organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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(E)-3-(4-Bromo-5-methyl­thio­phen-2-yl)acrylo­nitrile

aDepartment of Optometry, College of Applied Medical Sciences, King Saud University, PO Box 10219, Riyadh 11433, Saudi Arabia, bSchool of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, Wales, and cDepartment of Chemistry, College of Science for Women, University of Babylon, Babylon, Iraq
*Correspondence e-mail: gelhiti@ksu.edu.sa

(Received 10 July 2013; accepted 17 July 2013; online 7 August 2013)

In the title structure, C8H6BrNS, the molecules are planar with the exception of the methyl H atoms. In the crystal, molecules are linked by intermolecular C—H⋯N interactions to form ribbons parallel to the b axis. Groups of ribbons are arranged in a herringbone pattern to form a layered structure parallel to the ab plane.

Related literature

For related structures and their applications, see: Perner et al. (2003[Perner, R. J., Gu, Y.-G., Lee, C.-H., Bayburt, E. K., McKie, J., Alexander, K. M., Kohlhaas, K. L., Wismer, C. T., Mikusa, J., Jarvis, M. F., Kowaluk, E. A. & Bhagwat, S. S. (2003). J. Med. Chem. 46, 5249-5257.]); Kose (2004[Kose, M. (2004). J. Photochem. Photobiol. A, 165, 97-102.]); Chandra et al. (2006[Chandra, R., Kung, M.-P. & Kung, H. F. (2006). Bioorg. Med. Chem. Lett. 16, 1350-1352.]); Zhao et al. (2009[Zhao, J., Huang, L., Cheng, K. & Zhang, Y. (2009). Tetrahedron Lett. 50, 2758-2761.]); Pu et al. (2010[Pu, S., Liu, W. & Liu, G. (2010). Dyes Pigm. 87, 1-9.]); Dinçalp et al. (2011[Dinçalp, H., Aşkar, Z., Zafer, C. & İçli, S. (2011). Dyes Pigm. 91, 182-191.]).

[Scheme 1]

Experimental

Crystal data
  • C8H6BrNS

  • Mr = 228.11

  • Orthorhombic, P 21 21 21

  • a = 6.1347 (5) Å

  • b = 7.1124 (3) Å

  • c = 19.8245 (13) Å

  • V = 864.99 (10) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 4.92 mm−1

  • T = 150 K

  • 0.40 × 0.30 × 0.10 mm

Data collection
  • Nonius KappaCCD diffractometer

  • Absorption correction: empirical (using intensity measurements) (DENZO/SCALEPACK; Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]) Tmin = 0.243, Tmax = 0.639

  • 3294 measured reflections

  • 1910 independent reflections

  • 1769 reflections with I > 2σ(I)

  • Rint = 0.060

Refinement
  • R[F2 > 2σ(F2)] = 0.048

  • wR(F2) = 0.120

  • S = 1.05

  • 1910 reflections

  • 102 parameters

  • H-atom parameters constrained

  • Δρmax = 0.74 e Å−3

  • Δρmin = −1.12 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 699 Friedel pairs

  • Absolute structure parameter: 0.03 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C3—H3⋯N1i 0.93 2.59 3.501 (8) 166
Symmetry code: (i) [-x-1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}].

Data collection: COLLECT (Nonius, 2000[Nonius (2000). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]); software used to prepare material for publication: WinGX (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) and CHEMDRAW Ultra (Cambridge Soft, 2001[Cambridge Soft (2001). CHEMDRAW Ultra. Cambridge Soft Corporation, Cambridge, Massachusetts, USA.]).

Supporting information


Comment top

During the research focused on new synthetic routes towards novel substituted thiophene derivatives, we have synthesized the title compound (I), which was isolated in high yield. Thiophene derivatives are interesting compounds (Zhao et al., 2009). They can be used in a wide range of applications such as enzyme inhibitors (Perner et al., 2003), photochromic materials (Kose, 2004; Pu et al., 2010), bioprobes (Chandra et al., 2006) and dyes (Dinçalp et al., 2011).

In the structure, the molecules of (E)-3-(4-bromo-5-methylthiophen-2-yl)-acrylonitrile (I) are planar, except for H atoms of the methyl group (Fig. 1). The molecules are linked by C—H···N interactions (Table 1) to form corrugated ribbons. The ribbons run parallel to the b axis and, within a ribbon, the orientation of consecutive molecules alternates to the left and right (Fig. 2). Groups of ribbons are arranged in a herringbone pattern to form a layered structure with layers parallel to the ab plane (Fig. 3).

Related literature top

For related structures and their applications, see: Perner et al. (2003); Kose (2004); Chandra et al. (2006); Zhao et al. (2009); Pu et al. (2010); Dinçalp et al. (2011).

Experimental top

Synthesis of E-3-(4-bromo-5-methylthiophen-2-yl)acrylonitrile (I)

Diethyl (cyanomethyl)phosphonate (0.94 g, 5.3 mmol) was added to sodium hydride (6.25 mmol) suspended in dry THF (50 ml) under inert atmosphere. The mixture was stirred for 1 h, 3-bromo-2-methylthiophene-5-carboxaldehyde (1.00 g, 4.90 mmol) was added and stirring was continued overnight. Saturated aqueous ammonium chloride solution (25 ml) was added and the mixture was extracted with diethyl ether (4 × 50 ml). The organic phase was washed with saturated aqueous sodium hydrogen carbonate solution (50 ml) and brine (25 ml) and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure and the crude product was separated by column chromatography (silica gel, Et2O:hexane in 1:1 by volume) to give a mixture of E- and Z-isomers of 3-(4-bromo-5-methylthiophen-2-yl)acrylonitrile in 4:1 ratio. m.p. 80–81°C. 1H NMR (400 MHz, CDCl3, δ, p.p.m.): 7.23 (d, J = 16.3 Hz, 0.8H), 7.20 (d, J = 11.7 Hz, 0.2H), 6.98 (s, 1H), 5.46 (d, J = 16.3 Hz, 0.8H), 5.15 (d, J = 11.7 Hz, 0.2H), 2.37 (s, 0.6H), 2.35 (s, 2.4H). 13C NMR (100 MHz, CDCl3, δ, p.p.m.): 141.6 (d), 140.0 (d), 138.9 (s), 135.2 (s), 134.8 (d), 133.5 (d), 117.8 (s), 110.9 (s), 94.5 (d), 91.2 (d), 15.4 (q). EI–MS (m/z, %): 229 ([M 81Br]+, 80), 227 ([M 79Br]+, 78), 148 (100), 121 (10). HRMS (EI): Calculated for C8H6BrNS [M 79Br]+ 226.9404; found: 226.9402. FT–IR (νmax, cm-1): 2211. Recrystallization from diethyl ether gave colorless crystals of the E-isomer (I).

Refinement top

H atoms were positioned geometrically and refined using a riding model. For sp2 H atoms, Uiso(H) is constrained to 1.2 times the Ueq for the atoms they are bonded to and the C—H distance is 0.93 Å. For the methyl group, Uiso(H) is 1.5 times the Ueq for C atom they are bonded to and the C—H distance is 0.96 Å, with free rotation about the C—C bond.

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012) and CHEMDRAW Ultra (Cambridge Soft, 2001).

Figures top
[Figure 1] Fig. 1. A molecule of I showing atom labels and 50% probability displacement ellipsoids for non-H atoms.
[Figure 2] Fig. 2. A segment of the crystal structure showing C—H···N interactions as dashed lines.
[Figure 3] Fig. 3. A segment of the crystal structure of I showing the herringbone arrangement to form layers of ribbons.
(E)-3-(4-Bromo-5-methylthiophen-2-yl)acrylonitrile top
Crystal data top
C8H6BrNSF(000) = 448
Mr = 228.11Dx = 1.752 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 1769 reflections
a = 6.1347 (5) Åθ = 3.0–28.4°
b = 7.1124 (3) ŵ = 4.92 mm1
c = 19.8245 (13) ÅT = 150 K
V = 864.99 (10) Å3Plate, yellow
Z = 40.40 × 0.30 × 0.10 mm
Data collection top
Nonius KappaCCD
diffractometer
1910 independent reflections
Radiation source: fine-focus sealed tube1769 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.060
CCD scansθmax = 27.4°, θmin = 3.0°
Absorption correction: empirical (using intensity measurements)
(DENZO/SCALEPACK; Otwinowski & Minor, 1997)
h = 47
Tmin = 0.243, Tmax = 0.639k = 97
3294 measured reflectionsl = 2520
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.048 w = 1/[σ2(Fo2) + (0.0412P)2 + 2.3854P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.120(Δ/σ)max < 0.001
S = 1.05Δρmax = 0.74 e Å3
1910 reflectionsΔρmin = 1.12 e Å3
102 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.030 (3)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 699 Friedel pairs
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.03 (2)
Crystal data top
C8H6BrNSV = 864.99 (10) Å3
Mr = 228.11Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 6.1347 (5) ŵ = 4.92 mm1
b = 7.1124 (3) ÅT = 150 K
c = 19.8245 (13) Å0.40 × 0.30 × 0.10 mm
Data collection top
Nonius KappaCCD
diffractometer
1910 independent reflections
Absorption correction: empirical (using intensity measurements)
(DENZO/SCALEPACK; Otwinowski & Minor, 1997)
1769 reflections with I > 2σ(I)
Tmin = 0.243, Tmax = 0.639Rint = 0.060
3294 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.048H-atom parameters constrained
wR(F2) = 0.120Δρmax = 0.74 e Å3
S = 1.05Δρmin = 1.12 e Å3
1910 reflectionsAbsolute structure: Flack (1983), 699 Friedel pairs
102 parametersAbsolute structure parameter: 0.03 (2)
0 restraints
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
xyzUiso*/Ueq
C10.4336 (10)0.1420 (8)0.7590 (3)0.0265 (11)
C20.2429 (10)0.1841 (9)0.7200 (3)0.0264 (12)
H20.19590.30790.71590.032*
C30.1322 (9)0.0462 (8)0.6895 (3)0.0258 (12)
H30.18240.07640.69460.031*
C40.0617 (10)0.0763 (7)0.6489 (3)0.0235 (11)
C50.1860 (10)0.0569 (8)0.6186 (3)0.0222 (11)
H50.15530.18490.62030.027*
C60.3668 (10)0.0199 (8)0.5843 (3)0.0241 (12)
C70.3838 (8)0.2120 (7)0.5887 (2)0.0191 (11)
C80.5528 (11)0.3400 (7)0.5583 (3)0.0264 (12)
H8A0.50590.37910.51420.040*
H8B0.57130.44850.58650.040*
H8C0.68880.27410.55460.040*
N10.5883 (9)0.1203 (8)0.7912 (3)0.0331 (11)
S10.1701 (3)0.2987 (2)0.63524 (7)0.0246 (3)
Br10.57000 (10)0.12692 (8)0.53635 (3)0.0319 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.022 (3)0.028 (3)0.030 (3)0.001 (3)0.000 (2)0.000 (2)
C20.024 (3)0.027 (3)0.029 (3)0.003 (2)0.001 (2)0.005 (2)
C30.023 (3)0.025 (3)0.029 (3)0.006 (2)0.002 (2)0.003 (2)
C40.016 (2)0.025 (3)0.030 (3)0.003 (2)0.002 (2)0.001 (2)
C50.023 (3)0.018 (2)0.026 (3)0.004 (2)0.006 (2)0.006 (2)
C60.025 (3)0.024 (3)0.023 (3)0.001 (2)0.001 (2)0.004 (2)
C70.021 (3)0.019 (2)0.017 (2)0.002 (2)0.0057 (19)0.0017 (19)
C80.032 (3)0.019 (3)0.028 (3)0.002 (2)0.002 (2)0.003 (2)
N10.031 (3)0.031 (2)0.038 (3)0.008 (3)0.002 (2)0.004 (2)
S10.0240 (7)0.0207 (6)0.0291 (7)0.0007 (6)0.0021 (6)0.0004 (5)
Br10.0332 (3)0.0259 (3)0.0368 (3)0.0021 (3)0.0065 (3)0.0040 (2)
Geometric parameters (Å, º) top
C1—N11.154 (8)C5—H50.9300
C1—C21.434 (8)C6—C71.373 (7)
C2—C31.338 (8)C6—Br11.884 (6)
C2—H20.9300C7—C81.506 (8)
C3—C41.452 (8)C7—S11.717 (5)
C3—H30.9300C8—H8A0.9600
C4—C51.356 (8)C8—H8B0.9600
C4—S11.737 (5)C8—H8C0.9600
C5—C61.412 (8)
N1—C1—C2175.6 (7)C7—C6—C5114.5 (5)
C3—C2—C1120.3 (5)C7—C6—Br1122.3 (4)
C3—C2—H2119.8C5—C6—Br1123.3 (4)
C1—C2—H2119.8C6—C7—C8128.9 (5)
C2—C3—C4123.9 (5)C6—C7—S1109.5 (4)
C2—C3—H3118.0C8—C7—S1121.6 (4)
C4—C3—H3118.0C7—C8—H8A109.5
C5—C4—C3127.1 (5)C7—C8—H8B109.5
C5—C4—S1110.6 (4)H8A—C8—H8B109.5
C3—C4—S1122.3 (4)C7—C8—H8C109.5
C4—C5—C6112.6 (5)H8A—C8—H8C109.5
C4—C5—H5123.7H8B—C8—H8C109.5
C6—C5—H5123.7C7—S1—C492.8 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3···N1i0.932.593.501 (8)166
Symmetry code: (i) x1, y+1/2, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3···N1i0.932.593.501 (8)166.4
Symmetry code: (i) x1, y+1/2, z+3/2.
 

Footnotes

Additional correspondence author, email: kariukib@cardiff.ac.uk.

Acknowledgements

The authors extend their appreciation to the Deanship of Scientific Research at King Saud University for its funding for this research through Research Group Project No. RGP-VPP-239.

References

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First citationChandra, R., Kung, M.-P. & Kung, H. F. (2006). Bioorg. Med. Chem. Lett. 16, 1350–1352.  Web of Science CrossRef PubMed CAS
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First citationPerner, R. J., Gu, Y.-G., Lee, C.-H., Bayburt, E. K., McKie, J., Alexander, K. M., Kohlhaas, K. L., Wismer, C. T., Mikusa, J., Jarvis, M. F., Kowaluk, E. A. & Bhagwat, S. S. (2003). J. Med. Chem. 46, 5249–5257.  Web of Science CrossRef PubMed CAS
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First citationZhao, J., Huang, L., Cheng, K. & Zhang, Y. (2009). Tetrahedron Lett. 50, 2758–2761.  Web of Science CrossRef CAS

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