(E)-Ethyl 3-(3-bromo­phen­yl)-2-cyano­acrylate

Ye, Y.; Shen, W.-L.; Wei, X.-W.

doi:10.1107/S1600536809039518

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2636

https://doi.org/10.1107/S1600536809039518

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(E)-Ethyl 3-(3-bromophenyl)-2-cyanoacrylate

Yin Ye,^a ^* Wei-Li Shen ^a and Xian-Wen Wei ^a

^aCollege of Chemistry and Materials Science, Anhui Key Laboratory of Functional Molecular Solid, Anhui Normal University, Wuhu 241000, People's Republic of China
^*Correspondence e-mail: yeyin307@yahoo.com.cn

(Received 16 September 2009; accepted 29 September 2009; online 3 October 2009)

The title molecule, C₁₂H₁₀BrNO₂, adopts an E configuration with respect to the C=C bond of the acrylate unit. In the crystal structure, molecules are connected by a pair of intermolecular C—H⋯O hydrogen bonds, forming a centrosymmetric dimer.

Related literature

For the synthesis, see: Lapworth & Baker (1927 ). For the title compound as an intermediate in drug synthesis, see: Obniska et al. (2005 ).

Experimental

Crystal data

C₁₂H₁₀BrNO₂
M_r = 280.12
Monoclinic, P 2₁ /c
a = 7.6147 (7) Å
b = 21.6015 (19) Å
c = 7.6044 (7) Å
β = 110.370 (1)°
V = 1172.62 (18) Å³
Z = 4
Mo Kα radiation
μ = 3.49 mm⁻¹
T = 298 K
0.17 × 0.14 × 0.09 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.597, T_max = 0.751
10143 measured reflections
2698 independent reflections
1730 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.081
S = 1.00
2698 reflections
146 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
C6—H6⋯O1ⁱ	0.93	2.47	3.323 (3)	152
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809039518/is2461sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809039518/is2461Isup2.hkl

checkCIF report

Comment top

The title compound is an important intermediate in drugs synthesis (Obniska et al., 2005). In this paper, we report the structure of the title compound (I). In (I), the molecule adopts an E configuration. Both the C7═C8 and the cyano (C12≡N1) groups deviate from the mean plane of the benzene C1–C6 ring. The crystal packing is stabilized by intermolecular non-classic C—H···O hydrogen bonds.

Related literature top

For the synthesis, see: Lapworth & Baker (1927). For the title compound as an intermediate in drug synthesis, see: Obniska et al. (2005).

Experimental top

The compound (I) was obtained by reaction of 3-bromobenzaldehyde (36.8 g, 0.2 mol) and ethyl 2-cyanoacetate (22.6 g, 0.2 mol) in the absolute ethanol (180 ml) containing 3.2 ml triethylamine according to the reported method (Lapworth et al., 1927). Single crystals suitable for X-ray diffraction were obtained by evaporation of an ethanol solution at room temperature.

Structure description top

For the synthesis, see: Lapworth & Baker (1927). For the title compound as an intermediate in drug synthesis, see: Obniska et al. (2005).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A packing diagram of (I) viewed down the c axis. Dotted lines show the C—H···O hydrogen bonds.

(E)-Ethyl 3-(3-bromophenyl)-2-cyanoacrylate top

Crystal data top

C₁₂H₁₀BrNO₂	F(000) = 560
M_r = 280.12	D_x = 1.587 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2803 reflections
a = 7.6147 (7) Å	θ = 2.9–25.8°
b = 21.6015 (19) Å	µ = 3.49 mm⁻¹
c = 7.6044 (7) Å	T = 298 K
β = 110.370 (1)°	Block, colorless
V = 1172.62 (18) Å³	0.17 × 0.14 × 0.09 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2698 independent reflections
Radiation source: fine-focus sealed tube	1730 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
φ and ω scans	θ_max = 27.6°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.597, T_max = 0.751	k = −28→28
10143 measured reflections	l = −8→9

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.081	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0337P)² + 0.2149P] where P = (F_o² + 2F_c²)/3
2698 reflections	(Δ/σ)_max = 0.001
146 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₁₂H₁₀BrNO₂	V = 1172.62 (18) Å³
M_r = 280.12	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.6147 (7) Å	µ = 3.49 mm⁻¹
b = 21.6015 (19) Å	T = 298 K
c = 7.6044 (7) Å	0.17 × 0.14 × 0.09 mm
β = 110.370 (1)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2698 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1730 reflections with I > 2σ(I)
T_min = 0.597, T_max = 0.751	R_int = 0.038
10143 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.081	H-atom parameters constrained
S = 1.00	Δρ_max = 0.21 e Å⁻³
2698 reflections	Δρ_min = −0.33 e Å⁻³
146 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
Br1	1.32627 (4)	0.459872 (14)	0.80815 (5)	0.06743 (14)
C5	1.1401 (4)	0.40161 (12)	0.6781 (4)	0.0491 (7)
C6	0.9564 (4)	0.42010 (12)	0.6053 (4)	0.0464 (6)
H6	0.9240	0.4608	0.6193	0.056*
C7	0.6257 (4)	0.39971 (12)	0.4366 (4)	0.0481 (6)
H7	0.6060	0.4373	0.4862	0.058*
C1	0.8179 (3)	0.37725 (11)	0.5098 (4)	0.0460 (6)
N1	0.4728 (3)	0.27353 (12)	0.1299 (4)	0.0694 (7)
C8	0.4721 (3)	0.37490 (11)	0.3089 (3)	0.0438 (6)
C4	1.1939 (4)	0.34169 (14)	0.6612 (4)	0.0626 (8)
H4	1.3192	0.3301	0.7101	0.075*
C2	0.8709 (4)	0.31640 (13)	0.4958 (4)	0.0629 (8)
H2	0.7806	0.2870	0.4362	0.075*
C10	−0.0327 (4)	0.40634 (13)	0.0878 (4)	0.0579 (8)
H10A	−0.0360	0.4404	0.0035	0.069*
H10B	−0.0578	0.4225	0.1957	0.069*
C11	−0.1756 (4)	0.35851 (14)	−0.0101 (5)	0.0682 (9)
H11A	−0.1452	0.3412	−0.1122	0.102*
H11B	−0.2972	0.3774	−0.0577	0.102*
H11C	−0.1759	0.3263	0.0768	0.102*
C3	1.0573 (4)	0.29951 (14)	0.5701 (5)	0.0754 (10)
H3	1.0912	0.2588	0.5582	0.090*
O2	0.1493 (2)	0.37612 (8)	0.1469 (2)	0.0517 (5)
O1	0.2787 (3)	0.46073 (9)	0.3104 (3)	0.0703 (6)
C12	0.4724 (3)	0.31789 (13)	0.2110 (4)	0.0500 (7)
C9	0.2926 (4)	0.40931 (13)	0.2581 (4)	0.0493 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.04546 (19)	0.0595 (2)	0.0794 (2)	−0.00844 (14)	−0.00088 (15)	−0.00303 (16)
C5	0.0422 (15)	0.0497 (16)	0.0478 (16)	−0.0039 (12)	0.0061 (13)	0.0000 (12)
C6	0.0477 (16)	0.0381 (14)	0.0488 (16)	0.0000 (11)	0.0109 (12)	0.0000 (12)
C7	0.0445 (15)	0.0409 (14)	0.0548 (17)	−0.0001 (11)	0.0119 (13)	−0.0013 (12)
C1	0.0394 (14)	0.0436 (14)	0.0476 (16)	−0.0031 (11)	0.0058 (12)	0.0004 (12)
N1	0.0519 (15)	0.0609 (16)	0.092 (2)	−0.0110 (12)	0.0204 (14)	−0.0237 (15)
C8	0.0381 (14)	0.0438 (14)	0.0474 (16)	−0.0023 (11)	0.0123 (12)	−0.0003 (12)
C4	0.0421 (16)	0.0558 (17)	0.076 (2)	0.0073 (13)	0.0024 (15)	−0.0037 (15)
C2	0.0503 (17)	0.0469 (16)	0.074 (2)	−0.0019 (13)	−0.0010 (15)	−0.0078 (14)
C10	0.0349 (15)	0.0605 (18)	0.073 (2)	0.0057 (13)	0.0125 (14)	−0.0015 (15)
C11	0.0390 (16)	0.077 (2)	0.079 (2)	−0.0025 (15)	0.0092 (15)	0.0018 (17)
C3	0.0539 (19)	0.0490 (17)	0.102 (3)	0.0099 (14)	0.0000 (18)	−0.0102 (17)
O2	0.0350 (10)	0.0511 (11)	0.0634 (12)	−0.0005 (8)	0.0098 (9)	−0.0070 (9)
O1	0.0505 (12)	0.0600 (13)	0.0904 (16)	0.0028 (10)	0.0119 (11)	−0.0251 (11)
C12	0.0329 (14)	0.0529 (16)	0.0594 (18)	−0.0069 (12)	0.0098 (13)	−0.0009 (14)
C9	0.0410 (15)	0.0534 (17)	0.0505 (17)	−0.0041 (12)	0.0120 (13)	−0.0033 (13)

Geometric parameters (Å, º) top

Br1—C5	1.896 (2)	C4—H4	0.9300
C5—C6	1.372 (3)	C2—C3	1.382 (4)
C5—C4	1.377 (4)	C2—H2	0.9300
C6—C1	1.401 (3)	C10—O2	1.454 (3)
C6—H6	0.9300	C10—C11	1.497 (4)
C7—C8	1.344 (3)	C10—H10A	0.9700
C7—C1	1.456 (3)	C10—H10B	0.9700
C7—H7	0.9300	C11—H11A	0.9600
C1—C2	1.390 (4)	C11—H11B	0.9600
N1—C12	1.140 (3)	C11—H11C	0.9600
C8—C12	1.439 (4)	C3—H3	0.9300
C8—C9	1.484 (4)	O2—C9	1.333 (3)
C4—C3	1.374 (4)	O1—C9	1.197 (3)

C6—C5—C4	122.0 (2)	O2—C10—C11	107.1 (2)
C6—C5—Br1	119.3 (2)	O2—C10—H10A	110.3
C4—C5—Br1	118.7 (2)	C11—C10—H10A	110.3
C5—C6—C1	119.6 (2)	O2—C10—H10B	110.3
C5—C6—H6	120.2	C11—C10—H10B	110.3
C1—C6—H6	120.2	H10A—C10—H10B	108.6
C8—C7—C1	130.5 (2)	C10—C11—H11A	109.5
C8—C7—H7	114.8	C10—C11—H11B	109.5
C1—C7—H7	114.8	H11A—C11—H11B	109.5
C2—C1—C6	118.6 (2)	C10—C11—H11C	109.5
C2—C1—C7	124.5 (2)	H11A—C11—H11C	109.5
C6—C1—C7	116.9 (2)	H11B—C11—H11C	109.5
C7—C8—C12	123.9 (2)	C4—C3—C2	121.3 (3)
C7—C8—C9	118.6 (2)	C4—C3—H3	119.3
C12—C8—C9	117.5 (2)	C2—C3—H3	119.3
C3—C4—C5	118.2 (3)	C9—O2—C10	115.9 (2)
C3—C4—H4	120.9	N1—C12—C8	178.3 (3)
C5—C4—H4	120.9	O1—C9—O2	124.2 (3)
C3—C2—C1	120.2 (3)	O1—C9—C8	124.0 (2)
C3—C2—H2	119.9	O2—C9—C8	111.8 (2)
C1—C2—H2	119.9

C4—C5—C6—C1	−0.3 (4)	C7—C1—C2—C3	−179.9 (3)
Br1—C5—C6—C1	−179.72 (19)	C5—C4—C3—C2	0.5 (5)
C5—C6—C1—C2	1.6 (4)	C1—C2—C3—C4	0.9 (5)
C5—C6—C1—C7	179.8 (2)	C11—C10—O2—C9	−171.7 (2)
C8—C7—C1—C2	−17.9 (5)	C10—O2—C9—O1	0.5 (4)
C8—C7—C1—C6	164.1 (3)	C10—O2—C9—C8	−179.3 (2)
C1—C7—C8—C12	−1.8 (5)	C7—C8—C9—O1	7.3 (4)
C1—C7—C8—C9	−178.8 (3)	C12—C8—C9—O1	−169.9 (3)
C6—C5—C4—C3	−0.8 (5)	C7—C8—C9—O2	−172.8 (2)
Br1—C5—C4—C3	178.7 (2)	C12—C8—C9—O2	9.9 (3)
C6—C1—C2—C3	−1.9 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O1ⁱ	0.93	2.47	3.323 (3)	152

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₀BrNO₂
M_r	280.12
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	7.6147 (7), 21.6015 (19), 7.6044 (7)
β (°)	110.370 (1)
V (Å³)	1172.62 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.49
Crystal size (mm)	0.17 × 0.14 × 0.09

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.597, 0.751
No. of measured, independent and observed [I > 2σ(I)] reflections	10143, 2698, 1730
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.081, 1.00
No. of reflections	2698
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.33

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O1ⁱ	0.93	2.47	3.323 (3)	152

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

This work was supported by the Science and Technology Fund of Anhui Province for Outstanding Youth (No. 08040106906), the National Natural Science Foundation (No. 20671002) of China, the State Education Ministry (EYTP, SRF for ROCS, SRFDP 20070370001) and the Education Department (No. KJ2008B169) of Anhui Province.

References

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Lapworth, A. & Baker, W. (1927). Org. Synth. 7, 20–21. CAS Google Scholar
Obniska, J., Jurczyk, S., Zejc, A., Kamiński, K., Tatarczyńska, E. & Stachowicz, K. (2005). Pharmacol. Rep. 57, 170–175. Web of Science PubMed CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
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