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

El-Hiti, G.A.; Smith, K.; Balakit, A.A.; Masmali, A.; Kariuki, B.M.

doi:10.1107/S1600536813019752

organic compounds

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Volume 69| Part 9| September 2013| Page o1385

doi:10.1107/S1600536813019752

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

Gamal A. El-Hiti,^a ^* Keith Smith,^b Asim A. Balakit,^c Ali Masmali ^a and Benson M. Kariuki ^b ‡

^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 ); Kose (2004 ); Chandra et al. (2006 ); Zhao et al. (2009 ); Pu et al. (2010 ); Dinçalp et al. (2011 ).

Experimental

Crystal data

C₈H₆BrNS
M_r = 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 ) T_min = 0.243, T_max = 0.639
3294 measured reflections
1910 independent reflections
1769 reflections with I > 2σ(I)
R_int = 0.060

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.120
S = 1.05
1910 reflections
102 parameters
H-atom parameters constrained
Δρ_max = 0.74 e Å⁻³
Δρ_min = −1.12 e Å⁻³
Absolute structure: Flack (1983 ), 699 Friedel pairs
Absolute structure parameter: 0.03 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; 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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813019752/hg5330sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813019752/hg5330Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813019752/hg5330Isup3.cml

checkCIF report

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 (ν_max, cm^-1): 2211. Recrystallization from diethyl ether gave colorless crystals of the E-isomer (I).

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

	Fig. 1. A molecule of I showing atom labels and 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. A segment of the crystal structure showing C—H···N interactions as dashed lines.
	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

C₈H₆BrNS	F(000) = 448
M_r = 228.11	D_x = 1.752 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1769 reflections
a = 6.1347 (5) Å	θ = 3.0–28.4°
b = 7.1124 (3) Å	µ = 4.92 mm⁻¹
c = 19.8245 (13) Å	T = 150 K
V = 864.99 (10) Å³	Plate, yellow
Z = 4	0.40 × 0.30 × 0.10 mm

Data collection top

Nonius KappaCCD diffractometer	1910 independent reflections
Radiation source: fine-focus sealed tube	1769 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.060
CCD scans	θ_max = 27.4°, θ_min = 3.0°
Absorption correction: empirical (using intensity measurements) (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	h = −4→7
T_min = 0.243, T_max = 0.639	k = −9→7
3294 measured reflections	l = −25→20

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.048	w = 1/[σ²(F_o²) + (0.0412P)² + 2.3854P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.120	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.74 e Å⁻³
1910 reflections	Δρ_min = −1.12 e Å⁻³
102 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.030 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 699 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.03 (2)

Crystal data top

C₈H₆BrNS	V = 864.99 (10) Å³
M_r = 228.11	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.1347 (5) Å	µ = 4.92 mm⁻¹
b = 7.1124 (3) Å	T = 150 K
c = 19.8245 (13) Å	0.40 × 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)
T_min = 0.243, T_max = 0.639	R_int = 0.060
3294 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	H-atom parameters constrained
wR(F²) = 0.120	Δρ_max = 0.74 e Å⁻³
S = 1.05	Δρ_min = −1.12 e Å⁻³
1910 reflections	Absolute structure: Flack (1983), 699 Friedel pairs
102 parameters	Absolute 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

	x	y	z	U_iso*/U_eq
C1	−0.4336 (10)	−0.1420 (8)	0.7590 (3)	0.0265 (11)
C2	−0.2429 (10)	−0.1841 (9)	0.7200 (3)	0.0264 (12)
H2	−0.1959	−0.3079	0.7159	0.032*
C3	−0.1322 (9)	−0.0462 (8)	0.6895 (3)	0.0258 (12)
H3	−0.1824	0.0764	0.6946	0.031*
C4	0.0617 (10)	−0.0763 (7)	0.6489 (3)	0.0235 (11)
C5	0.1860 (10)	0.0569 (8)	0.6186 (3)	0.0222 (11)
H5	0.1553	0.1849	0.6203	0.027*
C6	0.3668 (10)	−0.0199 (8)	0.5843 (3)	0.0241 (12)
C7	0.3838 (8)	−0.2120 (7)	0.5887 (2)	0.0191 (11)
C8	0.5528 (11)	−0.3400 (7)	0.5583 (3)	0.0264 (12)
H8A	0.5059	−0.3791	0.5142	0.040*
H8B	0.5713	−0.4485	0.5865	0.040*
H8C	0.6888	−0.2741	0.5546	0.040*
N1	−0.5883 (9)	−0.1203 (8)	0.7912 (3)	0.0331 (11)
S1	0.1701 (3)	−0.2987 (2)	0.63524 (7)	0.0246 (3)
Br1	0.57000 (10)	0.12692 (8)	0.53635 (3)	0.0319 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.022 (3)	0.028 (3)	0.030 (3)	−0.001 (3)	0.000 (2)	0.000 (2)
C2	0.024 (3)	0.027 (3)	0.029 (3)	0.003 (2)	0.001 (2)	−0.005 (2)
C3	0.023 (3)	0.025 (3)	0.029 (3)	0.006 (2)	−0.002 (2)	−0.003 (2)
C4	0.016 (2)	0.025 (3)	0.030 (3)	0.003 (2)	−0.002 (2)	−0.001 (2)
C5	0.023 (3)	0.018 (2)	0.026 (3)	0.004 (2)	−0.006 (2)	−0.006 (2)
C6	0.025 (3)	0.024 (3)	0.023 (3)	−0.001 (2)	−0.001 (2)	−0.004 (2)
C7	0.021 (3)	0.019 (2)	0.017 (2)	0.002 (2)	−0.0057 (19)	0.0017 (19)
C8	0.032 (3)	0.019 (3)	0.028 (3)	0.002 (2)	0.002 (2)	0.003 (2)
N1	0.031 (3)	0.031 (2)	0.038 (3)	−0.008 (3)	0.002 (2)	−0.004 (2)
S1	0.0240 (7)	0.0207 (6)	0.0291 (7)	0.0007 (6)	0.0021 (6)	−0.0004 (5)
Br1	0.0332 (3)	0.0259 (3)	0.0368 (3)	−0.0021 (3)	0.0065 (3)	0.0040 (2)

Geometric parameters (Å, º) top

C1—N1	1.154 (8)	C5—H5	0.9300
C1—C2	1.434 (8)	C6—C7	1.373 (7)
C2—C3	1.338 (8)	C6—Br1	1.884 (6)
C2—H2	0.9300	C7—C8	1.506 (8)
C3—C4	1.452 (8)	C7—S1	1.717 (5)
C3—H3	0.9300	C8—H8A	0.9600
C4—C5	1.356 (8)	C8—H8B	0.9600
C4—S1	1.737 (5)	C8—H8C	0.9600
C5—C6	1.412 (8)

N1—C1—C2	175.6 (7)	C7—C6—C5	114.5 (5)
C3—C2—C1	120.3 (5)	C7—C6—Br1	122.3 (4)
C3—C2—H2	119.8	C5—C6—Br1	123.3 (4)
C1—C2—H2	119.8	C6—C7—C8	128.9 (5)
C2—C3—C4	123.9 (5)	C6—C7—S1	109.5 (4)
C2—C3—H3	118.0	C8—C7—S1	121.6 (4)
C4—C3—H3	118.0	C7—C8—H8A	109.5
C5—C4—C3	127.1 (5)	C7—C8—H8B	109.5
C5—C4—S1	110.6 (4)	H8A—C8—H8B	109.5
C3—C4—S1	122.3 (4)	C7—C8—H8C	109.5
C4—C5—C6	112.6 (5)	H8A—C8—H8C	109.5
C4—C5—H5	123.7	H8B—C8—H8C	109.5
C6—C5—H5	123.7	C7—S1—C4	92.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N1ⁱ	0.93	2.59	3.501 (8)	166

Symmetry code: (i) −x−1, y+1/2, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N1ⁱ	0.93	2.59	3.501 (8)	166.4

Symmetry code: (i) −x−1, 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.

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