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

Abstract

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,

• a = 27.6055 (6) Å

• b = 11.8164 (2) Å

• c = 8.2934 (1) Å

• β = 102.829 (2)°

• V = 2637.75 (8) ų

• 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[F ² > 2σ(F ²)] = 0.059

• wR(F ²) = 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

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.

Supplementary Material

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—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) ; (ii) ; (iii) .

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 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).

Experimental

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.

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.

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.

Crystal data

C13H13NO5	F000 = 1104
Mr = 263.24	Dx = 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 = 2.9–22.6º
b = 11.8164 (2) Å	µ = 0.10 mm−1
c = 8.29340 (10) Å	T = 298 (2) K
β = 102.829 (2)º	Block, colourless
V = 2637.75 (8) Å3	0.20 × 0.10 × 0.10 mm
Z = 8

Data collection

Bruker SMART CCD area-detector diffractometer	2593 independent reflections
Radiation source: fine-focus sealed tube	1793 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.138
T = 298(2) K	θmax = 26.0º
φ and ω scans	θmin = 1.5º
Absorption correction: multi-scan(SADABS; Sheldrick, 1997)	h = −34→30
Tmin = 0.980, Tmax = 0.990	k = −14→14
13516 measured reflections	l = −10→10

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.059	H-atom parameters constrained
wR(F2) = 0.158	w = 1/[σ2(Fo2) + (0.0987P)2] where P = (Fo2 + 2Fc2)/3
S = 0.97	(Δ/σ)max < 0.001
2593 reflections	Δρmax = 0.20 e Å−3
194 parameters	Δρmin = −0.26 e Å−3
6 restraints	Extinction correction: none
Primary atom site location: structure-invariant direct methods

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	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 (Ų)

	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, °)

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, °)

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.