(E)-Ethyl 2-cyano-3-(2,4-dimeth­oxy­phen­yl)prop-2-enoate

Abdelhamid, A.A.; Mohamed, S.K.; Khalilov, A.N.; Gurbanov, A.V.; Ng, S.W.

doi:10.1107/S1600536811040013

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o2830

doi:10.1107/S1600536811040013

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(E)-Ethyl 2-cyano-3-(2,4-dimethoxyphenyl)prop-2-enoate

Antar A. Abdelhamid,^a Shaaban K. Mohamed,^b Ali N. Khalilov,^a Atash V. Gurbanov ^a and Seik Weng Ng ^c,^d ^*

^aDepartment of Organic Chemistry, Baku State University, Baku, Azerbaijan, ^bSchool of Biology, Chemistry and Material Science, Manchester Metropolitan University, Manchester, UK, ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^dChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 26 September 2011; accepted 29 September 2011; online 5 October 2011)

The C=C bond in the title compound, C₁₄H₁₅NO₄, is in an E configuration. With the exception of the methyl C atoms, the non-H atoms of the molecule all lie approximately on a plane (r.m.s. deviation = 0.096 Å). π–π stacking is observed between parallel benzene rings of adjacent molecules, the centroid–centroid distance being 3.7924 (8) Å.

Related literature

For benzylidenecyanoacetate, see: Bodrikov et al. (1992 ) and for 3,4-dimethoxybenzylidenecyanoacetate, see: Nesterov et al. (2001 ).

Experimental

Crystal data

C₁₄H₁₅NO₄
M_r = 261.27
Monoclinic, P 2₁ /c
a = 10.5661 (6) Å
b = 6.9715 (4) Å
c = 18.4141 (10) Å
β = 101.858 (1)°
V = 1327.47 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 295 K
0.20 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEXII diffractometer
14924 measured reflections
3330 independent reflections
2382 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.134
S = 1.03
3330 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811040013/xu5338sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811040013/xu5338Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811040013/xu5338Isup3.cml

checkCIF report

Comment top

The synthesis of benzylidenecyanoacetate was reported by Bodrikov et al. in 1992; the compound was synthesized by a conventional route. In the present study, microwave radiation was used to initiate the condensation; 2,4-dimethoxylbenzaldehyde was used in place of the unsubstituted homolog. The carbon-carbon double-bond in C₁₄H₁₅NO₄ is of an E-configuration (Scheme I, Fig. 1). With the exception of the methyl C, the non-hydrogen atoms all lie on a plane. The features are similar to those of 3,4-dimethoxybenzylidenecyanoacetate (Bodrikov et al., 1992).

Related literature top

For benzylidenecyanoacetate, see: Bodrikov et al. (1992) and for 3,4-dimethoxybenzylidenecyanoacetate, see: Nesterov et al. (2001).

Experimental top

2,4-Dimethoxy benzaldehyde (10 mmol), ethyl cyanoacetate (10 mmol), and 2,4-pentanedione (100 mmol, aprox. 10 ml) dissolved in ethanol (50 ml) and the solution was irradiated by microwave irradiation for 5 minutes. The mixture was cooled and the product was recrystalized from ethanol in 90% yield; m.p. 405 K.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₁₄H₁₅NO₄ at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

(E)-Ethyl 2-cyano-3-(2,4-dimethoxyphenyl)prop-2-enoate top

Crystal data top

C₁₄H₁₅NO₄	F(000) = 552
M_r = 261.27	D_x = 1.307 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3565 reflections
a = 10.5661 (6) Å	θ = 2.3–27.7°
b = 6.9715 (4) Å	µ = 0.10 mm⁻¹
c = 18.4141 (10) Å	T = 295 K
β = 101.858 (1)°	Prism, colorless
V = 1327.47 (13) Å³	0.20 × 0.20 × 0.20 mm
Z = 4

Data collection top

Bruker SMART APEXII diffractometer	2382 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.026
Graphite monochromator	θ_max = 28.4°, θ_min = 2.0°
ϕ and ω scans	h = −14→14
14924 measured reflections	k = −9→9
3330 independent reflections	l = −24→24

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.134	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0663P)² + 0.2366P] where P = (F_o² + 2F_c²)/3
3330 reflections	(Δ/σ)_max = 0.001
172 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₄H₁₅NO₄	V = 1327.47 (13) Å³
M_r = 261.27	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.5661 (6) Å	µ = 0.10 mm⁻¹
b = 6.9715 (4) Å	T = 295 K
c = 18.4141 (10) Å	0.20 × 0.20 × 0.20 mm
β = 101.858 (1)°

Data collection top

Bruker SMART APEXII diffractometer	2382 reflections with I > 2σ(I)
14924 measured reflections	R_int = 0.026
3330 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.134	H-atom parameters constrained
S = 1.03	Δρ_max = 0.23 e Å⁻³
3330 reflections	Δρ_min = −0.21 e Å⁻³
172 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.31913 (10)	0.27747 (18)	0.55366 (6)	0.0536 (3)
O2	0.29391 (10)	0.12247 (17)	0.30174 (6)	0.0537 (3)
O3	0.87131 (11)	0.3785 (2)	0.71774 (6)	0.0628 (4)
O4	0.66774 (11)	0.4110 (2)	0.73311 (6)	0.0627 (3)
N1	0.89121 (15)	0.2321 (3)	0.55058 (9)	0.0804 (6)
C1	0.51259 (12)	0.25722 (18)	0.50966 (7)	0.0351 (3)
C2	0.37586 (13)	0.2438 (2)	0.49505 (8)	0.0377 (3)
C3	0.30758 (13)	0.1990 (2)	0.42512 (8)	0.0411 (3)
H3	0.2179	0.1899	0.4163	0.049*
C4	0.37162 (14)	0.1674 (2)	0.36783 (8)	0.0401 (3)
C5	0.50565 (14)	0.1815 (2)	0.37981 (8)	0.0434 (3)
H5	0.5489	0.1616	0.3413	0.052*
C6	0.57268 (13)	0.2257 (2)	0.45012 (8)	0.0417 (3)
H6	0.6623	0.2350	0.4582	0.050*
C7	0.18101 (15)	0.2627 (3)	0.54175 (10)	0.0631 (5)
H7A	0.1535	0.2895	0.5873	0.095*
H7B	0.1548	0.1353	0.5254	0.095*
H7C	0.1422	0.3535	0.5046	0.095*
C8	0.35279 (19)	0.0981 (3)	0.23941 (9)	0.0636 (5)
H8A	0.2877	0.0668	0.1965	0.095*
H8B	0.4151	−0.0038	0.2492	0.095*
H8C	0.3953	0.2150	0.2305	0.095*
C9	0.57905 (13)	0.30444 (19)	0.58405 (7)	0.0371 (3)
H9	0.5242	0.3340	0.6160	0.045*
C10	0.70570 (13)	0.3137 (2)	0.61586 (8)	0.0383 (3)
C11	0.74281 (14)	0.3727 (2)	0.69485 (8)	0.0446 (3)
C12	0.80883 (14)	0.2688 (2)	0.57949 (8)	0.0497 (4)
C13	0.92092 (19)	0.4426 (4)	0.79351 (10)	0.0773 (6)
H13A	0.8687	0.5488	0.8047	0.093*
H13B	1.0088	0.4886	0.7977	0.093*
C14	0.9198 (2)	0.2881 (4)	0.84808 (12)	0.0922 (8)
H14A	0.9534	0.3361	0.8971	0.138*
H14B	0.9725	0.1835	0.8378	0.138*
H14C	0.8327	0.2442	0.8449	0.138*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0315 (5)	0.0867 (8)	0.0439 (6)	−0.0039 (5)	0.0112 (4)	−0.0102 (5)
O2	0.0473 (6)	0.0751 (8)	0.0352 (5)	−0.0065 (5)	0.0001 (4)	0.0012 (5)
O3	0.0433 (6)	0.0943 (10)	0.0461 (6)	−0.0115 (6)	−0.0018 (5)	−0.0126 (6)
O4	0.0539 (7)	0.0885 (9)	0.0455 (6)	0.0063 (6)	0.0098 (5)	−0.0101 (6)
N1	0.0359 (7)	0.1402 (17)	0.0662 (10)	−0.0018 (9)	0.0134 (7)	−0.0185 (10)
C1	0.0305 (6)	0.0374 (7)	0.0368 (7)	−0.0007 (5)	0.0054 (5)	0.0033 (5)
C2	0.0339 (7)	0.0416 (7)	0.0385 (7)	0.0003 (5)	0.0095 (5)	0.0027 (6)
C3	0.0296 (6)	0.0488 (8)	0.0432 (7)	−0.0020 (6)	0.0036 (6)	0.0044 (6)
C4	0.0413 (7)	0.0416 (7)	0.0348 (7)	−0.0021 (6)	0.0020 (5)	0.0049 (6)
C5	0.0408 (7)	0.0549 (9)	0.0361 (7)	0.0000 (6)	0.0117 (6)	0.0035 (6)
C6	0.0301 (7)	0.0525 (8)	0.0425 (7)	−0.0001 (6)	0.0076 (6)	0.0035 (6)
C7	0.0323 (8)	0.1026 (15)	0.0569 (10)	−0.0057 (8)	0.0149 (7)	−0.0097 (10)
C8	0.0674 (11)	0.0851 (13)	0.0361 (8)	−0.0066 (9)	0.0059 (7)	−0.0056 (8)
C9	0.0342 (7)	0.0405 (7)	0.0371 (7)	0.0004 (5)	0.0081 (5)	0.0013 (6)
C10	0.0336 (7)	0.0421 (7)	0.0387 (7)	−0.0025 (6)	0.0065 (5)	0.0004 (6)
C11	0.0398 (8)	0.0509 (9)	0.0412 (8)	−0.0030 (6)	0.0041 (6)	−0.0011 (6)
C12	0.0329 (7)	0.0704 (11)	0.0432 (8)	−0.0058 (7)	0.0017 (6)	−0.0036 (7)
C13	0.0638 (12)	0.1100 (17)	0.0506 (10)	−0.0214 (11)	−0.0059 (8)	−0.0201 (11)
C14	0.0774 (15)	0.134 (2)	0.0547 (11)	−0.0001 (14)	−0.0103 (10)	−0.0037 (13)

Geometric parameters (Å, º) top

O1—C2	1.3584 (16)	C6—H6	0.9300
O1—C7	1.4342 (18)	C7—H7A	0.9600
O2—C4	1.3573 (17)	C7—H7B	0.9600
O2—C8	1.4238 (19)	C7—H7C	0.9600
O3—C11	1.3370 (18)	C8—H8A	0.9600
O3—C13	1.456 (2)	C8—H8B	0.9600
O4—C11	1.1945 (18)	C8—H8C	0.9600
N1—C12	1.139 (2)	C9—C10	1.3475 (19)
C1—C6	1.3925 (19)	C9—H9	0.9300
C1—C2	1.4172 (18)	C10—C12	1.426 (2)
C1—C9	1.4431 (19)	C10—C11	1.485 (2)
C2—C3	1.376 (2)	C13—C14	1.475 (3)
C3—C4	1.383 (2)	C13—H13A	0.9700
C3—H3	0.9300	C13—H13B	0.9700
C4—C5	1.391 (2)	C14—H14A	0.9600
C5—C6	1.377 (2)	C14—H14B	0.9600
C5—H5	0.9300	C14—H14C	0.9600

C2—O1—C7	117.86 (12)	O2—C8—H8B	109.5
C4—O2—C8	117.79 (12)	H8A—C8—H8B	109.5
C11—O3—C13	116.96 (13)	O2—C8—H8C	109.5
C6—C1—C2	116.87 (12)	H8A—C8—H8C	109.5
C6—C1—C9	124.86 (12)	H8B—C8—H8C	109.5
C2—C1—C9	118.26 (12)	C10—C9—C1	132.04 (13)
O1—C2—C3	123.40 (12)	C10—C9—H9	114.0
O1—C2—C1	115.90 (12)	C1—C9—H9	114.0
C3—C2—C1	120.70 (12)	C9—C10—C12	124.87 (13)
C2—C3—C4	120.35 (12)	C9—C10—C11	118.55 (12)
C2—C3—H3	119.8	C12—C10—C11	116.57 (12)
C4—C3—H3	119.8	O4—C11—O3	124.19 (14)
O2—C4—C3	114.83 (12)	O4—C11—C10	124.48 (14)
O2—C4—C5	124.54 (13)	O3—C11—C10	111.33 (12)
C3—C4—C5	120.63 (13)	N1—C12—C10	179.7 (2)
C6—C5—C4	118.36 (13)	O3—C13—C14	112.15 (18)
C6—C5—H5	120.8	O3—C13—H13A	109.2
C4—C5—H5	120.8	C14—C13—H13A	109.2
C5—C6—C1	123.09 (13)	O3—C13—H13B	109.2
C5—C6—H6	118.5	C14—C13—H13B	109.2
C1—C6—H6	118.5	H13A—C13—H13B	107.9
O1—C7—H7A	109.5	C13—C14—H14A	109.5
O1—C7—H7B	109.5	C13—C14—H14B	109.5
H7A—C7—H7B	109.5	H14A—C14—H14B	109.5
O1—C7—H7C	109.5	C13—C14—H14C	109.5
H7A—C7—H7C	109.5	H14A—C14—H14C	109.5
H7B—C7—H7C	109.5	H14B—C14—H14C	109.5
O2—C8—H8A	109.5

C7—O1—C2—C3	0.9 (2)	C4—C5—C6—C1	−0.1 (2)
C7—O1—C2—C1	−179.11 (14)	C2—C1—C6—C5	−0.6 (2)
C6—C1—C2—O1	−179.18 (12)	C9—C1—C6—C5	−179.78 (13)
C9—C1—C2—O1	0.05 (19)	C6—C1—C9—C10	−6.4 (2)
C6—C1—C2—C3	0.8 (2)	C2—C1—C9—C10	174.47 (15)
C9—C1—C2—C3	−179.93 (13)	C1—C9—C10—C12	−2.2 (3)
O1—C2—C3—C4	179.66 (13)	C1—C9—C10—C11	178.48 (14)
C1—C2—C3—C4	−0.4 (2)	C13—O3—C11—O4	−2.3 (3)
C8—O2—C4—C3	176.73 (14)	C13—O3—C11—C10	177.39 (15)
C8—O2—C4—C5	−3.5 (2)	C9—C10—C11—O4	0.9 (2)
C2—C3—C4—O2	179.36 (13)	C12—C10—C11—O4	−178.46 (16)
C2—C3—C4—C5	−0.4 (2)	C9—C10—C11—O3	−178.79 (14)
O2—C4—C5—C6	−179.10 (14)	C12—C10—C11—O3	1.84 (19)
C3—C4—C5—C6	0.6 (2)	C11—O3—C13—C14	81.1 (2)

Experimental details

Crystal data
Chemical formula	C₁₄H₁₅NO₄
M_r	261.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	10.5661 (6), 6.9715 (4), 18.4141 (10)
β (°)	101.858 (1)
V (Å³)	1327.47 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART APEXII diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	14924, 3330, 2382
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.134, 1.03
No. of reflections	3330
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.21

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Acknowledgements

We thank Manchester Metropolitan University, Baku State University and the University of Malaya for supporting this study.

References

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