(Z)-Ethyl 2-benzyl­idene-3-oxobutano­ate

Abstract

The title mol­ecule, C₁₃H₁₄O₃, adopts a Z conformation about the C=C double bond. In the crystal, weak inter­molecular C—H⋯O hydrogen bonds with phenyl –CH atoms functioning as donors and the carbonyl O atom of an ester group as acceptor are observed.

Related literature

For applications of β-keto ester derivatives, see: Benetti et al. (1995 ▶); Simon et al. (2004 ▶).

Experimental

Crystal data

• C₁₃H₁₄O₃

• M _r = 218.24

• Orthorhombic,

• a = 7.8406 (5) Å

• b = 16.8767 (12) Å

• c = 17.5420 (13) Å

• V = 2321.2 (3) ų

• Z = 8

• Mo Kα radiation

• μ = 0.09 mm⁻¹

• T = 296 K

• 0.03 × 0.03 × 0.02 mm

Data collection

• Bruker APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1998) ▶ T _min = 0.997, T _max = 0.998

• 17709 measured reflections

• 2515 independent reflections

• 1459 reflections with I > 2σ(I)

• R _int = 0.073

Refinement

• R[F ² > 2σ(F ²)] = 0.053

• wR(F ²) = 0.125

• S = 1.00

• 2515 reflections

• 147 parameters

• H-atom parameters constrained

• Δρ_max = 0.18 e Å⁻³

• Δρ_min = −0.17 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811024974/kp2335Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯O2	0.93	2.62	3.544 (3)	170
C5—H5A⋯O2	0.93	2.65	3.412 (3)	140

supplementary crystallographic information

Comment

β-Keto ester derivatives, as important synthetic intermediates, are widely applied in the synthesis of new heterocyclic derivatives presenting new pharmacological properties (Benetti et al., 1995; Simon et al., 2004). The molecular structure of the title compound adopts a Z-conformation at the carbon-carbon double bond (Fig. 1). The molecules are connected mainly by intermolecular C—H···O interactions (Table 1).

Experimental

Benzaldehyde (20 mmol) and acetoacetic ester (20 mmol) were dissolved in 20 mL ethanol. After adding 0.50 mL piperidine mixture was stirred at room tempertue for 10 h. White crystals were obtained. The crystals were filtered off and washed with ethanol. Then they were dissolved in ethanol (20 mL) and recrystallised to yield colourless block-shaped crystals of the title compound.

Refinement

All H atoms were positioned geometrically (C—H = 0.93–0.97 Å) and refined as riding, allowing for free rotation of the methyl groups. The constraint U_iso(H) = 1.2 U_eq(C) or 1.5 U_eq(C) (methyl C) was applied.

Figures

Fig. 1.

The molecular structure of the title compound, with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.

Crystal data

C13H14O3	F(000) = 928
Mr = 218.24	Dx = 1.249 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1409 reflections
a = 7.8406 (5) Å	θ = 2.3–21.4°
b = 16.8767 (12) Å	µ = 0.09 mm−1
c = 17.5420 (13) Å	T = 296 K
V = 2321.2 (3) Å3	Prism, colourless
Z = 8	0.03 × 0.03 × 0.02 mm

Data collection

Bruker APEXII CCD diffractometer	2515 independent reflections
Radiation source: fine-focus sealed tube	1459 reflections with I > 2σ(I)
graphite	Rint = 0.073
phi and ω scans	θmax = 27.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	h = −10→10
Tmin = 0.997, Tmax = 0.998	k = −21→21
17709 measured reflections	l = −22→22

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)] = 0.053	Hydrogen site location: difference Fourier map
wR(F2) = 0.125	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0409P)2 + 0.8814P] where P = (Fo2 + 2Fc2)/3
2515 reflections	(Δ/σ)max < 0.001
147 parameters	Δρmax = 0.18 e Å−3
0 restraints	Δρmin = −0.17 e Å−3

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	0.3871 (2)	0.22540 (10)	0.50159 (10)	0.0679 (5)
O2	0.4542 (2)	0.17527 (10)	0.66960 (9)	0.0577 (5)
O3	0.66163 (18)	0.11601 (9)	0.60314 (8)	0.0488 (4)
C1	0.3604 (3)	−0.03682 (12)	0.61668 (12)	0.0416 (5)
C2	0.4421 (3)	−0.02544 (14)	0.68650 (12)	0.0511 (6)
H2A	0.4778	0.0251	0.7004	0.061*
C3	0.4706 (3)	−0.08813 (15)	0.73500 (14)	0.0599 (7)
H3A	0.5266	−0.0798	0.7810	0.072*
C4	0.4170 (3)	−0.16243 (15)	0.71591 (15)	0.0620 (7)
H4A	0.4371	−0.2047	0.7488	0.074*
C5	0.3338 (3)	−0.17479 (15)	0.64858 (16)	0.0634 (7)
H5A	0.2960	−0.2254	0.6360	0.076*
C6	0.3056 (3)	−0.11284 (14)	0.59944 (14)	0.0510 (6)
H6A	0.2488	−0.1220	0.5538	0.061*
C7	0.3282 (3)	0.02582 (13)	0.56098 (12)	0.0417 (5)
H7A	0.2576	0.0111	0.5208	0.050*
C8	0.3835 (3)	0.10083 (13)	0.55822 (11)	0.0403 (5)
C9	0.5003 (3)	0.13555 (12)	0.61673 (12)	0.0410 (5)
C10	0.7862 (3)	0.14424 (16)	0.65832 (14)	0.0585 (7)
H10A	0.7593	0.1242	0.7087	0.070*
H10B	0.7859	0.2017	0.6601	0.070*
C11	0.9541 (3)	0.11498 (19)	0.63350 (16)	0.0738 (8)
H11A	1.0395	0.1312	0.6695	0.111*
H11B	0.9807	0.1365	0.5842	0.111*
H11C	0.9518	0.0582	0.6306	0.111*
C12	0.3325 (3)	0.15853 (15)	0.49856 (13)	0.0485 (6)
C13	0.2141 (3)	0.13393 (17)	0.43558 (14)	0.0677 (8)
H13A	0.1707	0.1802	0.4103	0.102*
H13B	0.1209	0.1041	0.4565	0.102*
H13C	0.2749	0.1017	0.3996	0.102*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0888 (13)	0.0502 (11)	0.0645 (11)	0.0025 (10)	−0.0006 (10)	0.0121 (9)
O2	0.0627 (11)	0.0574 (10)	0.0530 (10)	0.0107 (8)	0.0007 (8)	−0.0164 (8)
O3	0.0411 (8)	0.0639 (10)	0.0414 (9)	0.0030 (7)	−0.0003 (7)	−0.0061 (7)
C1	0.0414 (11)	0.0441 (13)	0.0392 (12)	0.0014 (10)	0.0031 (9)	−0.0016 (10)
C2	0.0671 (15)	0.0430 (13)	0.0433 (13)	−0.0046 (11)	−0.0060 (11)	0.0027 (11)
C3	0.0719 (17)	0.0594 (16)	0.0484 (15)	−0.0003 (13)	−0.0031 (13)	0.0102 (12)
C4	0.0742 (17)	0.0507 (15)	0.0609 (16)	0.0039 (13)	0.0113 (14)	0.0130 (13)
C5	0.0754 (18)	0.0447 (14)	0.0702 (18)	−0.0076 (13)	0.0139 (15)	−0.0028 (13)
C6	0.0534 (14)	0.0493 (14)	0.0501 (14)	−0.0056 (11)	0.0029 (11)	−0.0042 (12)
C7	0.0407 (11)	0.0483 (13)	0.0359 (11)	0.0035 (10)	−0.0023 (9)	−0.0031 (10)
C8	0.0379 (11)	0.0484 (13)	0.0347 (11)	0.0081 (10)	0.0010 (9)	−0.0003 (10)
C9	0.0455 (12)	0.0388 (11)	0.0386 (12)	0.0037 (10)	0.0046 (10)	0.0029 (10)
C10	0.0505 (14)	0.0740 (18)	0.0510 (14)	−0.0034 (13)	−0.0098 (11)	−0.0061 (13)
C11	0.0472 (15)	0.106 (2)	0.0685 (17)	0.0017 (15)	−0.0065 (13)	0.0004 (16)
C12	0.0501 (13)	0.0554 (15)	0.0401 (13)	0.0112 (12)	0.0055 (11)	0.0027 (11)
C13	0.0714 (18)	0.0825 (19)	0.0492 (14)	0.0105 (15)	−0.0126 (13)	0.0149 (14)

Geometric parameters (Å, °)

O1—C12	1.208 (3)	C6—H6A	0.9300
O2—C9	1.200 (2)	C7—C8	1.339 (3)
O3—C9	1.329 (2)	C7—H7A	0.9300
O3—C10	1.455 (3)	C8—C12	1.484 (3)
C1—C6	1.386 (3)	C8—C9	1.495 (3)
C1—C2	1.395 (3)	C10—C11	1.472 (3)
C1—C7	1.462 (3)	C10—H10A	0.9700
C2—C3	1.376 (3)	C10—H10B	0.9700
C2—H2A	0.9300	C11—H11A	0.9600
C3—C4	1.364 (4)	C11—H11B	0.9600
C3—H3A	0.9300	C11—H11C	0.9600
C4—C5	1.365 (4)	C12—C13	1.502 (3)
C4—H4A	0.9300	C13—H13A	0.9600
C5—C6	1.373 (3)	C13—H13B	0.9600
C5—H5A	0.9300	C13—H13C	0.9600
C9—O3—C10	116.00 (17)	O2—C9—O3	124.3 (2)
C6—C1—C2	117.5 (2)	O2—C9—C8	124.4 (2)
C6—C1—C7	118.0 (2)	O3—C9—C8	111.27 (18)
C2—C1—C7	124.5 (2)	O3—C10—C11	107.1 (2)
C3—C2—C1	120.8 (2)	O3—C10—H10A	110.3
C3—C2—H2A	119.6	C11—C10—H10A	110.3
C1—C2—H2A	119.6	O3—C10—H10B	110.3
C4—C3—C2	120.3 (2)	C11—C10—H10B	110.3
C4—C3—H3A	119.8	H10A—C10—H10B	108.6
C2—C3—H3A	119.8	C10—C11—H11A	109.5
C3—C4—C5	120.0 (2)	C10—C11—H11B	109.5
C3—C4—H4A	120.0	H11A—C11—H11B	109.5
C5—C4—H4A	120.0	C10—C11—H11C	109.5
C4—C5—C6	120.2 (2)	H11A—C11—H11C	109.5
C4—C5—H5A	119.9	H11B—C11—H11C	109.5
C6—C5—H5A	119.9	O1—C12—C8	119.1 (2)
C5—C6—C1	121.2 (2)	O1—C12—C13	120.7 (2)
C5—C6—H6A	119.4	C8—C12—C13	120.3 (2)
C1—C6—H6A	119.4	C12—C13—H13A	109.5
C8—C7—C1	130.7 (2)	C12—C13—H13B	109.5
C8—C7—H7A	114.6	H13A—C13—H13B	109.5
C1—C7—H7A	114.6	C12—C13—H13C	109.5
C7—C8—C12	124.0 (2)	H13A—C13—H13C	109.5
C7—C8—C9	122.95 (19)	H13B—C13—H13C	109.5
C12—C8—C9	113.07 (19)
C6—C1—C2—C3	1.7 (3)	C10—O3—C9—O2	1.5 (3)
C7—C1—C2—C3	−178.6 (2)	C10—O3—C9—C8	−177.80 (18)
C1—C2—C3—C4	−0.9 (4)	C7—C8—C9—O2	−97.9 (3)
C2—C3—C4—C5	−0.4 (4)	C12—C8—C9—O2	80.6 (3)
C3—C4—C5—C6	0.8 (4)	C7—C8—C9—O3	81.4 (2)
C4—C5—C6—C1	0.0 (4)	C12—C8—C9—O3	−100.1 (2)
C2—C1—C6—C5	−1.2 (3)	C9—O3—C10—C11	178.9 (2)
C7—C1—C6—C5	179.0 (2)	C7—C8—C12—O1	178.8 (2)
C6—C1—C7—C8	−171.0 (2)	C9—C8—C12—O1	0.3 (3)
C2—C1—C7—C8	9.3 (4)	C7—C8—C12—C13	−0.9 (3)
C1—C7—C8—C12	−177.4 (2)	C9—C8—C12—C13	−179.4 (2)
C1—C7—C8—C9	1.0 (4)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O2i	0.93	2.62	3.544 (3)	170
C5—H5A···O2ii	0.93	2.65	3.412 (3)	140

Symmetry codes: (i) ; (ii) .