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Acta Cryst. (2008). E64, o428    [ doi:10.1107/S1600536807065300 ]

(Z)-Ethyl 4-chloro-2-[(4-chlorophenyl)hydrazono]-3-oxobutanoate

G. Alpaslan, Ö. Özdamar, M. Odabasoglu, O. Büyükgüngör and A. Erdönmez

Abstract top

The title compound, C12H12Cl2N2O3, crystallizes as a non-merohedral twin with a twinning ratio of 0.51:0.49. The molecule adopts a keto-hydrazo tautomeric form stabilized by an intramolecular N-H...O hydrogen bond. The configuration around the N-N bond is trans.

Comment top

As part of our project to study the crystal structures of a series of phenylhydrazones and their stereochemistry, the crystal structure of the title compound, (I), has been determined. The overall view and atom-labelling of the molecule of (I) are displayed in Fig.1. Bond lenghts and angles are presented in Table 1 and hydrogen- bonding parametres are given in Table 2. The molecule is approximately planar with dihedral angle between the aromatic C1—C6 ring and the plane of the C7—C12/O1—O3/Cl1 aliphatic chain being 19.71 (12)°. Intramolecular N—H···O hydrogen bond generate S(6) ring motif (Bernstein et al., 1995).

Related literature top

For related literature, see: Bernstein et al. (1995); Odabaşoğlu et al. (2005).

Experimental top

The title compound was prepared as described by (Odabaşoğlu et al., 2005), using p-chloroaniline and ethyl 4-chloroacetoacetate as starting materials (yield 92%, m.p. 415–417 K). Crystals of (I) suitable for x-ray analysis were obtained by slow evaporation of an absolute acetic acid solution at room temperature.

Refinement top

The crystal was non-merohedral twin with a twinning ratio of 0.51:0.49 and the reflection data were measured for the two twin domains, scaled and combined together, but overlapping reflections could not be satisfactorily measured and were discarded, leading to a data completeness of only slightly over 49%. The dataset under investigation had 5614 identified reflections associated with component 1 only, 5636 reflections with component 2 only and 1674 are belonging to both components. The H atom bonded to N1 was refined freely. All other H atoms were placed in calculated positions and constrained to ride on their parent atoms, with C—H = 0.93–0.97 Å and Uiso(H) = 1.2 Ueq(C) [1.5Ueq(methyl C)]. The SHELXS EADP restrain applied to benzene ring to increase the Data/Parameter Ratio

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia,1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with the atom-numbering scheme, showing the intramolecular N—H···O hydrogen bond (dashed line). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
(Z)-Ethyl 4-chloro-2-[(4-chlorophenyl)hydrazono]-3-oxobutanoate top
Crystal data top
C12H12Cl2N2O3Z = 2
Mr = 303.14F000 = 312
Triclinic, P1Dx = 1.474 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 8.6454 (10) ÅCell parameters from 9294 reflections
b = 9.7251 (11) Åθ = 2.4–27.3º
c = 9.9939 (11) ŵ = 0.48 mm−1
α = 116.001 (8)ºT = 296 (2) K
β = 108.721 (8)ºPrism, red
γ = 96.453 (9)º0.68 × 0.49 × 0.18 mm
V = 682.91 (16) Å3
Data collection top
STOE IPDS-II
diffractometer		1325 independent reflections
Radiation source: fine-focus sealed tube991 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.068
Detector resolution: 6.67 pixels mm-1θmax = 26.0º
T = 296(2) Kθmin = 2.6º
rotation method scansh = −10→10
Absorption correction: integration
(X-RED32; Stoe & Cie, 2002)		k = −11→11
Tmin = 0.765, Tmax = 0.916l = −12→12
5532 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.050H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.138  w = 1/[σ2(Fo2) + (0.0717P)2 + 0.2407P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
1325 reflectionsΔρmax = 0.26 e Å−3
146 parametersΔρmin = −0.20 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C12H12Cl2N2O3γ = 96.453 (9)º
Mr = 303.14V = 682.91 (16) Å3
Triclinic, P1Z = 2
a = 8.6454 (10) ÅMo Kα
b = 9.7251 (11) ŵ = 0.48 mm−1
c = 9.9939 (11) ÅT = 296 (2) K
α = 116.001 (8)º0.68 × 0.49 × 0.18 mm
β = 108.721 (8)º
Data collection top
STOE IPDS-II
diffractometer		1325 independent reflections
Absorption correction: integration
(X-RED32; Stoe & Cie, 2002)		991 reflections with I > 2σ(I)
Tmin = 0.765, Tmax = 0.916Rint = 0.068
5532 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.050146 parameters
wR(F2) = 0.138H atoms treated by a mixture of
independent and constrained refinement
S = 1.04Δρmax = 0.26 e Å−3
1325 reflectionsΔρmin = −0.20 e Å−3
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
xyzUiso*/Ueq
C10.5661 (5)0.3299 (6)−0.0883 (6)0.0501 (4)
C20.7250 (5)0.4411 (6)−0.0047 (6)0.0501 (4)
H20.79430.46730.10120.060*
C30.7804 (5)0.5136 (5)−0.0808 (5)0.0501 (4)
H30.88720.5896−0.02550.060*
C40.6775 (5)0.4732 (6)−0.2378 (6)0.0501 (4)
C50.5195 (5)0.3614 (6)−0.3217 (6)0.0501 (4)
H50.45070.3333−0.42830.060*
C60.4649 (5)0.2915 (5)−0.2442 (5)0.0501 (4)
H60.35720.2169−0.29900.060*
C70.5520 (5)0.1834 (5)0.1806 (6)0.0427 (10)
C80.6923 (5)0.1826 (6)0.3131 (6)0.0461 (10)
C90.8672 (5)0.2758 (6)0.3529 (6)0.0501 (12)
H9A0.86800.38410.37750.060*
H9B0.89350.22650.25830.060*
C100.3677 (5)0.0997 (5)0.1201 (5)0.0426 (10)
C110.1601 (6)−0.0318 (7)0.1644 (7)0.0551 (14)
H11A0.1154−0.12440.05520.066*
H11B0.09130.04020.16340.066*
C120.1543 (7)−0.0832 (7)0.2848 (7)0.0682 (14)
H12A0.0381−0.13660.25480.102*
H12B0.19900.00930.39240.102*
H12C0.2220−0.15510.28420.102*
Cl11.02658 (14)0.28272 (16)0.52211 (16)0.0687 (4)
Cl20.74774 (17)0.56273 (16)−0.33405 (18)0.0700 (4)
N10.5022 (5)0.2540 (5)−0.0167 (5)0.0441 (8)
N20.6056 (4)0.2539 (4)0.1110 (4)0.0433 (7)
O10.6713 (4)0.1079 (6)0.3773 (5)0.0874 (13)
O20.2590 (3)0.0861 (4)−0.0001 (4)0.0541 (8)
O30.3374 (4)0.0489 (4)0.2148 (4)0.0528 (9)
H10.392 (8)0.198 (8)−0.068 (10)0.09 (2)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0478 (11)0.0566 (10)0.0507 (10)0.0105 (7)0.0182 (7)0.0336 (9)
C20.0478 (11)0.0566 (10)0.0507 (10)0.0105 (7)0.0182 (7)0.0336 (9)
C30.0478 (11)0.0566 (10)0.0507 (10)0.0105 (7)0.0182 (7)0.0336 (9)
C40.0478 (11)0.0566 (10)0.0507 (10)0.0105 (7)0.0182 (7)0.0336 (9)
C50.0478 (11)0.0566 (10)0.0507 (10)0.0105 (7)0.0182 (7)0.0336 (9)
C60.0478 (11)0.0566 (10)0.0507 (10)0.0105 (7)0.0182 (7)0.0336 (9)
C70.041 (3)0.044 (2)0.043 (2)0.0080 (17)0.0166 (18)0.024 (2)
C80.042 (3)0.053 (3)0.045 (2)0.0086 (18)0.0133 (18)0.030 (2)
C90.038 (3)0.065 (3)0.045 (3)0.0064 (19)0.0092 (17)0.034 (3)
C100.042 (3)0.044 (2)0.040 (2)0.0079 (17)0.0165 (18)0.020 (2)
C110.038 (3)0.070 (3)0.057 (3)0.001 (2)0.018 (2)0.036 (3)
C120.073 (4)0.073 (3)0.068 (3)0.008 (2)0.035 (3)0.042 (3)
Cl10.0491 (8)0.0800 (9)0.0655 (8)0.0080 (5)0.0017 (5)0.0454 (7)
Cl20.0865 (10)0.0747 (8)0.0828 (9)0.0238 (6)0.0491 (7)0.0572 (8)
N10.038 (2)0.053 (2)0.0418 (19)0.0072 (15)0.0128 (15)0.0287 (17)
N20.046 (2)0.0459 (19)0.0429 (19)0.0138 (13)0.0169 (13)0.0269 (16)
O10.055 (2)0.123 (3)0.093 (3)−0.0056 (17)0.0025 (16)0.089 (3)
O20.0368 (16)0.076 (2)0.0524 (18)0.0078 (13)0.0133 (12)0.0409 (17)
O30.041 (2)0.070 (2)0.058 (2)0.0090 (15)0.0194 (15)0.043 (2)
Geometric parameters (Å, °) top
C1—C61.369 (6)C8—C91.502 (6)
C1—C21.375 (6)C9—Cl11.774 (4)
C1—N11.410 (5)C9—H9A0.9700
C2—C31.392 (5)C9—H9B0.9700
C2—H20.9300C10—O21.204 (5)
C3—C41.375 (6)C10—O31.322 (5)
C3—H30.9300C11—O31.451 (5)
C4—C51.372 (6)C11—C121.504 (6)
C4—Cl21.744 (4)C11—H11A0.9700
C5—C61.382 (5)C11—H11B0.9700
C5—H50.9300C12—H12A0.9600
C6—H60.9300C12—H12B0.9600
C7—N21.312 (5)C12—H12C0.9600
C7—C81.485 (6)N1—N21.302 (5)
C7—C101.492 (6)N1—H10.89 (6)
C8—O11.194 (5)
C6—C1—C2120.2 (4)C8—C9—H9A109.3
C6—C1—N1118.3 (4)Cl1—C9—H9A109.3
C2—C1—N1121.5 (4)C8—C9—H9B109.3
C1—C2—C3119.0 (4)Cl1—C9—H9B109.3
C1—C2—H2120.5H9A—C9—H9B107.9
C3—C2—H2120.5O2—C10—O3124.5 (4)
C4—C3—C2120.1 (4)O2—C10—C7122.3 (3)
C4—C3—H3119.9O3—C10—C7113.1 (4)
C2—C3—H3119.9O3—C11—C12107.6 (4)
C5—C4—C3120.9 (4)O3—C11—H11A110.2
C5—C4—Cl2119.0 (3)C12—C11—H11A110.2
C3—C4—Cl2120.1 (3)O3—C11—H11B110.2
C4—C5—C6118.5 (4)C12—C11—H11B110.2
C4—C5—H5120.8H11A—C11—H11B108.5
C6—C5—H5120.8C11—C12—H12A109.5
C1—C6—C5121.3 (4)C11—C12—H12B109.5
C1—C6—H6119.3H12A—C12—H12B109.5
C5—C6—H6119.3C11—C12—H12C109.5
N2—C7—C8113.7 (4)H12A—C12—H12C109.5
N2—C7—C10122.2 (4)H12B—C12—H12C109.5
C8—C7—C10123.8 (3)N2—N1—C1120.4 (4)
O1—C8—C7123.8 (4)N2—N1—H1122 (5)
O1—C8—C9122.1 (4)C1—N1—H1118 (5)
C7—C8—C9114.0 (3)N1—N2—C7122.4 (4)
C8—C9—Cl1111.7 (3)C10—O3—C11116.1 (3)
C6—C1—C2—C30.2 (8)O1—C8—C9—Cl1−8.4 (7)
N1—C1—C2—C3−179.2 (4)C7—C8—C9—Cl1175.5 (4)
C1—C2—C3—C4−0.5 (7)N2—C7—C10—O23.4 (8)
C2—C3—C4—C50.0 (7)C8—C7—C10—O2−170.9 (5)
C2—C3—C4—Cl2−179.4 (4)N2—C7—C10—O3−174.3 (4)
C3—C4—C5—C60.8 (8)C8—C7—C10—O311.5 (7)
Cl2—C4—C5—C6−179.8 (3)C6—C1—N1—N2162.5 (4)
C2—C1—C6—C50.6 (8)C2—C1—N1—N2−18.2 (8)
N1—C1—C6—C5180.0 (4)C1—N1—N2—C7−179.3 (4)
C4—C5—C6—C1−1.1 (8)C8—C7—N2—N1173.9 (4)
N2—C7—C8—O1−170.5 (5)C10—C7—N2—N1−0.9 (7)
C10—C7—C8—O14.2 (8)O2—C10—O3—C111.6 (7)
N2—C7—C8—C95.5 (6)C7—C10—O3—C11179.2 (4)
C10—C7—C8—C9−179.8 (4)C12—C11—O3—C10178.6 (5)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O20.89 (6)1.96 (6)2.608 (4)129 (6)
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O20.89 (6)1.96 (6)2.608 (4)129 (6)
Acknowledgements top

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDSII diffractometer (purchased under grant No. F279 of the University Research Fund).

references
References top

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.

Odabaşoğlu, M., Özdamar, O. & Büyükgüngör, O. (2005). Acta Cryst. E61, o2065–o2067.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Stoe & Cie (2002). X-AREA (Version 1.18) and X-RED32 (Version 1.04). Stoe & Cie, Darmstadt, Germany.