(E)-2-Bromo­methyl-3-(o-tol­yl)acrylo­nitrile

Kanchanadevi, J.; Anbalagan, G.; Selvakumar, R.; Bakthadoss, M.; Gunasekaran, B.; Manivannan, V.

doi:10.1107/S1600536813021041

organic compounds

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Volume 69| Part 9| September 2013| Page o1367

doi:10.1107/S1600536813021041

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(E)-2-Bromomethyl-3-(o-tolyl)acrylonitrile

J. Kanchanadevi,^a G. Anbalagan,^b R. Selvakumar,^c M. Bakthadoss,^c B. Gunasekaran ^d and V. Manivannan ^e ^*

^aDepartment of Physics, Velammal Institute of Technology, Panchetty, Chennai 601 204, India, ^bDepartment of Physics, Presidency College (Autonomous), Chennai 600 005, India, ^cDepartment of Organic Chemistry, University of Madras, Guindy campus, Chennai 600 025, India, ^dDepartment of Physics & Nano Technology, SRM University, SRM Nagar, Kattankulathur, Kancheepuram Dist, Chennai 603 203 Tamil Nadu, India, and ^eDepartment of Research and Development, PRIST University, Vallam, Thanjavur 613 403, Tamil Nadu, India
^*Correspondence e-mail: phdguna@gmail.com, crystallography2010@gmail.com

(Received 3 July 2013; accepted 28 July 2013; online 3 August 2013)

The title compound C₁₁H₁₀BrN, has an E conformation at the C=C bond of the acrylonitrile unit. The vinyl group makes a dihedral angle of 44.53 (12)° with the benzene ring. In the crystal, weak C—H⋯π interactions involving the benzene ring are observed.

Related literature

For the biological activity of cyanoacrylates, see: Zhang et al. (2009 ); Obniska et al. (2005 ); For related structures, see: Ye et al. (2009 ); Suresh et al. (2012 ).

Experimental

Crystal data

C₁₁H₁₀BrN
M_r = 236.11
Monoclinic, P 2₁ /n
a = 7.5473 (8) Å
b = 11.7362 (10) Å
c = 11.5228 (11) Å
β = 96.436 (3)°
V = 1014.22 (17) Å³
Z = 4
Mo Kα radiation
μ = 4.00 mm⁻¹
T = 295 K
0.20 × 0.20 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.435, T_max = 0.535
8718 measured reflections
1960 independent reflections
1261 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.085
S = 1.00
1960 reflections
119 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯Cg1ⁱ	0.93	2.97	3.654 (7)	131
C11—H11B⋯Cg1ⁱⁱ	0.96	2.86	3.699 (1)	146
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x+2, -y, -z+1.

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablock I. DOI: 10.1107/S1600536813021041/gk2587sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813021041/gk2587Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813021041/gk2587Isup3.cml

checkCIF report

Comment top

Cyanoacrylates and its derivatives have been widely used as agrochemicals (Zhang et al., 2009) and are an important intermediate in drug synthesis (Obniska et al., 2005).

The geometric parameters of the title molecule (Fig. 1) agree well with reported similar structure (Ye et al., 2009; Suresh et al., 2012). The vinyl group makes a dihedral angle of 44.53 (12) ° with the benzene ring. The acrylonitrile (C7–C8) and cyano (C9–N1) groups deviate from the mean plane of the benzene (C1–C6) ring.

The crystal packing is controlled by weak C—H···π [C7—H7···Cg1(1 - x, -y, 1 - z) distance of 3.654 (7) Å, C11—H11B···Cg1(2 - x, -y, 1 - z) distance of 3.699 (1) Å, (Cg1 is the centroid of the ring defined by the atoms C1—C6)] interactions.

Related literature top

For the biological activity of cyanoacrylates, see: Zhang et al. (2009); Obniska et al. (2005); For related structures, see: Ye et al. (2009); Suresh et al. (2012)

Experimental top

To a stirred solution of 2-[hydroxy(o-tolyl)methyl]acrylonitrile (1 equivalent) in dichloromethane (DCM) was added a 48% hydrobromic acid (2 equivalent) solution and then a concentrated sulfuric acid solution (catalytic amount) at 273 K. After stirring overnight at room temperature, the mixture was diluted with DCM and water. The aqueous phase was extracted twice with DCM. The combined organic phase was washed twice with water an then dried with sodiumsulfate. Removal of the solvent led to the crude product which was purified through a pad of silica gel (100–200 mesh) using ethylacetate and hexanes (1:9) as solvents. The pure title compound was obtained as a colorless solid (yield 90%; m.p. 383-387 K).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The packing diagram showing C-H···π interactions as dashed lines.

(E)-2-Bromomethyl-3-(o-tolyl)acrylonitrile top

Crystal data top

C₁₁H₁₀BrN	F(000) = 472
M_r = 236.11	D_x = 1.546 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1980 reflections
a = 7.5473 (8) Å	θ = 2.5–25.8°
b = 11.7362 (10) Å	µ = 4.00 mm⁻¹
c = 11.5228 (11) Å	T = 295 K
β = 96.436 (3)°	Block, colourless
V = 1014.22 (17) Å³	0.20 × 0.20 × 0.15 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	1960 independent reflections
Radiation source: fine-focus sealed tube	1261 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 0 pixels mm^-1	θ_max = 25.9°, θ_min = 2.5°
ω and ϕ scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −14→13
T_min = 0.435, T_max = 0.535	l = −14→14
8718 measured reflections

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.085	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.036P)² + 0.5483P] where P = (F_o² + 2F_c²)/3
1960 reflections	(Δ/σ)_max < 0.001
119 parameters	Δρ_max = 0.46 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₁H₁₀BrN	V = 1014.22 (17) Å³
M_r = 236.11	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.5473 (8) Å	µ = 4.00 mm⁻¹
b = 11.7362 (10) Å	T = 295 K
c = 11.5228 (11) Å	0.20 × 0.20 × 0.15 mm
β = 96.436 (3)°

Data collection top

Bruker APEXII CCD diffractometer	1960 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1261 reflections with I > 2σ(I)
T_min = 0.435, T_max = 0.535	R_int = 0.034
8718 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.085	H-atom parameters constrained
S = 1.00	Δρ_max = 0.46 e Å⁻³
1960 reflections	Δρ_min = −0.26 e Å⁻³
119 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.7824 (4)	−0.0112 (3)	0.5604 (3)	0.0451 (8)
C2	0.8374 (5)	0.0182 (4)	0.6742 (3)	0.0587 (10)
H2	0.8886	−0.0372	0.7252	0.070*
C3	0.8186 (5)	0.1269 (4)	0.7146 (3)	0.0702 (12)
H3	0.8563	0.1443	0.7922	0.084*
C4	0.7448 (5)	0.2096 (4)	0.6414 (3)	0.0634 (11)
H4	0.7307	0.2831	0.6691	0.076*
C5	0.6911 (5)	0.1840 (3)	0.5260 (3)	0.0508 (9)
H5	0.6417	0.2406	0.4759	0.061*
C6	0.7101 (4)	0.0752 (3)	0.4843 (3)	0.0398 (8)
C7	0.6525 (4)	0.0464 (3)	0.3617 (3)	0.0411 (7)
H7	0.5936	−0.0227	0.3480	0.049*
C8	0.6760 (4)	0.1091 (3)	0.2682 (2)	0.0410 (8)
C9	0.7740 (5)	0.2128 (3)	0.2782 (3)	0.0496 (9)
C10	0.6063 (5)	0.0732 (3)	0.1480 (3)	0.0530 (9)
H10A	0.5312	0.1331	0.1112	0.064*
H10B	0.5336	0.0055	0.1521	0.064*
C11	0.8037 (5)	−0.1309 (3)	0.5196 (3)	0.0582 (9)
H11A	0.8550	−0.1767	0.5838	0.087*
H11B	0.8807	−0.1316	0.4587	0.087*
H11C	0.6892	−0.1611	0.4903	0.087*
N1	0.8572 (5)	0.2944 (3)	0.2831 (3)	0.0750 (10)
Br1	0.79897 (5)	0.04122 (4)	0.05323 (3)	0.07015 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0373 (19)	0.053 (2)	0.0457 (18)	−0.0111 (16)	0.0080 (14)	0.0050 (16)
C2	0.057 (2)	0.076 (3)	0.0429 (19)	−0.011 (2)	0.0049 (17)	0.0097 (18)
C3	0.071 (3)	0.101 (4)	0.039 (2)	−0.023 (3)	0.0111 (19)	−0.011 (2)
C4	0.069 (3)	0.069 (3)	0.057 (2)	−0.013 (2)	0.026 (2)	−0.022 (2)
C5	0.053 (2)	0.050 (2)	0.052 (2)	−0.0022 (17)	0.0165 (16)	−0.0044 (16)
C6	0.0321 (17)	0.049 (2)	0.0398 (16)	−0.0060 (14)	0.0106 (14)	−0.0021 (14)
C7	0.0353 (17)	0.043 (2)	0.0452 (17)	0.0012 (15)	0.0058 (14)	−0.0036 (15)
C8	0.0381 (18)	0.043 (2)	0.0412 (17)	0.0057 (16)	0.0041 (14)	0.0000 (15)
C9	0.062 (2)	0.048 (2)	0.0392 (18)	0.005 (2)	0.0082 (16)	0.0103 (16)
C10	0.051 (2)	0.062 (2)	0.0444 (18)	0.0072 (17)	−0.0035 (15)	−0.0007 (15)
C11	0.055 (2)	0.053 (2)	0.065 (2)	−0.0032 (18)	0.0013 (18)	0.0105 (18)
N1	0.099 (3)	0.059 (2)	0.068 (2)	−0.011 (2)	0.0173 (18)	0.0085 (17)
Br1	0.0798 (3)	0.0886 (4)	0.0435 (2)	0.0105 (2)	0.01345 (18)	−0.00341 (19)

Geometric parameters (Å, º) top

C1—C2	1.374 (4)	C7—C8	1.334 (4)
C1—C6	1.409 (4)	C7—H7	0.9300
C1—C11	1.495 (5)	C8—C9	1.422 (5)
C2—C3	1.371 (6)	C8—C10	1.486 (4)
C2—H2	0.9300	C9—N1	1.143 (4)
C3—C4	1.364 (6)	C10—Br1	1.950 (3)
C3—H3	0.9300	C10—H10A	0.9700
C4—C5	1.379 (5)	C10—H10B	0.9700
C4—H4	0.9300	C11—H11A	0.9600
C5—C6	1.378 (4)	C11—H11B	0.9600
C5—H5	0.9300	C11—H11C	0.9600
C6—C7	1.470 (4)

C2—C1—C6	117.9 (3)	C8—C7—H7	116.6
C2—C1—C11	120.2 (3)	C6—C7—H7	116.6
C6—C1—C11	121.8 (3)	C7—C8—C9	121.4 (3)
C3—C2—C1	121.7 (4)	C7—C8—C10	122.1 (3)
C3—C2—H2	119.2	C9—C8—C10	116.4 (3)
C1—C2—H2	119.2	N1—C9—C8	177.2 (4)
C4—C3—C2	120.2 (3)	C8—C10—Br1	111.6 (2)
C4—C3—H3	119.9	C8—C10—H10A	109.3
C2—C3—H3	119.9	Br1—C10—H10A	109.3
C3—C4—C5	119.8 (4)	C8—C10—H10B	109.3
C3—C4—H4	120.1	Br1—C10—H10B	109.3
C5—C4—H4	120.1	H10A—C10—H10B	108.0
C6—C5—C4	120.5 (3)	C1—C11—H11A	109.5
C6—C5—H5	119.8	C1—C11—H11B	109.5
C4—C5—H5	119.8	H11A—C11—H11B	109.5
C5—C6—C1	119.9 (3)	C1—C11—H11C	109.5
C5—C6—C7	121.1 (3)	H11A—C11—H11C	109.5
C1—C6—C7	119.0 (3)	H11B—C11—H11C	109.5
C8—C7—C6	126.7 (3)

C6—C1—C2—C3	1.8 (5)	C2—C1—C6—C7	179.2 (3)
C11—C1—C2—C3	−179.6 (3)	C11—C1—C6—C7	0.6 (4)
C1—C2—C3—C4	−0.4 (5)	C5—C6—C7—C8	41.9 (5)
C2—C3—C4—C5	−0.9 (5)	C1—C6—C7—C8	−139.4 (3)
C3—C4—C5—C6	0.5 (5)	C6—C7—C8—C9	3.9 (5)
C4—C5—C6—C1	1.0 (5)	C6—C7—C8—C10	−177.8 (3)
C4—C5—C6—C7	179.6 (3)	C7—C8—C10—Br1	−114.5 (3)
C2—C1—C6—C5	−2.1 (4)	C9—C8—C10—Br1	63.9 (3)
C11—C1—C6—C5	179.3 (3)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 ring

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···Cg1ⁱ	0.93	2.97	3.654 (7)	131
C11—H11B···Cg1ⁱⁱ	0.96	2.86	3.699 (1)	146

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 ring

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···Cg1ⁱ	0.93	2.97	3.654 (7)	131
C11—H11B···Cg1ⁱⁱ	0.96	2.86	3.699 (1)	146

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+2, −y, −z+1.

References

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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 9| September 2013| Page o1367

doi:10.1107/S1600536813021041

Open

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