(Z)-Methyl 3-(4-ethoxy-anilino)but-2-enoate.

The title compound, C(13)H(17)NO(3), was synthesized from methyl 3-oxobutanoate and 4-ethoxy-benzenamine using a catalytic amount of InBr(3) under solvent-free conditions. The 3-amino-but-2-enoic acid methyl ester group is planar and forms a dihedral angle of 83.4 (1)° with the benzene ring. The eth-oxy group is slightly twisted away from the benzene ring [dihedral angle = 13.8 (1)°]. An intra-molecular N-H⋯O hydrogen bond generating an S(6) ring is observed. Mol-ecules are linked into a chain along the b axis by inter-molecular C-H⋯O hydrogen bonding.

Related literature

For general background on β-enamino esters, see: Bartoli et al. (1994 ▶); Cimarelli & Palmieri (1996 ▶); Cimarelli et al. (1994 ▶); Elassar & El-Khair (2003 ▶); Greenhill (1977 ▶); Lubell et al. (1991 ▶); Michael et al. (1999 ▶); Paola et al. (2000 ▶); Rybarczyk-Pirek & Grabowski (2002 ▶); Yunus et al. (2008 ▶).

Experimental

Crystal data

C13H17NO3

M = 235.28

Monoclinic,

a = 12.421 (2) Å

b = 6.3372 (13) Å

c = 16.569 (3) Å

β = 96.519 (3)°

V = 1295.7 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 294 (2) K

0.30 × 0.26 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.942, T max = 0.990

6917 measured reflections

2628 independent reflections

1629 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.136

S = 1.00

2628 reflections

158 parameters

H-atom parameters constrained

Δρmax = 0.13 e Å−3

Δρmin = −0.11 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680800891X/ci2569sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680800891X/ci2569Isup2.hkl

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

C13H17NO3	F000 = 504
Mr = 235.28	Dx = 1.206 Mg m−3
Monoclinic, P21/n	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2289 reflections
a = 12.421 (2) Å	θ = 2.5–24.9º
b = 6.3372 (13) Å	µ = 0.09 mm−1
c = 16.569 (3) Å	T = 294 (2) K
β = 96.519 (3)º	Block, yellow
V = 1295.7 (4) Å3	0.30 × 0.26 × 0.20 mm
Z = 4

Bruker SMART CCD area-detector diffractometer	2628 independent reflections
Radiation source: fine-focus sealed tube	1629 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.031
T = 294(2) K	θmax = 26.3º
φ and ω scans	θmin = 2.0º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	h = −11→15
Tmin = 0.942, Tmax = 0.990	k = −7→6
6917 measured reflections	l = −20→20

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.042	w = 1/[σ2(Fo2) + (0.0697P)2 + 0.1223P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.136	(Δ/σ)max = 0.001
S = 1.00	Δρmax = 0.13 e Å−3
2628 reflections	Δρmin = −0.11 e Å−3
158 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.106 (7)
Secondary atom site location: difference Fourier map

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.

	x	y	z	Uiso*/Ueq
O1	0.11751 (9)	1.2475 (2)	1.03170 (8)	0.0714 (4)
O2	0.55147 (10)	0.4131 (2)	0.90568 (7)	0.0697 (4)
O3	0.60606 (12)	0.2866 (2)	0.79053 (8)	0.0872 (5)
N1	0.39962 (11)	0.7279 (2)	0.88382 (9)	0.0654 (4)
H1	0.4403	0.6528	0.9181	0.078*
C1	0.32646 (13)	0.8715 (3)	0.91658 (9)	0.0578 (4)
C2	0.21953 (14)	0.8158 (3)	0.92064 (10)	0.0660 (5)
H2	0.1934	0.6891	0.8979	0.079*
C3	0.15124 (13)	0.9455 (3)	0.95793 (11)	0.0642 (5)
H3	0.0794	0.9067	0.9600	0.077*
C4	0.18978 (13)	1.1339 (3)	0.99243 (10)	0.0562 (4)
C5	0.29584 (13)	1.1948 (3)	0.98654 (11)	0.0621 (5)
H5	0.3216	1.3232	1.0079	0.074*
C6	0.36297 (13)	1.0624 (3)	0.94847 (10)	0.0622 (5)
H6	0.4341	1.1032	0.9444	0.075*
C7	0.15753 (16)	1.4153 (3)	1.08352 (12)	0.0747 (6)
H7A	0.1915	1.5212	1.0526	0.090*
H7B	0.2113	1.3624	1.1257	0.090*
C8	0.06476 (18)	1.5100 (4)	1.12071 (12)	0.0860 (6)
H8A	0.0129	1.5654	1.0787	0.129*
H8B	0.0908	1.6218	1.1569	0.129*
H8C	0.0309	1.4036	1.1505	0.129*
C9	0.41069 (14)	0.6995 (3)	0.80498 (10)	0.0606 (5)
C10	0.34385 (18)	0.8388 (4)	0.74539 (12)	0.0856 (6)
H10A	0.2687	0.8250	0.7530	0.128*
H10B	0.3542	0.7976	0.6911	0.128*
H10C	0.3660	0.9830	0.7541	0.128*
C11	0.48003 (16)	0.5549 (3)	0.77912 (11)	0.0682 (5)
H11	0.4847	0.5450	0.7236	0.082*
C12	0.54568 (14)	0.4182 (3)	0.83178 (11)	0.0603 (5)
C13	0.66598 (19)	0.1247 (4)	0.83608 (13)	0.0913 (7)
H13A	0.7034	0.1842	0.8847	0.137*
H13B	0.7176	0.0641	0.8038	0.137*
H13C	0.6171	0.0170	0.8503	0.137*

	U11	U22	U33	U12	U13	U23
O1	0.0558 (7)	0.0803 (9)	0.0782 (8)	0.0017 (6)	0.0075 (6)	−0.0156 (7)
O2	0.0708 (8)	0.0769 (9)	0.0602 (8)	0.0030 (6)	0.0030 (6)	−0.0031 (6)
O3	0.1112 (11)	0.0823 (10)	0.0680 (8)	0.0315 (8)	0.0100 (7)	−0.0054 (7)
N1	0.0600 (9)	0.0757 (10)	0.0604 (9)	0.0114 (7)	0.0069 (7)	0.0021 (7)
C1	0.0526 (10)	0.0670 (11)	0.0537 (9)	−0.0002 (8)	0.0050 (7)	0.0037 (8)
C2	0.0572 (11)	0.0703 (12)	0.0701 (11)	−0.0124 (9)	0.0062 (8)	−0.0107 (9)
C3	0.0465 (9)	0.0752 (13)	0.0709 (11)	−0.0097 (8)	0.0067 (8)	−0.0097 (9)
C4	0.0497 (9)	0.0632 (10)	0.0546 (9)	0.0017 (8)	0.0015 (7)	0.0024 (8)
C5	0.0540 (10)	0.0603 (11)	0.0710 (11)	−0.0080 (8)	0.0030 (8)	−0.0018 (9)
C6	0.0481 (10)	0.0686 (12)	0.0698 (11)	−0.0075 (8)	0.0063 (8)	0.0057 (9)
C7	0.0787 (13)	0.0724 (13)	0.0724 (12)	0.0010 (10)	0.0071 (9)	−0.0102 (10)
C8	0.0949 (15)	0.0886 (15)	0.0745 (12)	0.0188 (12)	0.0097 (11)	−0.0090 (11)
C9	0.0589 (10)	0.0621 (11)	0.0613 (10)	−0.0050 (8)	0.0087 (8)	0.0037 (8)
C10	0.0966 (15)	0.0921 (15)	0.0697 (12)	0.0227 (12)	0.0170 (11)	0.0152 (11)
C11	0.0787 (13)	0.0715 (12)	0.0552 (10)	0.0040 (10)	0.0118 (9)	0.0015 (9)
C12	0.0607 (11)	0.0566 (10)	0.0642 (11)	−0.0066 (8)	0.0088 (8)	−0.0060 (9)
C13	0.1021 (16)	0.0811 (15)	0.0877 (15)	0.0275 (12)	−0.0022 (12)	−0.0071 (12)

O1—C4	1.371 (2)	C6—H6	0.93
O1—C7	1.420 (2)	C7—C8	1.493 (3)
O2—C12	1.2187 (19)	C7—H7A	0.97
O3—C12	1.357 (2)	C7—H7B	0.97
O3—C13	1.431 (2)	C8—H8A	0.96
N1—C9	1.341 (2)	C8—H8B	0.96
N1—C1	1.435 (2)	C8—H8C	0.96
N1—H1	0.86	C9—C11	1.360 (3)
C1—C6	1.376 (2)	C9—C10	1.503 (3)
C1—C2	1.383 (2)	C10—H10A	0.96
C2—C3	1.377 (3)	C10—H10B	0.96
C2—H2	0.93	C10—H10C	0.96
C3—C4	1.385 (2)	C11—C12	1.420 (3)
C3—H3	0.93	C11—H11	0.93
C4—C5	1.387 (2)	C13—H13A	0.96
C5—C6	1.384 (2)	C13—H13B	0.96
C5—H5	0.93	C13—H13C	0.96
C4—O1—C7	118.48 (14)	H7A—C7—H7B	108.4
C12—O3—C13	117.32 (15)	C7—C8—H8A	109.5
C9—N1—C1	126.37 (15)	C7—C8—H8B	109.5
C9—N1—H1	116.8	H8A—C8—H8B	109.5
C1—N1—H1	116.8	C7—C8—H8C	109.5
C6—C1—C2	118.81 (16)	H8A—C8—H8C	109.5
C6—C1—N1	120.47 (15)	H8B—C8—H8C	109.5
C2—C1—N1	120.63 (16)	N1—C9—C11	122.43 (16)
C3—C2—C1	120.90 (17)	N1—C9—C10	116.80 (16)
C3—C2—H2	119.6	C11—C9—C10	120.76 (16)
C1—C2—H2	119.6	C9—C10—H10A	109.5
C2—C3—C4	119.86 (16)	C9—C10—H10B	109.5
C2—C3—H3	120.1	H10A—C10—H10B	109.5
C4—C3—H3	120.1	C9—C10—H10C	109.5
O1—C4—C3	115.74 (15)	H10A—C10—H10C	109.5
O1—C4—C5	124.43 (16)	H10B—C10—H10C	109.5
C3—C4—C5	119.83 (16)	C9—C11—C12	123.90 (16)
C6—C5—C4	119.30 (17)	C9—C11—H11	118.0
C6—C5—H5	120.4	C12—C11—H11	118.0
C4—C5—H5	120.4	O2—C12—O3	121.13 (16)
C1—C6—C5	121.23 (16)	O2—C12—C11	126.71 (16)
C1—C6—H6	119.4	O3—C12—C11	112.16 (16)
C5—C6—H6	119.4	O3—C13—H13A	109.5
O1—C7—C8	108.47 (16)	O3—C13—H13B	109.5
O1—C7—H7A	110.0	H13A—C13—H13B	109.5
C8—C7—H7A	110.0	O3—C13—H13C	109.5
O1—C7—H7B	110.0	H13A—C13—H13C	109.5
C8—C7—H7B	110.0	H13B—C13—H13C	109.5
C9—N1—C1—C6	−100.4 (2)	N1—C1—C6—C5	−174.42 (15)
C9—N1—C1—C2	83.0 (2)	C4—C5—C6—C1	−0.1 (3)
C6—C1—C2—C3	−1.9 (3)	C4—O1—C7—C8	−178.42 (16)
N1—C1—C2—C3	174.69 (16)	C1—N1—C9—C11	−177.96 (17)
C1—C2—C3—C4	−0.4 (3)	C1—N1—C9—C10	3.2 (3)
C7—O1—C4—C3	165.99 (15)	N1—C9—C11—C12	1.1 (3)
C7—O1—C4—C5	−13.3 (2)	C10—C9—C11—C12	179.97 (18)
C2—C3—C4—O1	−176.87 (16)	C13—O3—C12—O2	7.7 (3)
C2—C3—C4—C5	2.5 (3)	C13—O3—C12—C11	−172.85 (18)
O1—C4—C5—C6	177.09 (16)	C9—C11—C12—O2	−1.7 (3)
C3—C4—C5—C6	−2.2 (2)	C9—C11—C12—O3	178.90 (18)
C2—C1—C6—C5	2.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	2.08	2.741 (2)	133
C6—H6···O2i	0.93	2.57	3.362 (3)	143

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.86	2.08	2.741 (2)	133
C6—H6⋯O2i	0.93	2.57	3.362 (3)	143

Symmetry code: (i) .