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

Shi, X.

doi:10.1107/S1600536808039172

organic compounds

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Volume 64| Part 12| December 2008| Page o2462

doi:10.1107/S1600536808039172

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

Xiaopeng Shi ^a ^*

^aDepartment of Chemistry and Biology, Xiangfan University, Xiangfan 441053, People's Republic of China
^*Correspondence e-mail: chemch@163.com

(Received 20 November 2008; accepted 21 November 2008; online 26 November 2008)

The title molecule, C₁₃H₁₃NO₅, adopts a Z conformation at the C= C double bond. The ethoxy atoms of the ethyl ester group are disordered over two orientations in a 3:2 ratio. Weak intermolecular C—H⋯O hydrogen bonds help to establish the packing.

Related literature

For applications of β-keto ester derivatives, see: Benetti et al. (1995 ); Simon et al. (2004 ). For the preparation of the title compound, see Correa & Scott (2001 ).

Experimental

Crystal data

C₁₃H₁₃NO₅
M_r = 263.24
Monoclinic, C 2/c
a = 27.6055 (6) Å
b = 11.8164 (2) Å
c = 8.2934 (1) Å
β = 102.829 (2)°
V = 2637.75 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 (2) K
0.20 × 0.10 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ) T_min = 0.980, T_max = 0.990
13516 measured reflections
2593 independent reflections
1793 reflections with I > 2σ(I)
R_int = 0.138

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.158
S = 0.97
2593 reflections
194 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O2ⁱ	0.93	2.57	3.414 (3)	152
C6—H6⋯O3ⁱⁱ	0.93	2.49	3.381 (2)	161
C10—H10C⋯O4ⁱⁱⁱ	0.96	2.44	3.350 (3)	159
Symmetry codes: (i) -x, -y+1, -z-1; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Data collection: SMART (Bruker, 1997 ); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808039172/cv2486sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808039172/cv2486Isup2.hkl

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 is shown in Fig. 1. It adopts a Z-conformation at the carbon-carbon double bond. The EtO atoms of the ethyl ester group are disordered over two orientations with a ratio 3:2. 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). For the preparation of the title compound, see Correa & Scott (2001).

Experimental top

The title compound was synthesized as previously described by Correa & Scott (2001) via Knoevenagel reaction. Colourless crystals suitable for X-ray data collection were obtained by slow evaporation of a 2:5 ratio CH₂Cl₂:cyclohexane solution at room temperture.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); 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 (Sheldrick, 2008).

Figures top

Fig. 1. View of the title molecule showing the atom-labelling scheme. The displacement ellipsoids are drawn at the 30% probability level. Only major parts of disordered atoms are shown.

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

Crystal data top

C₁₃H₁₃NO₅	F(000) = 1104
M_r = 263.24	D_x = 1.326 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4029 reflections
a = 27.6055 (6) Å	θ = 2.9–22.6°
b = 11.8164 (2) Å	µ = 0.10 mm⁻¹
c = 8.2934 (1) Å	T = 298 K
β = 102.829 (2)°	Block, colourless
V = 2637.75 (8) Å³	0.20 × 0.10 × 0.10 mm
Z = 8

Data collection top

Bruker SMART CCD area-detector diffractometer	2593 independent reflections
Radiation source: fine-focus sealed tube	1793 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.138
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −34→30
T_min = 0.980, T_max = 0.990	k = −14→14
13516 measured reflections	l = −10→10

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.158	H-atom parameters constrained
S = 0.97	w = 1/[σ²(F_o²) + (0.0987P)²] where P = (F_o² + 2F_c²)/3
2593 reflections	(Δ/σ)_max < 0.001
194 parameters	Δρ_max = 0.20 e Å⁻³
6 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₃H₁₃NO₅	V = 2637.75 (8) Å³
M_r = 263.24	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 27.6055 (6) Å	µ = 0.10 mm⁻¹
b = 11.8164 (2) Å	T = 298 K
c = 8.2934 (1) Å	0.20 × 0.10 × 0.10 mm
β = 102.829 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2593 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	1793 reflections with I > 2σ(I)
T_min = 0.980, T_max = 0.990	R_int = 0.138
13516 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	6 restraints
wR(F²) = 0.158	H-atom parameters constrained
S = 0.97	Δρ_max = 0.20 e Å⁻³
2593 reflections	Δρ_min = −0.27 e Å⁻³
194 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	Occ. (<1)
C1	0.15219 (6)	0.41046 (14)	−0.0533 (2)	0.0538 (4)
C2	0.11986 (7)	0.33560 (15)	−0.1504 (2)	0.0614 (5)
H2	0.1256	0.2581	−0.1407	0.074*
C3	0.07915 (7)	0.37643 (16)	−0.2614 (2)	0.0628 (5)
C4	0.06861 (7)	0.49032 (17)	−0.2811 (2)	0.0680 (5)
H4	0.0404	0.5158	−0.3555	0.082*
C5	0.10111 (8)	0.56415 (16)	−0.1875 (3)	0.0712 (6)
H5	0.0952	0.6415	−0.1992	0.085*
C6	0.14224 (7)	0.52611 (15)	−0.0766 (2)	0.0633 (5)
H6	0.1641	0.5783	−0.0154	0.076*
C7	0.19594 (6)	0.37627 (15)	0.0721 (2)	0.0560 (5)
H7	0.2201	0.4319	0.1028	0.067*
C8	0.20630 (6)	0.27679 (14)	0.1490 (2)	0.0527 (4)
C9	0.25275 (7)	0.25541 (17)	0.2757 (2)	0.0606 (5)
C10	0.28732 (8)	0.3502 (2)	0.3368 (3)	0.0772 (6)
H10A	0.3155	0.3219	0.4159	0.116*
H10B	0.2705	0.4060	0.3884	0.116*
H10C	0.2982	0.3838	0.2456	0.116*
C11	0.17337 (7)	0.17457 (15)	0.1156 (2)	0.0560 (5)
C12	0.1062 (3)	0.0766 (7)	0.1660 (8)	0.080 (2)	0.59
H12A	0.1222	0.0066	0.2095	0.095*	0.59
H12B	0.0951	0.0698	0.0469	0.095*	0.59
C13	0.0635 (2)	0.1021 (5)	0.2428 (10)	0.116 (2)	0.59
H13A	0.0755	0.1136	0.3595	0.174*	0.59
H13B	0.0406	0.0399	0.2245	0.174*	0.59
H13C	0.0470	0.1694	0.1939	0.174*	0.59
C13'	0.0614 (2)	0.1029 (7)	0.1166 (11)	0.104 (2)	0.41
H13D	0.0468	0.1698	0.1514	0.156*	0.41
H13E	0.0393	0.0399	0.1158	0.156*	0.41
H13F	0.0668	0.1142	0.0074	0.156*	0.41
C12'	0.1100 (3)	0.0790 (8)	0.2341 (10)	0.067 (2)	0.41
H12C	0.1061	0.0758	0.3473	0.081*	0.41
H12D	0.1241	0.0082	0.2071	0.081*	0.41
N1	0.04577 (8)	0.29598 (17)	−0.3646 (2)	0.0920 (6)
O1	0.05676 (9)	0.19660 (18)	−0.3537 (3)	0.1630 (11)
O2	0.00831 (7)	0.33048 (16)	−0.4573 (2)	0.1147 (7)
O3	0.26098 (5)	0.15976 (13)	0.32832 (18)	0.0838 (5)
O4	0.17660 (6)	0.10267 (12)	0.01722 (17)	0.0800 (5)
O5	0.14066 (5)	0.17397 (11)	0.20985 (18)	0.0728 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0544 (10)	0.0450 (9)	0.0619 (10)	0.0003 (7)	0.0128 (8)	0.0058 (7)
C2	0.0653 (12)	0.0393 (9)	0.0735 (11)	0.0063 (8)	0.0024 (9)	0.0045 (8)
C3	0.0621 (11)	0.0530 (11)	0.0668 (10)	0.0034 (9)	0.0007 (9)	0.0049 (8)
C4	0.0647 (12)	0.0584 (12)	0.0762 (12)	0.0116 (9)	0.0056 (10)	0.0173 (9)
C5	0.0826 (14)	0.0425 (10)	0.0851 (13)	0.0066 (9)	0.0114 (11)	0.0132 (9)
C6	0.0693 (12)	0.0425 (10)	0.0757 (11)	−0.0043 (9)	0.0112 (10)	0.0082 (8)
C7	0.0508 (10)	0.0484 (10)	0.0657 (10)	−0.0028 (7)	0.0067 (8)	0.0023 (8)
C8	0.0510 (9)	0.0478 (9)	0.0574 (9)	0.0034 (7)	0.0081 (7)	0.0014 (7)
C9	0.0547 (10)	0.0651 (13)	0.0608 (10)	0.0036 (9)	0.0103 (8)	0.0054 (9)
C10	0.0618 (12)	0.0905 (16)	0.0716 (12)	−0.0141 (11)	−0.0020 (10)	0.0072 (11)
C11	0.0587 (11)	0.0434 (10)	0.0609 (10)	0.0077 (7)	0.0027 (8)	0.0047 (8)
C12	0.079 (4)	0.064 (3)	0.098 (5)	−0.026 (2)	0.023 (4)	−0.008 (3)
C13	0.076 (3)	0.080 (3)	0.200 (6)	−0.016 (3)	0.048 (4)	0.004 (5)
C13'	0.063 (4)	0.069 (4)	0.167 (7)	−0.001 (3)	−0.003 (5)	−0.006 (6)
C12'	0.075 (5)	0.052 (3)	0.075 (5)	−0.002 (3)	0.017 (4)	0.010 (4)
N1	0.0897 (14)	0.0633 (12)	0.1012 (14)	0.0036 (10)	−0.0255 (11)	−0.0002 (10)
O1	0.167 (2)	0.0637 (13)	0.196 (2)	0.0117 (12)	−0.0941 (17)	−0.0253 (12)
O2	0.0937 (12)	0.0909 (12)	0.1271 (14)	0.0037 (10)	−0.0454 (11)	0.0030 (10)
O3	0.0748 (10)	0.0686 (10)	0.0951 (10)	0.0104 (7)	−0.0090 (8)	0.0172 (8)
O4	0.1037 (12)	0.0516 (8)	0.0834 (9)	0.0019 (7)	0.0182 (8)	−0.0095 (7)
O5	0.0674 (9)	0.0496 (8)	0.1055 (10)	−0.0087 (6)	0.0277 (8)	−0.0052 (7)

Geometric parameters (Å, º) top

C1—C2	1.382 (2)	C10—H10C	0.9600
C1—C6	1.399 (2)	C11—O4	1.195 (2)
C1—C7	1.465 (2)	C11—O5	1.319 (2)
C2—C3	1.372 (3)	C12—O5	1.486 (6)
C2—H2	0.9300	C12—C13	1.487 (7)
C3—C4	1.379 (3)	C12—H12A	0.9700
C3—N1	1.461 (3)	C12—H12B	0.9700
C4—C5	1.364 (3)	C13—H13A	0.9600
C4—H4	0.9300	C13—H13B	0.9600
C5—C6	1.369 (3)	C13—H13C	0.9600
C5—H5	0.9300	C13'—C12'	1.500 (8)
C6—H6	0.9300	C13'—H13D	0.9600
C7—C8	1.338 (2)	C13'—H13E	0.9600
C7—H7	0.9300	C13'—H13F	0.9600
C8—C9	1.488 (3)	C12'—O5	1.446 (8)
C8—C11	1.500 (2)	C12'—H12C	0.9700
C9—O3	1.215 (2)	C12'—H12D	0.9700
C9—C10	1.485 (3)	N1—O1	1.211 (3)
C10—H10A	0.9600	N1—O2	1.213 (2)
C10—H10B	0.9600

C2—C1—C6	117.59 (17)	C9—C10—H10C	109.5
C2—C1—C7	124.16 (16)	H10A—C10—H10C	109.5
C6—C1—C7	118.25 (16)	H10B—C10—H10C	109.5
C3—C2—C1	119.53 (16)	O4—C11—O5	124.43 (17)
C3—C2—H2	120.2	O4—C11—C8	124.37 (17)
C1—C2—H2	120.2	O5—C11—C8	111.19 (14)
C2—C3—C4	122.85 (18)	O5—C12—C13	105.2 (5)
C2—C3—N1	118.70 (17)	O5—C12—H12A	110.7
C4—C3—N1	118.44 (17)	C13—C12—H12A	110.7
C5—C4—C3	117.52 (17)	O5—C12—H12B	110.7
C5—C4—H4	121.2	C13—C12—H12B	110.7
C3—C4—H4	121.2	H12A—C12—H12B	108.8
C4—C5—C6	121.01 (18)	C12'—C13'—H13D	109.5
C4—C5—H5	119.5	C12'—C13'—H13E	109.5
C6—C5—H5	119.5	H13D—C13'—H13E	109.5
C5—C6—C1	121.46 (18)	C12'—C13'—H13F	109.5
C5—C6—H6	119.3	H13D—C13'—H13F	109.5
C1—C6—H6	119.3	H13E—C13'—H13F	109.5
C8—C7—C1	129.51 (17)	O5—C12'—C13'	103.4 (6)
C8—C7—H7	115.2	O5—C12'—H12C	111.1
C1—C7—H7	115.2	C13'—C12'—H12C	111.1
C7—C8—C9	123.05 (17)	O5—C12'—H12D	111.1
C7—C8—C11	124.25 (16)	C13'—C12'—H12D	111.1
C9—C8—C11	112.68 (15)	H12C—C12'—H12D	109.1
O3—C9—C10	121.61 (18)	O1—N1—O2	122.5 (2)
O3—C9—C8	118.35 (17)	O1—N1—C3	118.14 (19)
C10—C9—C8	120.03 (17)	O2—N1—C3	119.4 (2)
C9—C10—H10A	109.5	C11—O5—C12'	125.8 (4)
C9—C10—H10B	109.5	C11—O5—C12	110.2 (3)
H10A—C10—H10B	109.5

C6—C1—C2—C3	−1.6 (3)	C11—C8—C9—C10	−173.76 (16)
C7—C1—C2—C3	178.23 (17)	C7—C8—C11—O4	91.9 (2)
C1—C2—C3—C4	−0.1 (3)	C9—C8—C11—O4	−87.0 (2)
C1—C2—C3—N1	179.14 (17)	C7—C8—C11—O5	−88.6 (2)
C2—C3—C4—C5	1.4 (3)	C9—C8—C11—O5	92.48 (17)
N1—C3—C4—C5	−177.85 (18)	C2—C3—N1—O1	−3.5 (3)
C3—C4—C5—C6	−0.9 (3)	C4—C3—N1—O1	175.8 (2)
C4—C5—C6—C1	−0.9 (3)	C2—C3—N1—O2	176.3 (2)
C2—C1—C6—C5	2.1 (3)	C4—C3—N1—O2	−4.4 (3)
C7—C1—C6—C5	−177.72 (17)	O4—C11—O5—C12'	12.4 (5)
C2—C1—C7—C8	−20.0 (3)	C8—C11—O5—C12'	−167.1 (4)
C6—C1—C7—C8	159.84 (18)	O4—C11—O5—C12	−4.6 (4)
C1—C7—C8—C9	−179.60 (16)	C8—C11—O5—C12	175.9 (4)
C1—C7—C8—C11	1.6 (3)	C13'—C12'—O5—C11	−98.1 (7)
C7—C8—C9—O3	−173.65 (17)	C13'—C12'—O5—C12	−49.8 (16)
C11—C8—C9—O3	5.3 (2)	C13—C12—O5—C11	−164.4 (4)
C7—C8—C9—C10	7.3 (3)	C13—C12—O5—C12'	55.7 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O2ⁱ	0.93	2.57	3.414 (3)	152
C6—H6···O3ⁱⁱ	0.93	2.49	3.381 (2)	161
C10—H10C···O4ⁱⁱⁱ	0.96	2.44	3.350 (3)	159

Symmetry codes: (i) −x, −y+1, −z−1; (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x+1/2, −y+1/2, −z.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₃NO₅
M_r	263.24
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	27.6055 (6), 11.8164 (2), 8.2934 (1)
β (°)	102.829 (2)
V (Å³)	2637.75 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1997)
T_min, T_max	0.980, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	13516, 2593, 1793
R_int	0.138
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.158, 0.97
No. of reflections	2593
No. of parameters	194
No. of restraints	6
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.27

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O2ⁱ	0.93	2.57	3.414 (3)	151.6
C6—H6···O3ⁱⁱ	0.93	2.49	3.381 (2)	160.9
C10—H10C···O4ⁱⁱⁱ	0.96	2.44	3.350 (3)	159.1

Symmetry codes: (i) −x, −y+1, −z−1; (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x+1/2, −y+1/2, −z.

Acknowledgements

The author is grateful to Hua Cheng for helpful discussions.

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
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Bruker (1999). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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