Ethyl (E)-2-acetyl-3-amino-3-phenyl-2-propyl­enoate

The title compound, C₁₃H₁₅NO₃, is an E isomer and the phenyl ring does not conjugate with C=C. Both intra- and intermolecular N—H...O hydrogen bonds are found, and the infinite molecular chains stretch along the b axis.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.047
• wR factor = 0.118
• Data-to-parameter ratio = 18.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

The title compound, (I), is a by-product obtained in the synthesis of ethyl 3-acetamido-3-phenyl-propylenoate, a prochiral olefinic substrate for producing β-amino acids and derivatives by asymmetric hydrogenation (Hackler et al., 1985; Lubell et al., 1991). The structure determination of (I) was determined in order to obtain more stereochemical information about β-amino acids and their derivatives. In the structure of (I) (Fig. 1), the C1—C2—C3—C8 and C1—C2—C3—C4 torsion angles are 59.0 (2) and −124.07 (18)°, respectively. This shows that the phenyl ring does not completely conjugate with the C1═C2 double bond in the solid state; the C12—C1—C2—N1, C2—C1—C12—O3 and C2—C1—C12—C13 torsion angles are 5.3 (3), −2.1 (3) and 179.52 (17)°, respectively. This illustrates that O3—C12—C1—C2—N1—H are almost coplanar and the C12═O3 double bond and C═C form a conjugated system (Table 1). As shown in Table 2 and the packing diagram (Fig. 2), the crystal structure of (I) is stabilized by both intra- and intermolecular hydrogen bonds, and infinite molecular chains stretch along the b axis.

S2. Experimental

The title compound was synthesized according to Zhu et al. (1999). A crystal suitable for X-ray analysis was slowly grown in a mixed solvent of ethyl acetate and hexane at room temperature. ¹H NMR (400 MHz, acetone-d₆, Bruker): δ 0.63–0.67 (t, J = 7.1 Hz, 3H), 2.24 (s, 3H), 3.64–3.69 (q, J = 7.1 Hz, 2H), 7.35–7.49 (m, 5H), 11.02 (br, 1H).

S3. Refinement

H atoms were included in the riding-model approximation, with U_iso values equal to the U_eq value of the atom to which they were bound.

Computing details

Data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SHELXTL (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of (I), showing ellipsoids at the 50% probability level (Siemens, 1995).
	Fig. 2. Packing diagram for (I). Hydrogen bonds are indicated by dashed lines.

(I)

Crystal data

C13H15NO3	Dx = 1.261 Mg m^−3
Mr = 233.26	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 4270 reflections
a = 17.158 (3) Å	θ = 1–27.5°
b = 7.6070 (12) Å	µ = 0.09 mm^−1
c = 18.823 (3) Å	T = 294 K
V = 2456.8 (7) Å^3	Block, colorless
Z = 8	0.50 × 0.46 × 0.30 mm
F(000) = 992

Data collection

Siemens CCD area-detector diffractometer	2820 independent reflections
Radiation source: fine-focus sealed tube	1423 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.056
ϕ and ω scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −22→22
Tmin = 0.956, Tmax = 0.974	k = −9→9
15490 measured reflections	l = −24→21

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.047	H-atom parameters constrained
wR(F^2) = 0.118	w = 1/[σ^2(Fo^2) + (0.05P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
2820 reflections	Δρmax = 0.16 e Å^−3
157 parameters	Δρmin = −0.26 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0249 (15)

Special details

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.

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

	x	y	z	Uiso*/Ueq
O1	0.14627 (8)	0.10722 (15)	0.23232 (7)	0.0672 (4)
O2	0.07113 (7)	0.29759 (15)	0.29087 (6)	0.0541 (4)
O3	0.16365 (9)	0.5175 (2)	0.08088 (6)	0.0838 (5)
N1	0.15867 (9)	0.72069 (18)	0.19130 (7)	0.0599 (5)
H1A	0.1603	0.7161	0.1457	0.072*
H1B	0.1626	0.8202	0.2127	0.072*
C1	0.14337 (9)	0.4088 (2)	0.19660 (8)	0.0440 (4)
C2	0.15009 (9)	0.5743 (2)	0.22871 (8)	0.0439 (4)
C3	0.15158 (10)	0.6015 (2)	0.30711 (8)	0.0434 (4)
C4	0.09829 (12)	0.7123 (2)	0.33890 (9)	0.0600 (5)
H4	0.0603	0.7672	0.3116	0.072*
C5	0.10137 (15)	0.7419 (2)	0.41122 (10)	0.0738 (7)
H5	0.0647	0.8149	0.4325	0.089*
C6	0.15778 (14)	0.6649 (3)	0.45182 (10)	0.0718 (6)
H6	0.1598	0.6865	0.5004	0.086*
C7	0.21172 (13)	0.5552 (3)	0.42060 (9)	0.0626 (5)
H7	0.2503	0.5030	0.4481	0.075*
C8	0.20845 (11)	0.5228 (2)	0.34860 (8)	0.0507 (5)
H8	0.2446	0.4476	0.3278	0.061*
C9	0.12282 (11)	0.2559 (2)	0.24018 (9)	0.0467 (4)
C10	0.05537 (13)	0.1672 (3)	0.34468 (10)	0.0701 (6)
H10A	0.1033	0.1090	0.3587	0.084*
H10B	0.0196	0.0792	0.3266	0.084*
C11	0.02021 (16)	0.2600 (3)	0.40655 (10)	0.0948 (8)
H11A	0.0581	0.3375	0.4272	0.142*
H11B	0.0039	0.1753	0.4413	0.142*
H11C	−0.0240	0.3269	0.3910	0.142*
C12	0.15219 (11)	0.3890 (2)	0.12037 (10)	0.0559 (5)
C13	0.14568 (14)	0.2117 (3)	0.08559 (10)	0.0789 (7)
H13A	0.1473	0.2254	0.0349	0.118*
H13B	0.0973	0.1577	0.0990	0.118*
H13C	0.1883	0.1388	0.1006	0.118*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0933 (11)	0.0332 (7)	0.0751 (9)	0.0091 (7)	0.0029 (7)	−0.0035 (6)
O2	0.0644 (8)	0.0389 (7)	0.0590 (8)	−0.0013 (6)	0.0085 (6)	0.0035 (6)
O3	0.1432 (14)	0.0649 (10)	0.0434 (8)	−0.0010 (9)	0.0057 (7)	0.0027 (7)
N1	0.1003 (13)	0.0349 (8)	0.0446 (8)	−0.0020 (8)	−0.0027 (8)	0.0014 (7)
C1	0.0588 (11)	0.0340 (9)	0.0393 (9)	0.0034 (8)	−0.0047 (8)	−0.0030 (8)
C2	0.0538 (11)	0.0350 (10)	0.0429 (10)	0.0028 (8)	−0.0019 (8)	0.0010 (8)
C3	0.0619 (11)	0.0279 (8)	0.0404 (9)	−0.0029 (8)	0.0008 (8)	−0.0006 (7)
C4	0.0822 (15)	0.0436 (11)	0.0540 (12)	0.0148 (10)	0.0041 (10)	−0.0007 (9)
C5	0.118 (2)	0.0482 (12)	0.0553 (13)	0.0187 (13)	0.0242 (12)	−0.0048 (10)
C6	0.1233 (19)	0.0535 (13)	0.0386 (11)	−0.0088 (13)	0.0052 (12)	−0.0046 (10)
C7	0.0834 (15)	0.0570 (12)	0.0475 (11)	−0.0069 (11)	−0.0114 (10)	0.0040 (10)
C8	0.0613 (11)	0.0455 (10)	0.0454 (10)	0.0027 (9)	0.0023 (8)	−0.0007 (8)
C9	0.0563 (10)	0.0358 (10)	0.0481 (10)	0.0003 (9)	−0.0088 (9)	−0.0054 (8)
C10	0.0802 (15)	0.0526 (12)	0.0774 (14)	−0.0129 (10)	0.0113 (11)	0.0169 (11)
C11	0.1080 (19)	0.1011 (19)	0.0751 (15)	−0.0256 (16)	0.0248 (14)	0.0062 (14)
C12	0.0718 (13)	0.0486 (11)	0.0471 (11)	0.0067 (10)	−0.0062 (9)	−0.0069 (9)
C13	0.1143 (19)	0.0666 (15)	0.0560 (13)	0.0042 (13)	−0.0082 (11)	−0.0244 (11)

Geometric parameters (Å, º)

O1—C9	1.2098 (19)	C5—H5	0.9300
O2—C9	1.341 (2)	C6—C7	1.378 (3)
O2—C10	1.443 (2)	C6—H6	0.9300
O3—C12	1.244 (2)	C7—C8	1.379 (2)
N1—C2	1.3255 (19)	C7—H7	0.9300
N1—H1A	0.8600	C8—H8	0.9300
N1—H1B	0.8600	C10—C11	1.489 (3)
C1—C2	1.401 (2)	C10—H10A	0.9700
C1—C12	1.451 (2)	C10—H10B	0.9700
C1—C9	1.466 (2)	C11—H11A	0.9600
C2—C3	1.490 (2)	C11—H11B	0.9600
C3—C4	1.380 (2)	C11—H11C	0.9600
C3—C8	1.386 (2)	C12—C13	1.504 (3)
C4—C5	1.381 (2)	C13—H13A	0.9600
C4—H4	0.9300	C13—H13B	0.9600
C5—C6	1.365 (3)	C13—H13C	0.9600
C9—O2—C10	117.45 (14)	C7—C8—H8	119.8
C2—N1—H1A	120.0	C3—C8—H8	119.8
C2—N1—H1B	120.0	O1—C9—O2	121.87 (16)
H1A—N1—H1B	120.0	O1—C9—C1	126.39 (17)
C2—C1—C12	120.74 (15)	O2—C9—C1	111.71 (14)
C2—C1—C9	119.41 (14)	O2—C10—C11	107.38 (16)
C12—C1—C9	119.76 (14)	O2—C10—H10A	110.2
N1—C2—C1	122.32 (14)	C11—C10—H10A	110.2
N1—C2—C3	114.07 (14)	O2—C10—H10B	110.2
C1—C2—C3	123.57 (14)	C11—C10—H10B	110.2
C4—C3—C8	119.08 (15)	H10A—C10—H10B	108.5
C4—C3—C2	120.17 (15)	C10—C11—H11A	109.5
C8—C3—C2	120.68 (15)	C10—C11—H11B	109.5
C3—C4—C5	120.11 (18)	H11A—C11—H11B	109.5
C3—C4—H4	119.9	C10—C11—H11C	109.5
C5—C4—H4	119.9	H11A—C11—H11C	109.5
C6—C5—C4	120.61 (19)	H11B—C11—H11C	109.5
C6—C5—H5	119.7	O3—C12—C1	121.76 (16)
C4—C5—H5	119.7	O3—C12—C13	117.16 (16)
C5—C6—C7	119.81 (17)	C1—C12—C13	121.06 (18)
C5—C6—H6	120.1	C12—C13—H13A	109.5
C7—C6—H6	120.1	C12—C13—H13B	109.5
C6—C7—C8	120.02 (18)	H13A—C13—H13B	109.5
C6—C7—H7	120.0	C12—C13—H13C	109.5
C8—C7—H7	120.0	H13A—C13—H13C	109.5
C7—C8—C3	120.35 (17)	H13B—C13—H13C	109.5
C12—C1—C2—N1	5.3 (3)	C4—C3—C8—C7	−0.1 (3)
C9—C1—C2—N1	−171.24 (16)	C2—C3—C8—C7	176.87 (16)
C12—C1—C2—C3	−172.12 (15)	C10—O2—C9—O1	11.7 (2)
C9—C1—C2—C3	11.4 (3)	C10—O2—C9—C1	−170.17 (14)
N1—C2—C3—C4	58.4 (2)	C2—C1—C9—O1	−144.98 (18)
C1—C2—C3—C4	−124.07 (18)	C12—C1—C9—O1	38.5 (3)
N1—C2—C3—C8	−118.61 (18)	C2—C1—C9—O2	37.0 (2)
C1—C2—C3—C8	59.0 (2)	C12—C1—C9—O2	−139.56 (15)
C8—C3—C4—C5	−0.8 (3)	C9—O2—C10—C11	160.57 (16)
C2—C3—C4—C5	−177.85 (18)	C2—C1—C12—O3	−2.1 (3)
C3—C4—C5—C6	1.2 (3)	C9—C1—C12—O3	174.39 (17)
C4—C5—C6—C7	−0.7 (3)	C2—C1—C12—C13	179.52 (17)
C5—C6—C7—C8	−0.3 (3)	C9—C1—C12—C13	−4.0 (3)
C6—C7—C8—C3	0.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3	0.86	1.94	2.592 (2)	131
N1—H1B···O1^i	0.86	2.23	3.048 (2)	158

Symmetry code: (i) x, y+1, z.