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

Ismiyev, A.I.

doi:10.1107/S1600536811024974

organic compounds

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Volume 67| Part 7| July 2011| Page o1863

doi:10.1107/S1600536811024974

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

Arif I. Ismiyev ^a ^*

^aBaku State University, Z. Khalilov St. 23, Baku AZ-1148, Azerbaijan
^*Correspondence e-mail: Lab7-Bsu@mail.ru

(Received 10 June 2011; accepted 25 June 2011; online 30 June 2011)

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, P b c a
a = 7.8406 (5) Å
b = 16.8767 (12) Å
c = 17.5420 (13) Å
V = 2321.2 (3) Å³
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[F² > 2σ(F²)] = 0.053
wR(F²) = 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

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

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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811024974/kp2335sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811024974/kp2335Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811024974/kp2335Isup3.cml

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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.

Computing details top

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

Figures top

Fig. 1. The molecular structure of the title compound, with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.

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

Crystal data top

C₁₃H₁₄O₃	F(000) = 928
M_r = 218.24	D_x = 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 top

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

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)] = 0.053	Hydrogen site location: difference Fourier map
wR(F²) = 0.125	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0409P)² + 0.8814P] where P = (F_o² + 2F_c²)/3
2515 reflections	(Δ/σ)_max < 0.001
147 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₃H₁₄O₃	V = 2321.2 (3) Å³
M_r = 218.24	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 7.8406 (5) Å	µ = 0.09 mm⁻¹
b = 16.8767 (12) Å	T = 296 K
c = 17.5420 (13) Å	0.03 × 0.03 × 0.02 mm

Data collection top

Bruker APEXII CCD diffractometer	2515 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	1459 reflections with I > 2σ(I)
T_min = 0.997, T_max = 0.998	R_int = 0.073
17709 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.125	H-atom parameters constrained
S = 1.00	Δρ_max = 0.18 e Å⁻³
2515 reflections	Δρ_min = −0.17 e Å⁻³
147 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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, º) top

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₄O₃
M_r	218.24
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	7.8406 (5), 16.8767 (12), 17.5420 (13)
V (Å³)	2321.2 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.03 × 0.03 × 0.02

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1998)
T_min, T_max	0.997, 0.998
No. of measured, independent and observed [I > 2σ(I)] reflections	17709, 2515, 1459
R_int	0.073
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.125, 1.00
No. of reflections	2515
No. of parameters	147
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.17

Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2001), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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	2.648	3.412 (3)	140

Acknowledgements

The author thanks Professor Victor N. Khrustalev for fruitful discussions and help in this work.

References

Benetti, S., Romagnoli, R., Risi, C. D., Spalluto, G. & Zanirato, V. (1995). Chem. Rev. 95, 1065–1114. CrossRef CAS Web of Science Google Scholar
Bruker (2001). SAINT-Plus. Bruke AXS Inc., Madison, Wisconsin, USA. Google Scholar
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