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

Abstract

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,

• a = 10.5661 (6) Å

• b = 6.9715 (4) Å

• c = 18.4141 (10) Å

• β = 101.858 (1)°

• V = 1327.47 (13) ų

• 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[F ² > 2σ(F ²)] = 0.046

• wR(F ²) = 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 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811040013/xu5338Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

Carbon-bound H-atoms were placed in calculated positions [C–H 0.93 to 0.97 Å; U(H) 1.2 to 1.5U(C)] and were included in the refinement in the riding model approximation, with U(H) set to 1.2 to 1.5U(C).

Figures

Fig. 1.

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

Crystal data

C14H15NO4	F(000) = 552
Mr = 261.27	Dx = 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

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

Refinement

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(Fo2) + (0.0663P)2 + 0.2366P] where P = (Fo2 + 2Fc2)/3
3330 reflections	(Δ/σ)max = 0.001
172 parameters	Δρmax = 0.23 e Å−3
0 restraints	Δρmin = −0.21 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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)