Ethyl (2E)-2-cyano-3-(4-meth­oxy­phen­yl)acrylate

Suchetan, P.A.; Palakshamurthy, B.S.; Mohan, N.R.; Madan Kumar, S.; Lokanath, N.K.; Sreenivasa, S.

doi:10.1107/S1600536813026871

organic compounds

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ISSN: 2056-9890

Volume 69| Part 11| November 2013| Page o1610

doi:10.1107/S1600536813026871

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Ethyl (2E)-2-cyano-3-(4-methoxyphenyl)acrylate

P. A. Suchetan,^a B. S. Palakshamurthy,^b N. R. Mohan,^c S. Madan Kumar,^d N. K. Lokanath ^d and S. Sreenivasa ^c ^*

^aDepartment of Studies and Research in Chemistry, U.C.S., Tumkur University, Tumkur, Karnataka 572 103, India, ^bDepartment of Studies and Research in Physics, U.C.S., Tumkur University, Tumkur, Karnataka 572 103, India, ^cDepartment of Studies and Research in Chemistry, Tumkur University, Tumkur, Karnataka 572 103, India, and ^dDepartment of Studies in Physics, University of Mysore, Manasagangotri, Mysore, India
^*Correspondence e-mail: drsreenivasa@yahoo.co.in

(Received 27 September 2013; accepted 30 September 2013; online 5 October 2013)

In the title compound, C₁₃H₁₃NO₃, the conformation across the C=C bond is synperiplanar, the torsion angle of the segment C(ring)—C=C—C(N) being 3.2 (5)°. In the crystal, molecules are linked into inversion dimers, arranged in a zigzag pattern, through two C—H⋯O interactions generating R₂²(10) and R₂²(14) motifs. These dimers are arranged in a zigzag pattern in the crystal structure. The molecules are further linked along the c axis through weak C—H⋯π interactions, and weak π⋯π interactions [centroid–centroid separation = 3.9986 (17) Å] are also observed.

CCDC reference: 963839

Related literature

For use of the title compound in the synthesis of prop-2-enoylamides, see: Santos et al.. (2004 ). For use of the title compound in the synthesis of prop-2-enoates, see: Sousa et al. (2006 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₃H₁₃NO₃
M_r = 231.24
Monoclinic, P 2₁ /n
a = 8.4889 (12) Å
b = 8.3552 (16) Å
c = 17.143 (3) Å
β = 91.294 (11)°
V = 1215.6 (3) Å³
Z = 4
Cu Kα radiation
μ = 0.74 mm⁻¹
T = 296 K
0.40 × 0.33 × 0.27 mm

Data collection

Bruker APEXII CCD diffractometer
4798 measured reflections
1937 independent reflections
1354 reflections with I > 2σ(I)
R_int = 0.069

Refinement

R[F² > 2σ(F²)] = 0.067
wR(F²) = 0.201
S = 1.02
1937 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C1–C6 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O2ⁱ	0.93	2.54	3.414 (3)	157
C8—H8⋯O2ⁱ	0.93	2.59	3.475 (3)	159
C12—H12A⋯Cgⁱⁱ	0.97	2.90	3.803 (3)	156
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x+1, y, z.

Data collection: APEX2 (Bruker, 2009 ); cell refinement: APEX2 and SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus and XPREP; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97.

Supporting information

CCDC reference: 963839

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536813026871/sj5355sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813026871/sj5355Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813026871/sj5355Isup3.cml

checkCIF report

Comment top

Ethyl (2E)-2-cyano-3-(4-methoxyphenyl)acrylate is an important starting material for the synthesis of biologically and pharmacologically important 2-propenoylamides (Santos et al.., 2004) and 2-propenoates (Sousa et al., 2006). Keeping this in mind, the title compound was synthesized.

In the title compound, C₁₃H₁₃NO₃, the conformation across the C=C bond is syn-periplanar (Fig.1), the C4—C8—C9—C10 torsion angle being 3.2 (5)°. The molecules are linked into inversion dimers (Fig.2) through C3—H3···O2 and C8—H8···O2 interactions, generating R₂²(10) and R₂²(14) ring motifs (Bernstein et al., 1995). These dimers are arranged in a zigzag pattern in the crystal structure (Fig.3). The molecules are further linked along the c axis through weak C12—H12A···Cg interactions (Fig.4), and weak Cg···Cg interactions (centroid···centroid separation = 3.9986 (17) Å) are also observed (Fig.5).

Related literature top

For use of the title compound in the synthesis of prop-2-enoylamides, see: Santos et al.. (2004). For use of the title compound in the synthesis of prop-2-enoates, see: Sousa et al. (2006). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

A mixture of tetra-n-butylammonium bromide (TBAB) (3.47 g, 10 mmol), palladium acetate (0.060 g, 0.27 mmol), triphenylphosphine (2.97 g, 11 mmol), 1-bromo-4-methoxybenzene (1 g, 5.4 mmol) and potassium carbonate (1.12 g, 8.1 mmol) were dissolved in 10 ml of DMF in a three-necked round bottom flask and the reaction mixture was heated to 120 °C under nitrogen atmosphere with constant stirring for 10–15 minutes until a yellowish brown solution was obtained. Ethyl-2-cyanoacrylate (0.81 g, 6.4 mmol) was added to the solution and the reaction mixture was heated to 120 °C for 10 h, cooled and filtered under vacuum to obtain the crude compound. This was further purified by column chromatography using petroleum ether: ethyl acetate (7:3) as eluent (Rf value = 0.69), to yield pale green colored crystals.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: APEX2 and SAINT-Plus (Bruker, 2009); data reduction: SAINTPlus and XPREP (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound, showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Molecular packing in the title compound displaying R₂²(10) and R₂²(14)rings chains. H atoms not involved in H-bonding are omitted for clarity.
	Fig. 3. The zigzag pattern of inversion dimers viewed along a.
	Fig. 4. Linking of molecules along the c axis through C—H···Cg interactions.
	Fig. 5. π-π stacking interactions observed in the crystal structure. H atoms are omitted for clarity.

Ethyl (2E)-2-cyano-3-(4-methoxyphenyl)acrylate top

Crystal data top

C₁₃H₁₃NO₃	Prism
M_r = 231.24	D_x = 1.264 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 401 K
Hall symbol: -P 2yn	Cu Kα radiation, λ = 1.54178 Å
a = 8.4889 (12) Å	Cell parameters from 776 reflections
b = 8.3552 (16) Å	θ = 5.2–64.3°
c = 17.143 (3) Å	µ = 0.74 mm⁻¹
β = 91.294 (11)°	T = 296 K
V = 1215.6 (3) Å³	Prism, green
Z = 4	0.40 × 0.33 × 0.27 mm
F(000) = 488

Data collection top

Bruker APEXII CCD diffractometer	1354 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.069
Graphite monochromator	θ_max = 64.3°, θ_min = 5.2°
Detector resolution: 1 pixels mm^-1	h = −9→3
ϕ and ω scans	k = −9→9
4798 measured reflections	l = −19→19
1937 independent 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)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.201	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.124P)²] where P = (F_o² + 2F_c²)/3
1937 reflections	(Δ/σ)_max = 0.012
156 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₃H₁₃NO₃	V = 1215.6 (3) Å³
M_r = 231.24	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 8.4889 (12) Å	µ = 0.74 mm⁻¹
b = 8.3552 (16) Å	T = 296 K
c = 17.143 (3) Å	0.40 × 0.33 × 0.27 mm
β = 91.294 (11)°

Data collection top

Bruker APEXII CCD diffractometer	1354 reflections with I > 2σ(I)
4798 measured reflections	R_int = 0.069
1937 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.067	0 restraints
wR(F²) = 0.201	H-atom parameters constrained
S = 1.02	Δρ_max = 0.18 e Å⁻³
1937 reflections	Δρ_min = −0.25 e Å⁻³
156 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	1.1331 (3)	0.3418 (3)	0.46205 (14)	0.0559 (7)
C2	1.0569 (3)	0.2415 (4)	0.51365 (14)	0.0599 (7)
H2	1.1067	0.2089	0.5599	0.072*
C3	0.9066 (3)	0.1912 (4)	0.49517 (14)	0.0597 (7)
H3	0.8547	0.1266	0.5305	0.072*
C4	0.8284 (3)	0.2330 (3)	0.42574 (13)	0.0510 (7)
C5	0.9065 (3)	0.3398 (4)	0.37625 (14)	0.0593 (7)
H5	0.8566	0.3743	0.3304	0.071*
C6	1.0549 (3)	0.3931 (4)	0.39481 (14)	0.0621 (7)
H6	1.1040	0.4650	0.3618	0.074*
C7	1.3670 (3)	0.3435 (5)	0.54148 (17)	0.0817 (10)
H7A	1.3118	0.3761	0.5871	0.122*
H7B	1.4705	0.3899	0.5425	0.122*
H7C	1.3756	0.2289	0.5407	0.122*
C8	0.6735 (3)	0.1658 (3)	0.41146 (14)	0.0550 (7)
H8	0.6320	0.1138	0.4543	0.066*
C9	0.5784 (3)	0.1645 (3)	0.34770 (14)	0.0540 (7)
C10	0.6207 (3)	0.2301 (4)	0.27376 (14)	0.0639 (8)
C11	0.4219 (3)	0.0864 (4)	0.35228 (14)	0.0577 (7)
C12	0.1752 (3)	0.0439 (4)	0.28684 (17)	0.0698 (8)
H12A	0.1221	0.0730	0.3343	0.084*
H12B	0.1790	−0.0720	0.2835	0.084*
C13	0.0891 (3)	0.1113 (5)	0.21740 (18)	0.0856 (11)
H13A	0.0878	0.2259	0.2209	0.128*
H13B	−0.0171	0.0717	0.2159	0.128*
H13C	0.1413	0.0795	0.1708	0.128*
N1	0.6549 (3)	0.2803 (5)	0.21466 (14)	0.0962 (11)
O1	1.2826 (2)	0.3962 (3)	0.47346 (11)	0.0737 (7)
O2	0.3775 (2)	0.0120 (3)	0.40764 (12)	0.0812 (7)
O3	0.33402 (18)	0.1098 (3)	0.28756 (9)	0.0649 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0466 (14)	0.0676 (18)	0.0535 (13)	−0.0088 (12)	0.0015 (10)	−0.0033 (12)
C2	0.0525 (14)	0.078 (2)	0.0488 (13)	−0.0068 (13)	−0.0061 (10)	0.0058 (12)
C3	0.0525 (14)	0.0777 (19)	0.0489 (13)	−0.0081 (13)	−0.0002 (10)	0.0077 (12)
C4	0.0431 (13)	0.0640 (16)	0.0458 (12)	−0.0001 (11)	0.0003 (9)	−0.0013 (11)
C5	0.0536 (15)	0.0757 (19)	0.0486 (13)	−0.0014 (13)	−0.0028 (10)	0.0082 (12)
C6	0.0575 (15)	0.077 (2)	0.0520 (13)	−0.0105 (14)	0.0036 (11)	0.0077 (13)
C7	0.0549 (16)	0.118 (3)	0.0713 (18)	−0.0178 (17)	−0.0162 (13)	0.0095 (17)
C8	0.0470 (13)	0.0680 (18)	0.0501 (13)	0.0007 (12)	0.0017 (10)	0.0037 (11)
C9	0.0402 (13)	0.0707 (17)	0.0512 (13)	0.0026 (11)	0.0027 (10)	−0.0018 (11)
C10	0.0443 (13)	0.099 (2)	0.0477 (14)	0.0013 (14)	−0.0023 (10)	−0.0015 (14)
C11	0.0454 (13)	0.0742 (19)	0.0534 (13)	0.0030 (12)	−0.0029 (11)	−0.0020 (13)
C12	0.0458 (15)	0.079 (2)	0.0841 (18)	−0.0014 (13)	−0.0088 (13)	−0.0056 (15)
C13	0.0530 (16)	0.128 (3)	0.0748 (19)	0.0064 (17)	−0.0112 (13)	−0.0004 (19)
N1	0.0689 (16)	0.167 (3)	0.0526 (14)	−0.0126 (17)	0.0023 (11)	0.0125 (16)
O1	0.0546 (11)	0.0997 (17)	0.0665 (11)	−0.0192 (10)	−0.0074 (8)	0.0085 (11)
O2	0.0605 (12)	0.1123 (19)	0.0705 (12)	−0.0192 (11)	−0.0087 (9)	0.0250 (12)
O3	0.0449 (10)	0.0925 (16)	0.0570 (10)	−0.0033 (9)	−0.0067 (8)	0.0006 (9)

Geometric parameters (Å, º) top

C1—O1	1.358 (3)	C7—H7C	0.9600
C1—C6	1.385 (4)	C8—C9	1.344 (3)
C1—C2	1.389 (4)	C8—H8	0.9300
C2—C3	1.374 (3)	C9—C10	1.434 (4)
C2—H2	0.9300	C9—C11	1.483 (4)
C3—C4	1.394 (3)	C10—N1	1.140 (3)
C3—H3	0.9300	C11—O2	1.203 (3)
C4—C5	1.407 (4)	C11—O3	1.337 (3)
C4—C8	1.446 (3)	C12—O3	1.456 (3)
C5—C6	1.367 (4)	C12—C13	1.493 (4)
C5—H5	0.9300	C12—H12A	0.9700
C6—H6	0.9300	C12—H12B	0.9700
C7—O1	1.425 (3)	C13—H13A	0.9600
C7—H7A	0.9600	C13—H13B	0.9600
C7—H7B	0.9600	C13—H13C	0.9600

O1—C1—C6	116.4 (2)	C9—C8—C4	131.9 (2)
O1—C1—C2	123.9 (2)	C9—C8—H8	114.0
C6—C1—C2	119.7 (2)	C4—C8—H8	114.0
C3—C2—C1	118.8 (2)	C8—C9—C10	123.9 (2)
C3—C2—H2	120.6	C8—C9—C11	118.9 (2)
C1—C2—H2	120.6	C10—C9—C11	117.2 (2)
C2—C3—C4	122.8 (2)	N1—C10—C9	179.1 (4)
C2—C3—H3	118.6	O2—C11—O3	123.4 (2)
C4—C3—H3	118.6	O2—C11—C9	124.5 (2)
C3—C4—C5	116.9 (2)	O3—C11—C9	112.1 (2)
C3—C4—C8	117.4 (2)	O3—C12—C13	107.5 (3)
C5—C4—C8	125.7 (2)	O3—C12—H12A	110.2
C6—C5—C4	120.7 (2)	C13—C12—H12A	110.2
C6—C5—H5	119.6	O3—C12—H12B	110.2
C4—C5—H5	119.6	C13—C12—H12B	110.2
C5—C6—C1	121.0 (2)	H12A—C12—H12B	108.5
C5—C6—H6	119.5	C12—C13—H13A	109.5
C1—C6—H6	119.5	C12—C13—H13B	109.5
O1—C7—H7A	109.5	H13A—C13—H13B	109.5
O1—C7—H7B	109.5	C12—C13—H13C	109.5
H7A—C7—H7B	109.5	H13A—C13—H13C	109.5
O1—C7—H7C	109.5	H13B—C13—H13C	109.5
H7A—C7—H7C	109.5	C1—O1—C7	117.7 (2)
H7B—C7—H7C	109.5	C11—O3—C12	116.8 (2)

O1—C1—C2—C3	−178.6 (3)	C4—C8—C9—C10	3.2 (5)
C6—C1—C2—C3	2.1 (4)	C4—C8—C9—C11	−178.8 (3)
C1—C2—C3—C4	1.8 (4)	C8—C9—C11—O2	−6.2 (5)
C2—C3—C4—C5	−4.2 (4)	C10—C9—C11—O2	171.9 (3)
C2—C3—C4—C8	176.9 (2)	C8—C9—C11—O3	173.1 (2)
C3—C4—C5—C6	2.8 (4)	C10—C9—C11—O3	−8.8 (4)
C8—C4—C5—C6	−178.5 (3)	C6—C1—O1—C7	−179.0 (3)
C4—C5—C6—C1	1.0 (4)	C2—C1—O1—C7	1.7 (4)
O1—C1—C6—C5	177.2 (3)	O2—C11—O3—C12	1.7 (4)
C2—C1—C6—C5	−3.5 (4)	C9—C11—O3—C12	−177.6 (2)
C3—C4—C8—C9	−169.8 (3)	C13—C12—O3—C11	168.8 (3)
C5—C4—C8—C9	11.4 (5)

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C1···C6 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2ⁱ	0.93	2.54	3.414 (3)	157
C8—H8···O2ⁱ	0.93	2.59	3.475 (3)	159
C12—H12A···Cgⁱⁱ	0.97	2.90	3.803 (3)	156

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

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C1···C6 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2ⁱ	0.93	2.54	3.414 (3)	157
C8—H8···O2ⁱ	0.93	2.59	3.475 (3)	159
C12—H12A···Cgⁱⁱ	0.97	2.90	3.803 (3)	156

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

Acknowledgements

The authors acknowledge the IOE X-ray diffractometer Facility, University of Mysore, Mysore, for the data collection.

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