6	0.2304 (2)	0.21756 (17)	0.23886 (19)	0.0555 (7)
C11	0.2729 (3)	0.07369 (18)	0.3645 (2)	0.0625 (8)
C12	0.4481 (3)	−0.0246 (3)	0.3446 (3)	0.0906 (14)
C13	0.4140 (4)	−0.1191 (3)	0.3858 (4)	0.1036 (16)
C41	−0.0332 (2)	0.25631 (16)	0.01031 (17)	0.0507 (6)
C42	−0.0759 (2)	0.20198 (18)	−0.08178 (19)	0.0563 (7)
C43	−0.1466 (2)	0.2436 (2)	−0.1692 (2)	0.0652 (8)
C44	−0.1767 (2)	0.3402 (2)	−0.1636 (2)	0.0660 (8)
C45	−0.1361 (3)	0.3956 (2)	−0.0745 (2)	0.0679 (9)
C46	−0.0639 (3)	0.35454 (18)	0.0122 (2)	0.0606 (8)
C61	0.3109 (2)	0.27847 (18)	0.3204 (2)	0.0591 (7)
C62	0.2639 (3)	0.3446 (2)	0.3907 (2)	0.0695 (9)
C63	0.3395 (4)	0.3930 (2)	0.4700 (3)	0.0869 (13)
C64	0.4603 (4)	0.3765 (3)	0.4805 (3)	0.1013 (14)
C65	0.5093 (4)	0.3114 (3)	0.4118 (4)	0.1105 (18)
C66	0.4355 (3)	0.2627 (3)	0.3320 (3)	0.0862 (11)
H1	0.12304	0.16247	0.35470	0.0661*
H3	−0.02300	0.07976	0.08038	0.0668*
H5A	0.08663	0.31299	0.22186	0.0657*
H5B	0.16886	0.31918	0.12331	0.0657*
H6	0.28296	0.18886	0.18667	0.0666*
H12A	0.50529	−0.03357	0.28925	0.1087*
H12B	0.48887	0.01232	0.40502	0.1087*
H13A	0.36252	−0.11051	0.44476	0.1555*
H13B	0.48618	−0.15375	0.41285	0.1555*
H13C	0.37100	−0.15507	0.32702	0.1555*
H42	−0.05654	0.13658	−0.08455	0.0676*
H43	−0.17342	0.20688	−0.23080	0.0782*
H45	−0.15706	0.46075	−0.07220	0.0815*
H46	−0.03540	0.39252	0.07225	0.0727*
H62	0.18046	0.35672	0.38471	0.0834*
H63	0.30635	0.43742	0.51638	0.1042*
H64	0.51027	0.40899	0.53407	0.1213*
H65	0.59279	0.29993	0.41900	0.1324*
H66	0.46998	0.21897	0.28568	0.1035*

	U11	U22	U33	U12	U13	U23
Br4	0.0719 (3)	0.1319 (4)	0.0941 (3)	0.0257 (2)	−0.0167 (2)	0.0314 (2)
O2	0.1103 (15)	0.0451 (9)	0.0678 (11)	−0.0123 (9)	−0.0079 (10)	0.0056 (8)
O11	0.1096 (16)	0.0750 (12)	0.0560 (10)	−0.0024 (11)	−0.0120 (10)	0.0079 (9)
O12	0.0890 (14)	0.0775 (13)	0.0723 (12)	0.0158 (10)	−0.0011 (10)	0.0013 (10)
C1	0.0685 (14)	0.0503 (12)	0.0456 (10)	−0.0019 (10)	0.0009 (9)	0.0000 (9)
C2	0.0775 (15)	0.0471 (12)	0.0503 (11)	−0.0053 (10)	0.0027 (10)	−0.0011 (9)
C3	0.0682 (14)	0.0496 (12)	0.0475 (11)	−0.0090 (9)	−0.0043 (9)	−0.0053 (9)
C4	0.0591 (12)	0.0482 (11)	0.0402 (9)	−0.0027 (9)	0.0030 (8)	−0.0034 (8)
C5	0.0703 (14)	0.0475 (11)	0.0451 (10)	−0.0086 (10)	−0.0021 (9)	0.0012 (8)
C6	0.0626 (13)	0.0533 (12)	0.0498 (11)	−0.0047 (10)	0.0007 (9)	0.0007 (9)
C11	0.0781 (16)	0.0532 (12)	0.0545 (13)	−0.0045 (11)	−0.0037 (11)	0.0041 (10)
C12	0.078 (2)	0.084 (2)	0.106 (3)	0.0031 (16)	−0.0120 (17)	0.0005 (18)
C13	0.095 (3)	0.083 (2)	0.129 (3)	0.0085 (19)	−0.010 (2)	0.007 (2)
C41	0.0544 (11)	0.0529 (11)	0.0445 (10)	−0.0013 (9)	0.0026 (8)	−0.0026 (8)
C42	0.0595 (12)	0.0544 (12)	0.0531 (11)	−0.0012 (9)	−0.0052 (9)	−0.0029 (9)
C43	0.0588 (13)	0.0758 (16)	0.0582 (13)	−0.0011 (11)	−0.0094 (10)	−0.0044 (11)
C44	0.0493 (12)	0.0841 (18)	0.0631 (13)	0.0084 (11)	−0.0031 (10)	0.0144 (12)
C45	0.0711 (16)	0.0611 (14)	0.0717 (16)	0.0136 (11)	0.0071 (13)	0.0066 (12)
C46	0.0731 (15)	0.0542 (12)	0.0539 (12)	0.0043 (11)	0.0021 (10)	−0.0038 (10)
C61	0.0628 (13)	0.0575 (13)	0.0550 (12)	−0.0112 (10)	−0.0059 (10)	0.0093 (10)
C62	0.0751 (16)	0.0719 (16)	0.0597 (13)	−0.0180 (13)	−0.0038 (12)	−0.0048 (12)
C63	0.124 (3)	0.0730 (19)	0.0598 (15)	−0.0308 (17)	−0.0129 (16)	0.0008 (13)
C64	0.111 (3)	0.086 (2)	0.096 (2)	−0.036 (2)	−0.051 (2)	0.0200 (19)
C65	0.076 (2)	0.104 (3)	0.143 (4)	−0.020 (2)	−0.036 (2)	0.022 (3)
C66	0.0666 (17)	0.084 (2)	0.105 (2)	−0.0064 (14)	−0.0087 (16)	0.0123 (18)

Br4—C44	1.891 (2)	C62—C63	1.387 (5)
O2—C2	1.214 (3)	C63—C64	1.345 (6)
O11—C11	1.187 (3)	C64—C65	1.371 (6)
O12—C11	1.323 (4)	C65—C66	1.382 (6)
O12—C12	1.471 (4)	C1—H1	0.9800
C1—C2	1.523 (3)	C3—H3	0.9300
C1—C6	1.542 (3)	C5—H5A	0.9700
C1—C11	1.528 (4)	C5—H5B	0.9700
C2—C3	1.448 (3)	C6—H6	0.9800
C3—C4	1.345 (3)	C12—H12A	0.9700
C4—C5	1.508 (3)	C12—H12B	0.9700
C4—C41	1.479 (3)	C13—H13A	0.9600
C5—C6	1.525 (3)	C13—H13B	0.9600
C6—C61	1.522 (3)	C13—H13C	0.9600
C12—C13	1.460 (6)	C42—H42	0.9300
C41—C42	1.393 (3)	C43—H43	0.9300
C41—C46	1.400 (3)	C45—H45	0.9300
C42—C43	1.384 (3)	C46—H46	0.9300
C43—C44	1.379 (4)	C62—H62	0.9300
C44—C45	1.368 (4)	C63—H63	0.9300
C45—C46	1.383 (4)	C64—H64	0.9300
C61—C62	1.383 (4)	C65—H65	0.9300
C61—C66	1.384 (4)	C66—H66	0.9300
Br4···C63i	3.720 (3)	C62···H1	2.9700
Br4···C3ii	3.622 (2)	C63···H6vii	2.9800
Br4···H64iii	3.1100	C64···H64ix	2.9900
Br4···H12Aiv	3.2500	C65···H13Bx	3.0400
O2···O12	3.035 (3)	H1···C62	2.9700
O2···C42v	3.276 (3)	H1···C41vii	2.9000
O11···C61	3.382 (3)	H1···C42vii	3.0300
O11···C13	3.147 (5)	H1···C46vii	2.9400
O11···C45vi	3.288 (4)	H3···C42	2.6200
O12···C66	3.386 (5)	H3···H42	2.1500
O12···O2	3.035 (3)	H5A···C46	2.9700
O2···H46vi	2.6300	H5A···C62	2.7400
O2···H43v	2.9000	H5A···H46	2.4200
O2···H42v	2.5800	H5A···H62	2.2300
O11···H13A	2.6500	H5A···C43vii	3.0900
O11···H12B	2.5200	H5B···C46	2.8300
O11···H5Bvii	2.8800	H5B···H46	2.4900
O11···H45vi	2.5400	H5B···O11ii	2.8800
O12···H6	2.6100	H6···O12	2.6100
C2···C44vii	3.589 (4)	H6···C3	2.9900
C3···Br4vii	3.622 (2)	H6···H66	2.3300
C11···C66	3.212 (5)	H6···C63ii	2.9800
C13···O11	3.147 (5)	H12A···Br4xi	3.2500
C42···O2v	3.276 (3)	H12B···O11	2.5200
C44···C2ii	3.589 (4)	H12B···C12x	3.0600
C45···O11viii	3.288 (4)	H12B···C13x	3.0500
C61···O11	3.382 (3)	H12B···H12Bx	2.3200
C63···Br4i	3.720 (3)	H13A···O11	2.6500
C64···C64ix	3.545 (6)	H13A···C11	2.8700
C66···C11	3.212 (5)	H13A···C45vi	3.0700
C66···O12	3.386 (5)	H13B···C65x	3.0400
C3···H6	2.9900	H13C···H43v	2.4800
C3···H42	2.6800	H42···C3	2.6800
C5···H62	2.8300	H42···H3	2.1500
C5···H46	2.6600	H42···O2v	2.5800
C11···H13A	2.8700	H43···O2v	2.9000
C12···H12Bx	3.0600	H43···H13Cv	2.4800
C13···H12Bx	3.0500	H45···O11viii	2.5400
C41···H1ii	2.9000	H46···C5	2.6600
C42···H62ii	3.0000	H46···H5A	2.4200
C42···H1ii	3.0300	H46···H5B	2.4900
C42···H3	2.6200	H46···O2viii	2.6300
C43···H5Aii	3.0900	H62···C5	2.8300
C45···H13Aviii	3.0700	H62···H5A	2.2300
C46···H1ii	2.9400	H62···C42vii	3.0000
C46···H5A	2.9700	H64···Br4xii	3.1100
C46···H5B	2.8300	H64···C64ix	2.9900
C62···H5A	2.7400	H66···H6	2.3300
C11—O12—C12	117.5 (2)	C2—C3—H3	118.00
C2—C1—C6	112.10 (18)	C4—C3—H3	118.00
C2—C1—C11	110.8 (2)	C4—C5—H5A	109.00
C6—C1—C11	110.61 (19)	C4—C5—H5B	109.00
O2—C2—C1	121.2 (2)	C6—C5—H5A	109.00
O2—C2—C3	121.8 (2)	C6—C5—H5B	109.00
C1—C2—C3	116.8 (2)	H5A—C5—H5B	108.00
C2—C3—C4	123.7 (2)	C1—C6—H6	108.00
C3—C4—C5	121.35 (19)	C5—C6—H6	108.00
C3—C4—C41	120.8 (2)	C61—C6—H6	108.00
C5—C4—C41	117.81 (19)	O12—C12—H12A	109.00
C4—C5—C6	112.93 (18)	O12—C12—H12B	109.00
C1—C6—C5	110.24 (18)	C13—C12—H12A	109.00
C1—C6—C61	109.59 (19)	C13—C12—H12B	109.00
C5—C6—C61	114.11 (19)	H12A—C12—H12B	108.00
O11—C11—O12	125.8 (3)	C12—C13—H13A	109.00
O11—C11—C1	123.4 (3)	C12—C13—H13B	109.00
O12—C11—C1	110.8 (2)	C12—C13—H13C	109.00
O12—C12—C13	112.5 (3)	H13A—C13—H13B	109.00
C4—C41—C42	120.7 (2)	H13A—C13—H13C	110.00
C4—C41—C46	121.1 (2)	H13B—C13—H13C	110.00
C42—C41—C46	118.1 (2)	C41—C42—H42	119.00
C41—C42—C43	121.2 (2)	C43—C42—H42	119.00
C42—C43—C44	119.1 (2)	C42—C43—H43	120.00
Br4—C44—C43	119.30 (18)	C44—C43—H43	121.00
Br4—C44—C45	119.5 (2)	C44—C45—H45	120.00
C43—C44—C45	121.2 (2)	C46—C45—H45	120.00
C44—C45—C46	119.8 (3)	C41—C46—H46	120.00
C41—C46—C45	120.6 (2)	C45—C46—H46	120.00
C6—C61—C62	122.6 (2)	C61—C62—H62	120.00
C6—C61—C66	119.5 (2)	C63—C62—H62	120.00
C62—C61—C66	117.7 (3)	C62—C63—H63	120.00
C61—C62—C63	120.9 (3)	C64—C63—H63	120.00
C62—C63—C64	120.7 (3)	C63—C64—H64	120.00
C63—C64—C65	119.6 (4)	C65—C64—H64	120.00
C64—C65—C66	120.5 (4)	C64—C65—H65	120.00
C61—C66—C65	120.6 (3)	C66—C65—H65	120.00
C2—C1—H1	108.00	C61—C66—H66	120.00
C6—C1—H1	108.00	C65—C66—H66	120.00
C11—C1—H1	108.00
C12—O12—C11—O11	−2.1 (4)	C4—C5—C6—C1	−48.4 (2)
C12—O12—C11—C1	175.5 (2)	C4—C5—C6—C61	−172.20 (18)
C11—O12—C12—C13	78.0 (4)	C1—C6—C61—C62	−77.1 (3)
C6—C1—C2—O2	154.3 (3)	C1—C6—C61—C66	97.7 (3)
C6—C1—C2—C3	−30.8 (3)	C5—C6—C61—C62	47.1 (3)
C11—C1—C2—O2	30.2 (4)	C5—C6—C61—C66	−138.2 (3)
C11—C1—C2—C3	−154.9 (2)	C4—C41—C42—C43	−180.0 (2)
C2—C1—C6—C5	53.5 (3)	C46—C41—C42—C43	0.1 (3)
C2—C1—C6—C61	179.9 (2)	C4—C41—C46—C45	−179.1 (3)
C11—C1—C6—C5	177.74 (18)	C42—C41—C46—C45	0.9 (4)
C11—C1—C6—C61	−55.9 (2)	C41—C42—C43—C44	−1.1 (3)
C2—C1—C11—O11	−121.9 (3)	C42—C43—C44—Br4	−179.29 (17)
C2—C1—C11—O12	60.5 (3)	C42—C43—C44—C45	1.3 (4)
C6—C1—C11—O11	113.2 (3)	Br4—C44—C45—C46	−179.7 (2)
C6—C1—C11—O12	−64.5 (3)	C43—C44—C45—C46	−0.3 (4)
O2—C2—C3—C4	176.6 (3)	C44—C45—C46—C41	−0.8 (4)
C1—C2—C3—C4	1.6 (4)	C6—C61—C62—C63	174.7 (3)
C2—C3—C4—C5	3.8 (4)	C66—C61—C62—C63	−0.1 (4)
C2—C3—C4—C41	−173.9 (2)	C6—C61—C66—C65	−174.6 (3)
C3—C4—C5—C6	20.8 (3)	C62—C61—C66—C65	0.4 (5)
C41—C4—C5—C6	−161.42 (19)	C61—C62—C63—C64	−0.2 (5)
C3—C4—C41—C42	−29.7 (3)	C62—C63—C64—C65	0.3 (6)
C3—C4—C41—C46	150.3 (2)	C63—C64—C65—C66	0.0 (6)
C5—C4—C41—C42	152.5 (2)	C64—C65—C66—C61	−0.3 (6)
C5—C4—C41—C46	−27.5 (3)

Cg is the centroid of the C41–C46 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C42—H42···O2v	0.93	2.58	3.276 (3)	132
C45—H45···O11viii	0.93	2.54	3.288 (4)	138
C1—H1···Cgvii	0.98	2.77	3.648 (2)	150

Table 1

Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C41–C46 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C42—H42⋯O2i	0.93	2.58	3.276 (3)	132
C45—H45⋯O11ii	0.93	2.54	3.288 (4)	138
C1—H1⋯Cgiii	0.98	2.77	3.648 (2)	150

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