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Acta Crystallogr Sect E Struct Rep Online. 2009 June 1; 65(Pt 6): o1320–o1321.
Published online 2009 May 20. doi:  10.1107/S160053680901784X
PMCID: PMC2969699

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

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

An external file that holds a picture, illustration, etc.
Object name is e-65-o1320-scheme1.jpg

Experimental

Crystal data

  • C12H13ClN2O3
  • M r = 268.69
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1320-efi1.jpg
  • 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 [triangle]) 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
  • Δρmax = 0.75 e Å−3
  • Δρmin = −0.27 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

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

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.

Refinement

The hydrazone H atom was located in a difference map and refined isotropically. The remaining H atoms were placed in calculated positions with d(C—H) = 0.93 Å for aromatic, 0.97 for CH2 and 0.96 Å for CH3 atoms. The Uiso values were constrained to be 1.5Ueq of the carrier atom for methyl H atoms and 1.2Ueq for the remaining H atoms. A rotating group model was used for the methyl groups. The highest residual electron density peak is located at 0.86 Å from Cl1 and the deepest hole is located at 1.19 Å from C2. The difference electron density map also indicated possible tautomerism with the docking site (N2). However, the 1H NMR experiments did not confirm this tautomerism. Moreover it would be difficult to model a resonance structure that would be in agreement with the presumed tautomerism.

Figures

Fig. 1.
A view of the title molecule, showing 50% probability displacement ellipsoids and the atom-numbering scheme. The N—H···O hydrogen bond is depicted as a dashed line.
Fig. 2.
The packing diagram of the title compound, viewed along the a axis, showing the molecular ribbons. Hydrogen bonds are drawn as dashed lines.

Crystal data

C12H13ClN2O3Z = 2
Mr = 268.69F(000) = 280
Triclinic, P1Dx = 1.409 Mg m3
Hall symbol: -P 1Melting point: 360 K
a = 4.0826 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.3196 (4) ÅCell parameters from 3678 reflections
c = 15.1469 (6) Åθ = 1.4–30.0°
α = 88.336 (3)°µ = 0.30 mm1
β = 87.033 (3)°T = 120 K
γ = 83.734 (2)°Needle, yellow
V = 633.31 (5) Å30.39 × 0.11 × 0.06 mm

Data collection

Bruker APEXII CCD area-detector diffractometer3678 independent reflections
Radiation source: sealed tube2732 reflections with I > 2σ(I)
graphiteRint = 0.036
[var phi] and ω scansθmax = 30.0°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −5→5
Tmin = 0.890, Tmax = 0.981k = −14→14
11030 measured reflectionsl = −18→21

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139H atoms treated by a mixture of independent and constrained refinement
S = 1.05w = 1/[σ2(Fo2) + (0.0778P)2 + 0.1165P] where P = (Fo2 + 2Fc2)/3
3678 reflections(Δ/σ)max = 0.001
169 parametersΔρmax = 0.75 e Å3
0 restraintsΔρmin = −0.27 e Å3

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 120.0 (1) K.
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)

xyzUiso*/Ueq
Cl11.05405 (13)1.38226 (4)0.08494 (3)0.02972 (15)
O10.6525 (4)0.66454 (13)0.29235 (9)0.0307 (3)
O20.6912 (3)0.82739 (12)0.19234 (8)0.0233 (3)
O31.2031 (4)0.86080 (13)0.46009 (9)0.0300 (3)
N11.1619 (4)1.03691 (14)0.33708 (10)0.0199 (3)
N20.9988 (3)0.95997 (13)0.29359 (10)0.0189 (3)
C11.1244 (4)1.20062 (16)0.21705 (11)0.0207 (3)
H1A1.01551.14750.18260.025*
C21.1889 (4)1.32389 (17)0.18746 (12)0.0207 (3)
C31.3528 (4)1.40505 (16)0.23737 (12)0.0226 (4)
H3A1.39041.48800.21630.027*
C41.4591 (4)1.35961 (17)0.31912 (12)0.0229 (4)
H4A1.57321.41200.35280.027*
C51.3972 (4)1.23677 (16)0.35144 (12)0.0206 (3)
H5A1.46761.20690.40650.025*
C61.2282 (4)1.15919 (16)0.30004 (11)0.0185 (3)
C70.9369 (4)0.84466 (16)0.32803 (11)0.0190 (3)
C81.0544 (4)0.79195 (17)0.41344 (12)0.0222 (4)
C91.0059 (5)0.65572 (17)0.44501 (13)0.0260 (4)
H9A1.11620.63670.49910.039*
H9B1.09610.59500.40100.039*
H9C0.77450.64840.45510.039*
C100.7486 (4)0.76823 (16)0.27083 (11)0.0201 (3)
C110.5170 (5)0.75610 (17)0.13154 (12)0.0248 (4)
H11A0.32380.72470.16130.030*
H11B0.65960.68190.10890.030*
C120.4174 (5)0.8497 (2)0.05750 (14)0.0331 (4)
H12A0.30630.80570.01480.050*
H12B0.61030.88170.02970.050*
H12C0.27190.92140.08070.050*
H1N11.211 (6)1.016 (3)0.3940 (17)0.043 (7)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0420 (3)0.0212 (2)0.0261 (2)−0.00346 (18)−0.00707 (18)0.00680 (16)
O10.0434 (8)0.0159 (6)0.0353 (7)−0.0126 (6)−0.0079 (6)0.0038 (5)
O20.0281 (6)0.0170 (6)0.0259 (6)−0.0066 (5)−0.0059 (5)0.0027 (5)
O30.0436 (8)0.0185 (6)0.0290 (7)−0.0051 (6)−0.0111 (6)0.0037 (5)
N10.0242 (7)0.0112 (6)0.0246 (8)−0.0018 (5)−0.0046 (6)0.0020 (5)
N20.0187 (7)0.0114 (6)0.0264 (7)−0.0006 (5)−0.0016 (6)−0.0006 (5)
C10.0244 (8)0.0139 (8)0.0245 (8)−0.0038 (6)−0.0033 (7)−0.0013 (6)
C20.0242 (8)0.0145 (8)0.0225 (8)0.0019 (6)−0.0025 (7)0.0036 (6)
C30.0271 (9)0.0108 (7)0.0303 (9)−0.0052 (6)−0.0001 (7)0.0018 (6)
C40.0249 (9)0.0138 (8)0.0310 (9)−0.0042 (6)−0.0045 (7)−0.0044 (7)
C50.0220 (8)0.0158 (8)0.0238 (8)0.0000 (6)−0.0039 (6)0.0007 (6)
C60.0198 (8)0.0105 (7)0.0249 (8)−0.0006 (6)0.0001 (6)0.0008 (6)
C70.0203 (8)0.0114 (7)0.0253 (8)−0.0016 (6)−0.0012 (6)0.0014 (6)
C80.0250 (8)0.0149 (8)0.0257 (9)0.0009 (6)−0.0005 (7)0.0019 (6)
C90.0306 (9)0.0157 (8)0.0310 (9)−0.0004 (7)−0.0026 (7)0.0052 (7)
C100.0195 (8)0.0153 (8)0.0254 (8)−0.0014 (6)−0.0012 (6)0.0005 (6)
C110.0276 (9)0.0185 (8)0.0292 (9)−0.0049 (7)−0.0045 (7)−0.0031 (7)
C120.0368 (11)0.0286 (10)0.0349 (11)−0.0045 (8)−0.0116 (9)0.0023 (8)

Geometric parameters (Å, °)

Cl1—C21.7432 (18)C4—H4A0.9300
O1—C101.210 (2)C5—C61.391 (2)
O2—C101.340 (2)C5—H5A0.9300
O2—C111.455 (2)C7—C81.472 (2)
O3—C81.241 (2)C7—C101.485 (2)
N1—N21.303 (2)C8—C91.502 (2)
N1—C61.414 (2)C9—H9A0.9600
N1—H1N10.91 (3)C9—H9B0.9600
N2—C71.330 (2)C9—H9C0.9600
C1—C21.384 (2)C11—C121.501 (3)
C1—C61.388 (2)C11—H11A0.9700
C1—H1A0.9300C11—H11B0.9700
C2—C31.390 (2)C12—H12A0.9600
C3—C41.385 (2)C12—H12B0.9600
C3—H3A0.9300C12—H12C0.9600
C4—C51.390 (2)
C10—O2—C11115.77 (13)C8—C7—C10121.60 (14)
N2—N1—C6120.27 (15)O3—C8—C7119.29 (15)
N2—N1—H1N1119.6 (16)O3—C8—C9118.90 (16)
C6—N1—H1N1119.7 (16)C7—C8—C9121.80 (15)
N1—N2—C7120.48 (15)C8—C9—H9A109.5
C2—C1—C6117.59 (15)C8—C9—H9B109.5
C2—C1—H1A121.2H9A—C9—H9B109.5
C6—C1—H1A121.2C8—C9—H9C109.5
C1—C2—C3122.41 (16)H9A—C9—H9C109.5
C1—C2—Cl1119.40 (13)H9B—C9—H9C109.5
C3—C2—Cl1118.17 (13)O1—C10—O2123.08 (16)
C4—C3—C2118.50 (15)O1—C10—C7124.24 (16)
C4—C3—H3A120.8O2—C10—C7112.67 (14)
C2—C3—H3A120.8O2—C11—C12106.71 (14)
C3—C4—C5120.83 (15)O2—C11—H11A110.4
C3—C4—H4A119.6C12—C11—H11A110.4
C5—C4—H4A119.6O2—C11—H11B110.4
C4—C5—C6118.93 (16)C12—C11—H11B110.4
C4—C5—H5A120.5H11A—C11—H11B108.6
C6—C5—H5A120.5C11—C12—H12A109.5
C1—C6—C5121.71 (15)C11—C12—H12B109.5
C1—C6—N1121.53 (15)H12A—C12—H12B109.5
C5—C6—N1116.75 (15)C11—C12—H12C109.5
N2—C7—C8124.09 (15)H12A—C12—H12C109.5
N2—C7—C10114.25 (15)H12B—C12—H12C109.5
C6—N1—N2—C7179.76 (15)N1—N2—C7—C8−2.8 (3)
C6—C1—C2—C30.4 (3)N1—N2—C7—C10179.91 (14)
C6—C1—C2—Cl1−178.31 (13)N2—C7—C8—O34.8 (3)
C1—C2—C3—C40.9 (3)C10—C7—C8—O3−178.06 (16)
Cl1—C2—C3—C4179.64 (13)N2—C7—C8—C9−173.83 (16)
C2—C3—C4—C5−1.3 (3)C10—C7—C8—C93.3 (3)
C3—C4—C5—C60.4 (3)C11—O2—C10—O1−2.8 (2)
C2—C1—C6—C5−1.3 (3)C11—O2—C10—C7178.04 (14)
C2—C1—C6—N1177.53 (16)N2—C7—C10—O1−175.72 (16)
C4—C5—C6—C10.9 (3)C8—C7—C10—O16.9 (3)
C4—C5—C6—N1−177.98 (16)N2—C7—C10—O23.4 (2)
N2—N1—C6—C1−0.3 (2)C8—C7—C10—O2−173.96 (15)
N2—N1—C6—C5178.63 (15)C10—O2—C11—C12168.38 (16)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1N1···O30.91 (3)1.87 (3)2.564 (2)132 (3)
C3—H3A···O1i0.932.543.211 (2)129
C5—H5A···O3ii0.932.523.433 (2)166

Symmetry codes: (i) x+1, y+1, z; (ii) −x+3, −y+2, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FB2150).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Alpaslan, G., Özdamar, O., Odabaşogˇlu, M., Ersanlı, C. C., Erdönmez, A. & Ocak Ískeleli, N. (2005a). Acta Cryst E61, o3442–o3444.
  • Alpaslan, G., Özdamar, O., Odabaşoğlu, M., Ersanlı, C. C., Erdönmez, A. & Ocak Ískeleli, N. (2005b). Acta Cryst E61, o3648–o3650.
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  • Fun, H.-K., Chantrapromma, S., Padaki, M., Radhika & Isloor, A. M. (2009). Acta Cryst. E65, o1029. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]
  • Stancho, S., Georgi, M., Frank, J. & Ilia, M. (2008). Eur. J. Med. Chem 43, 694–706. [PubMed]

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