Ethyl 2-[(3-chloro­phen­yl)hydrazono]-3-oxobutanoate

Hoong-Kun Fun; Mahesh Padaki; Sowmya; Arun M Isloor; Suchada Chantrapromma

doi:10.1107/S160053680901784X

. 2009 May 20;65(Pt 6):o1320–o1321. doi: 10.1107/S160053680901784X

Ethyl 2-[(3-chlorophenyl)hydrazono]-3-oxobutanoate

Hoong-Kun Fun ^a,^*,^‡, Mahesh Padaki ^b, Sowmya ^b, Arun M Isloor ^b, Suchada Chantrapromma ^c,^§

PMCID: PMC2969699 PMID: 21583177

Abstract

The molecule of the title oxobutanoate derivative, C₁₂H₁₃ClN₂O₃, adopts a keto–hydrazo tautomeric form and is roughly planar, the angle between the benzene ring and the mean plane through the hydrazone and aliphatic chain being 1.49 (6)°. This planarity is further aided by the formation of an intramolecular N—H⋯O hydrogen bond which generates an S(6) ring motif. The aromatic ring and aliphatic chain have a trans configuration with respect to the N—N bond. In the crystal packing, centrosymmetric R ₂ ²(16) dimers are formed through pairs of weak C—H⋯O(3-oxo) interactions. These dimers are linked together through weak C—H⋯O(carboxylate C=O) interactions into ribbons along the b-axis direction. These ribbons are stacked along the a-axis direction. The crystal also exhibits Cl⋯Cl [3.4988 (6) Å] and C⋯O [3.167 (2)–3.335 (2) Å] short contacts.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For background to the bioactivity and applications of oxobutanoate derivatives, see: Alpaslan et al. (2005a ▶,b ▶); Stancho et al. (2008 ▶). For related structures, see: Alpaslan et al. (2005a ▶,b ▶); Fun et al. (2009 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer, (1986 ▶).

Experimental

Crystal data

C₁₂H₁₃ClN₂O₃
M _r = 268.69
Triclinic,
a = 4.0826 (2) Å
b = 10.3196 (4) Å
c = 15.1469 (6) Å
α = 88.336 (3)°
β = 87.033 (3)°
γ = 83.734 (2)°
V = 633.31 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 120 K
0.39 × 0.11 × 0.06 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.890, T _max = 0.981
11030 measured reflections
3678 independent reflections
2732 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.139
S = 1.05
3678 reflections
169 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.75 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; 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 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680901784X/fb2150sup1.cif

e-65-o1320-sup1.cif^{(17.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680901784X/fb2150Isup2.hkl

e-65-o1320-Isup2.hkl^{(180.3KB, hkl)}

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
N1—H1N1⋯O3	0.91 (3)	1.87 (3)	2.564 (2)	132 (3)
C3—H3A⋯O1ⁱ	0.93	2.54	3.211 (2)	129
C5—H5A⋯O3ⁱⁱ	0.93	2.52	3.433 (2)	166

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

AMI is grateful to the Head of the Chemistry Department and the Director, NITK, Surathkal, India, for providing research facilities. SC thanks Prince of Songkla University for financial support through the Crystal Materials Research Unit. The authors thank Universiti Sains Malaysia for the Research University Golden Goose Grant No. 1001/PFIZIK/811012.

supplementary crystallographic information

Comment

In recent years, the chemistry of hydrazones have been the subject of intense study mostly due to their biological significance. Some oxobutanoate derviatives exhibit cytotoxicity (Stancho et al., 2008). We previously reported the crystal structure of the ethyl 2-[(4-chlorophenyl)hydrazono]-3-oxobutanoate (I) (Fun et al., 2009). As part of our on going research on the synthesis and biological activity of oxobutanoates, we report here the synthesis and crystal structure of the title compound, ethyl 2-[(3-chlorophenyl)hydrazono]-3-oxobutanoate (II).

The molecule of the title oxobutanoate derivative (II), C₁₂H₁₃ClN₂O₃, adopts a keto-hydrazo tautomeric form and is roughly planar as indicated by the interplanar angle between the benzene ring and the mean plane through the hydrazone and aliphatic chain (N1–N2/O1–O3/C7–C12) being 1.49 (6)°. The aromatic ring and aliphatic chain have a trans configuration with respect to the N—N bond as evidenced by the torsion angle C6–N1–N2–C7 being 179.76 (15)°. The orientations of 3-oxobutanoate and ethyl group are determined by the torsion angles C10–C7–C8–C9 = 3.3 (3)° and C10–O2–C11–C12 = 168.38 (10)° [the corresponding angles are 2.81 (15)° and 170.6 (9)° in (I) (Fun et al., 2009)]. The intramolecular N1—H1···O1 hydrogen bond generates an S(6) ring motif (Bernstein et al., 1995) (Table 1). The bond distances in (II) have normal values (Allen et al., 1987) and are comparable to those in closely related structures (Alpaslan et al., 2005a, b; Fun et al., 2009).

In the crystal packing (Fig. 2), the molecules are present as centrosymmetric R₂²(16) dimers being joined by weak, centrosymmetrically related C5—H5A···O3 interactions involving the 3-oxo group (Table 1). These dimers are linked together through weak C3—H3A···O1 (carboxylate C═O) interactions (Table 1) into ribbons along the b direction. These ribbons are stacked along the a direction. The crystal also shows Cl···Cl [3.4988 (6) Å; symmetry code: 2 - x, 3 - y, -z] and C···O [3.167 (2)–3.335 (2) Å; symmetry code: -1 + x, y, z] short contacts.

Experimental

The title compound was prepared by disolving 3-chloroaniline (1.27 g, 10 mmol) in dilute hydrochloric acid (11.0 ml), obtained by mixing 4.5 ml of 12 M HCl and 6.5 ml water. The solution was cooled to 273 K in ice bath. To this, a cold solution of sodium nitrite (1.6 g, 23.1 mmol in 5.0 ml water) was added. The temperature of reaction mixture was not allowed to rise above 323 K. The diazonium salt solution so formed was poured through a filter into a cooled solution of ethylacetoacetate (1.7 ml) and sodium acetate (3.5 g) in ethanol (50 ml). The resulting yellow solid was filtered, washed with ice cold water, dried in air and recrystallized from methanol. Yield was found to be 1.70 g (70 %), M.p. 360 K.