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Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): o2636.
Published online 2009 October 3. doi:  10.1107/S1600536809039518
PMCID: PMC2971297

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

Abstract

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 [triangle]). For the title compound as an inter­mediate in drug synthesis, see: Obniska et al. (2005 [triangle]).

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Object name is e-65-o2636-scheme1.jpg

Experimental

Crystal data

  • C12H10BrNO2
  • M r = 280.12
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2636-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.034
  • wR(F 2) = 0.081
  • S = 1.00
  • 2698 reflections
  • 146 parameters
  • H-atom parameters constrained
  • Δρmax = 0.21 e Å−3
  • Δρmin = −0.33 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT (Bruker, 2000 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809039518/is2461Isup2.hkl

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

Acknowledgments

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.

supplementary crystallographic information

Comment

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[equivalent]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.

Experimental

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.

Refinement

H atoms bonded to C atoms were introduced at calculated positions (C—H = 0.93–0.97 Å) and refined using a riding model, with Uiso(H) = 1.2Ueq(C).

Figures

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.

Crystal data

C12H10BrNO2F(000) = 560
Mr = 280.12Dx = 1.587 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2803 reflections
a = 7.6147 (7) Åθ = 2.9–25.8°
b = 21.6015 (19) ŵ = 3.49 mm1
c = 7.6044 (7) ÅT = 298 K
β = 110.370 (1)°Block, colorless
V = 1172.62 (18) Å30.17 × 0.14 × 0.09 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer2698 independent reflections
Radiation source: fine-focus sealed tube1730 reflections with I > 2σ(I)
graphiteRint = 0.038
[var phi] and ω scansθmax = 27.6°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −9→9
Tmin = 0.597, Tmax = 0.751k = −28→28
10143 measured reflectionsl = −8→9

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.081H-atom parameters constrained
S = 1.00w = 1/[σ2(Fo2) + (0.0337P)2 + 0.2149P] where P = (Fo2 + 2Fc2)/3
2698 reflections(Δ/σ)max = 0.001
146 parametersΔρmax = 0.21 e Å3
0 restraintsΔρmin = −0.33 e Å3

Special details

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)

xyzUiso*/Ueq
Br11.32627 (4)0.459872 (14)0.80815 (5)0.06743 (14)
C51.1401 (4)0.40161 (12)0.6781 (4)0.0491 (7)
C60.9564 (4)0.42010 (12)0.6053 (4)0.0464 (6)
H60.92400.46080.61930.056*
C70.6257 (4)0.39971 (12)0.4366 (4)0.0481 (6)
H70.60600.43730.48620.058*
C10.8179 (3)0.37725 (11)0.5098 (4)0.0460 (6)
N10.4728 (3)0.27353 (12)0.1299 (4)0.0694 (7)
C80.4721 (3)0.37490 (11)0.3089 (3)0.0438 (6)
C41.1939 (4)0.34169 (14)0.6612 (4)0.0626 (8)
H41.31920.33010.71010.075*
C20.8709 (4)0.31640 (13)0.4958 (4)0.0629 (8)
H20.78060.28700.43620.075*
C10−0.0327 (4)0.40634 (13)0.0878 (4)0.0579 (8)
H10A−0.03600.44040.00350.069*
H10B−0.05780.42250.19570.069*
C11−0.1756 (4)0.35851 (14)−0.0101 (5)0.0682 (9)
H11A−0.14520.3412−0.11220.102*
H11B−0.29720.3774−0.05770.102*
H11C−0.17590.32630.07680.102*
C31.0573 (4)0.29951 (14)0.5701 (5)0.0754 (10)
H31.09120.25880.55820.090*
O20.1493 (2)0.37612 (8)0.1469 (2)0.0517 (5)
O10.2787 (3)0.46073 (9)0.3104 (3)0.0703 (6)
C120.4724 (3)0.31789 (13)0.2110 (4)0.0500 (7)
C90.2926 (4)0.40931 (13)0.2581 (4)0.0493 (7)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.04546 (19)0.0595 (2)0.0794 (2)−0.00844 (14)−0.00088 (15)−0.00303 (16)
C50.0422 (15)0.0497 (16)0.0478 (16)−0.0039 (12)0.0061 (13)0.0000 (12)
C60.0477 (16)0.0381 (14)0.0488 (16)0.0000 (11)0.0109 (12)0.0000 (12)
C70.0445 (15)0.0409 (14)0.0548 (17)−0.0001 (11)0.0119 (13)−0.0013 (12)
C10.0394 (14)0.0436 (14)0.0476 (16)−0.0031 (11)0.0058 (12)0.0004 (12)
N10.0519 (15)0.0609 (16)0.092 (2)−0.0110 (12)0.0204 (14)−0.0237 (15)
C80.0381 (14)0.0438 (14)0.0474 (16)−0.0023 (11)0.0123 (12)−0.0003 (12)
C40.0421 (16)0.0558 (17)0.076 (2)0.0073 (13)0.0024 (15)−0.0037 (15)
C20.0503 (17)0.0469 (16)0.074 (2)−0.0019 (13)−0.0010 (15)−0.0078 (14)
C100.0349 (15)0.0605 (18)0.073 (2)0.0057 (13)0.0125 (14)−0.0015 (15)
C110.0390 (16)0.077 (2)0.079 (2)−0.0025 (15)0.0092 (15)0.0018 (17)
C30.0539 (19)0.0490 (17)0.102 (3)0.0099 (14)0.0000 (18)−0.0102 (17)
O20.0350 (10)0.0511 (11)0.0634 (12)−0.0005 (8)0.0098 (9)−0.0070 (9)
O10.0505 (12)0.0600 (13)0.0904 (16)0.0028 (10)0.0119 (11)−0.0251 (11)
C120.0329 (14)0.0529 (16)0.0594 (18)−0.0069 (12)0.0098 (13)−0.0009 (14)
C90.0410 (15)0.0534 (17)0.0505 (17)−0.0041 (12)0.0120 (13)−0.0033 (13)

Geometric parameters (Å, °)

Br1—C51.896 (2)C4—H40.9300
C5—C61.372 (3)C2—C31.382 (4)
C5—C41.377 (4)C2—H20.9300
C6—C11.401 (3)C10—O21.454 (3)
C6—H60.9300C10—C111.497 (4)
C7—C81.344 (3)C10—H10A0.9700
C7—C11.456 (3)C10—H10B0.9700
C7—H70.9300C11—H11A0.9600
C1—C21.390 (4)C11—H11B0.9600
N1—C121.140 (3)C11—H11C0.9600
C8—C121.439 (4)C3—H30.9300
C8—C91.484 (4)O2—C91.333 (3)
C4—C31.374 (4)O1—C91.197 (3)
C6—C5—C4122.0 (2)O2—C10—C11107.1 (2)
C6—C5—Br1119.3 (2)O2—C10—H10A110.3
C4—C5—Br1118.7 (2)C11—C10—H10A110.3
C5—C6—C1119.6 (2)O2—C10—H10B110.3
C5—C6—H6120.2C11—C10—H10B110.3
C1—C6—H6120.2H10A—C10—H10B108.6
C8—C7—C1130.5 (2)C10—C11—H11A109.5
C8—C7—H7114.8C10—C11—H11B109.5
C1—C7—H7114.8H11A—C11—H11B109.5
C2—C1—C6118.6 (2)C10—C11—H11C109.5
C2—C1—C7124.5 (2)H11A—C11—H11C109.5
C6—C1—C7116.9 (2)H11B—C11—H11C109.5
C7—C8—C12123.9 (2)C4—C3—C2121.3 (3)
C7—C8—C9118.6 (2)C4—C3—H3119.3
C12—C8—C9117.5 (2)C2—C3—H3119.3
C3—C4—C5118.2 (3)C9—O2—C10115.9 (2)
C3—C4—H4120.9N1—C12—C8178.3 (3)
C5—C4—H4120.9O1—C9—O2124.2 (3)
C3—C2—C1120.2 (3)O1—C9—C8124.0 (2)
C3—C2—H2119.9O2—C9—C8111.8 (2)
C1—C2—H2119.9
C4—C5—C6—C1−0.3 (4)C7—C1—C2—C3−179.9 (3)
Br1—C5—C6—C1−179.72 (19)C5—C4—C3—C20.5 (5)
C5—C6—C1—C21.6 (4)C1—C2—C3—C40.9 (5)
C5—C6—C1—C7179.8 (2)C11—C10—O2—C9−171.7 (2)
C8—C7—C1—C2−17.9 (5)C10—O2—C9—O10.5 (4)
C8—C7—C1—C6164.1 (3)C10—O2—C9—C8−179.3 (2)
C1—C7—C8—C12−1.8 (5)C7—C8—C9—O17.3 (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—C3178.7 (2)C12—C8—C9—O29.9 (3)
C6—C1—C2—C3−1.9 (5)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C6—H6···O1i0.932.473.323 (3)152

Symmetry codes: (i) −x+1, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IS2461).

References

  • Bruker (2000). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Lapworth, A. & Baker, W. (1927). Org. Synth.7, 20–21.
  • Obniska, J., Jurczyk, S., Zejc, A., Kamiński, K., Tatarczyńska, E. & Stachowicz, K. (2005). Pharmacol. Rep.57, 170–175. [PubMed]
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography