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

Alpaslan, G.; Özdamar, Ö.; Odabaşoğlu, M.; Büyükgüngör, O.; Erdönmez, A.

doi:10.1107/S1600536807065300

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o428

doi:10.1107/S1600536807065300

Open

access

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

Gökhan Alpaslan,^a Özgür Özdamar,^b Mustafa Odabaşoğlu,^b Orhan Büyükgüngör ^a and Ahmet Erdönmez ^a ^*

^aDepartment of Physics, Faculty of Arts & Science, Ondokuz Mayıs University, TR-55139 Kurupelit-Samsun, Turkey, and ^bDepartment of Chemistry, Faculty of Arts & Science, Ondokuz Mayıs University, TR-55139 Kurupelit-Samsun, Turkey
^*Correspondence e-mail: gokhana@omu.edu.tr

(Received 13 November 2007; accepted 3 December 2007; online 11 January 2008)

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.

Related literature

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

Experimental

Crystal data

C₁₂H₁₂Cl₂N₂O₃
M_r = 303.14
Triclinic, $[P \overline 1]$
a = 8.6454 (10) Å
b = 9.7251 (11) Å
c = 9.9939 (11) Å
α = 116.001 (8)°
β = 108.721 (8)°
γ = 96.453 (9)°
V = 682.91 (16) Å³
Z = 2
Mo Kα radiation
μ = 0.48 mm⁻¹
T = 296 (2) K
0.68 × 0.49 × 0.18 mm

Data collection

Stoe IPDSII diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ) T_min = 0.765, T_max = 0.916
5532 measured reflections
1325 independent reflections
991 reflections with I > 2σ(I)
R_int = 0.068

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.138
S = 1.04
1325 reflections
146 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.89 (6)	1.96 (6)	2.608 (4)	129 (6)

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; 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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807065300/fj2075sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536807065300/fj2075Isup2.hkl

checkCIF report

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.

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

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

C₁₂H₁₂Cl₂N₂O₃	Z = 2
M_r = 303.14	F(000) = 312
Triclinic, P1	D_x = 1.474 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.6454 (10) Å	Cell parameters from 9294 reflections
b = 9.7251 (11) Å	θ = 2.4–27.3°
c = 9.9939 (11) Å	µ = 0.48 mm⁻¹
α = 116.001 (8)°	T = 296 K
β = 108.721 (8)°	Prism, red
γ = 96.453 (9)°	0.68 × 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 tube	991 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.068
Detector resolution: 6.67 pixels mm^-1	θ_max = 26.0°, θ_min = 2.6°
rotation method scans	h = −10→10
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −11→11
T_min = 0.765, T_max = 0.916	l = −12→12
5532 measured reflections

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.138	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0717P)² + 0.2407P] where P = (F_o² + 2F_c²)/3
1325 reflections	(Δ/σ)_max < 0.001
146 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₂H₁₂Cl₂N₂O₃	γ = 96.453 (9)°
M_r = 303.14	V = 682.91 (16) Å³
Triclinic, P1	Z = 2
a = 8.6454 (10) Å	Mo Kα radiation
b = 9.7251 (11) Å	µ = 0.48 mm⁻¹
c = 9.9939 (11) Å	T = 296 K
α = 116.001 (8)°	0.68 × 0.49 × 0.18 mm
β = 108.721 (8)°

Data collection top

STOE IPDS-II diffractometer	1325 independent reflections
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	991 reflections with I > 2σ(I)
T_min = 0.765, T_max = 0.916	R_int = 0.068
5532 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.138	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.26 e Å⁻³
1325 reflections	Δρ_min = −0.20 e Å⁻³
146 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
C1	0.5661 (5)	0.3299 (6)	−0.0883 (6)	0.0501 (4)
C2	0.7250 (5)	0.4411 (6)	−0.0047 (6)	0.0501 (4)
H2	0.7943	0.4673	0.1012	0.060*
C3	0.7804 (5)	0.5136 (5)	−0.0808 (5)	0.0501 (4)
H3	0.8872	0.5896	−0.0255	0.060*
C4	0.6775 (5)	0.4732 (6)	−0.2378 (6)	0.0501 (4)
C5	0.5195 (5)	0.3614 (6)	−0.3217 (6)	0.0501 (4)
H5	0.4507	0.3333	−0.4283	0.060*
C6	0.4649 (5)	0.2915 (5)	−0.2442 (5)	0.0501 (4)
H6	0.3572	0.2169	−0.2990	0.060*
C7	0.5520 (5)	0.1834 (5)	0.1806 (6)	0.0427 (10)
C8	0.6923 (5)	0.1826 (6)	0.3131 (6)	0.0461 (10)
C9	0.8672 (5)	0.2758 (6)	0.3529 (6)	0.0501 (12)
H9A	0.8680	0.3841	0.3775	0.060*
H9B	0.8935	0.2265	0.2583	0.060*
C10	0.3677 (5)	0.0997 (5)	0.1201 (5)	0.0426 (10)
C11	0.1601 (6)	−0.0318 (7)	0.1644 (7)	0.0551 (14)
H11A	0.1154	−0.1244	0.0552	0.066*
H11B	0.0913	0.0402	0.1634	0.066*
C12	0.1543 (7)	−0.0832 (7)	0.2848 (7)	0.0682 (14)
H12A	0.0381	−0.1366	0.2548	0.102*
H12B	0.1990	0.0093	0.3924	0.102*
H12C	0.2220	−0.1551	0.2842	0.102*
Cl1	1.02658 (14)	0.28272 (16)	0.52211 (16)	0.0687 (4)
Cl2	0.74774 (17)	0.56273 (16)	−0.33405 (18)	0.0700 (4)
N1	0.5022 (5)	0.2540 (5)	−0.0167 (5)	0.0441 (8)
N2	0.6056 (4)	0.2539 (4)	0.1110 (4)	0.0433 (7)
O1	0.6713 (4)	0.1079 (6)	0.3773 (5)	0.0874 (13)
O2	0.2590 (3)	0.0861 (4)	−0.0001 (4)	0.0541 (8)
O3	0.3374 (4)	0.0489 (4)	0.2148 (4)	0.0528 (9)
H1	0.392 (8)	0.198 (8)	−0.068 (10)	0.09 (2)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0478 (11)	0.0566 (10)	0.0507 (10)	0.0105 (7)	0.0182 (7)	0.0336 (9)
C2	0.0478 (11)	0.0566 (10)	0.0507 (10)	0.0105 (7)	0.0182 (7)	0.0336 (9)
C3	0.0478 (11)	0.0566 (10)	0.0507 (10)	0.0105 (7)	0.0182 (7)	0.0336 (9)
C4	0.0478 (11)	0.0566 (10)	0.0507 (10)	0.0105 (7)	0.0182 (7)	0.0336 (9)
C5	0.0478 (11)	0.0566 (10)	0.0507 (10)	0.0105 (7)	0.0182 (7)	0.0336 (9)
C6	0.0478 (11)	0.0566 (10)	0.0507 (10)	0.0105 (7)	0.0182 (7)	0.0336 (9)
C7	0.041 (3)	0.044 (2)	0.043 (2)	0.0080 (17)	0.0166 (18)	0.024 (2)
C8	0.042 (3)	0.053 (3)	0.045 (2)	0.0086 (18)	0.0133 (18)	0.030 (2)
C9	0.038 (3)	0.065 (3)	0.045 (3)	0.0064 (19)	0.0092 (17)	0.034 (3)
C10	0.042 (3)	0.044 (2)	0.040 (2)	0.0079 (17)	0.0165 (18)	0.020 (2)
C11	0.038 (3)	0.070 (3)	0.057 (3)	0.001 (2)	0.018 (2)	0.036 (3)
C12	0.073 (4)	0.073 (3)	0.068 (3)	0.008 (2)	0.035 (3)	0.042 (3)
Cl1	0.0491 (8)	0.0800 (9)	0.0655 (8)	0.0080 (5)	0.0017 (5)	0.0454 (7)
Cl2	0.0865 (10)	0.0747 (8)	0.0828 (9)	0.0238 (6)	0.0491 (7)	0.0572 (8)
N1	0.038 (2)	0.053 (2)	0.0418 (19)	0.0072 (15)	0.0128 (15)	0.0287 (17)
N2	0.046 (2)	0.0459 (19)	0.0429 (19)	0.0138 (13)	0.0169 (13)	0.0269 (16)
O1	0.055 (2)	0.123 (3)	0.093 (3)	−0.0056 (17)	0.0025 (16)	0.089 (3)
O2	0.0368 (16)	0.076 (2)	0.0524 (18)	0.0078 (13)	0.0133 (12)	0.0409 (17)
O3	0.041 (2)	0.070 (2)	0.058 (2)	0.0090 (15)	0.0194 (15)	0.043 (2)

Geometric parameters (Å, º) top

C1—C6	1.369 (6)	C8—C9	1.502 (6)
C1—C2	1.375 (6)	C9—Cl1	1.774 (4)
C1—N1	1.410 (5)	C9—H9A	0.9700
C2—C3	1.392 (5)	C9—H9B	0.9700
C2—H2	0.9300	C10—O2	1.204 (5)
C3—C4	1.375 (6)	C10—O3	1.322 (5)
C3—H3	0.9300	C11—O3	1.451 (5)
C4—C5	1.372 (6)	C11—C12	1.504 (6)
C4—Cl2	1.744 (4)	C11—H11A	0.9700
C5—C6	1.382 (5)	C11—H11B	0.9700
C5—H5	0.9300	C12—H12A	0.9600
C6—H6	0.9300	C12—H12B	0.9600
C7—N2	1.312 (5)	C12—H12C	0.9600
C7—C8	1.485 (6)	N1—N2	1.302 (5)
C7—C10	1.492 (6)	N1—H1	0.89 (6)
C8—O1	1.194 (5)

C6—C1—C2	120.2 (4)	C8—C9—H9A	109.3
C6—C1—N1	118.3 (4)	Cl1—C9—H9A	109.3
C2—C1—N1	121.5 (4)	C8—C9—H9B	109.3
C1—C2—C3	119.0 (4)	Cl1—C9—H9B	109.3
C1—C2—H2	120.5	H9A—C9—H9B	107.9
C3—C2—H2	120.5	O2—C10—O3	124.5 (4)
C4—C3—C2	120.1 (4)	O2—C10—C7	122.3 (3)
C4—C3—H3	119.9	O3—C10—C7	113.1 (4)
C2—C3—H3	119.9	O3—C11—C12	107.6 (4)
C5—C4—C3	120.9 (4)	O3—C11—H11A	110.2
C5—C4—Cl2	119.0 (3)	C12—C11—H11A	110.2
C3—C4—Cl2	120.1 (3)	O3—C11—H11B	110.2
C4—C5—C6	118.5 (4)	C12—C11—H11B	110.2
C4—C5—H5	120.8	H11A—C11—H11B	108.5
C6—C5—H5	120.8	C11—C12—H12A	109.5
C1—C6—C5	121.3 (4)	C11—C12—H12B	109.5
C1—C6—H6	119.3	H12A—C12—H12B	109.5
C5—C6—H6	119.3	C11—C12—H12C	109.5
N2—C7—C8	113.7 (4)	H12A—C12—H12C	109.5
N2—C7—C10	122.2 (4)	H12B—C12—H12C	109.5
C8—C7—C10	123.8 (3)	N2—N1—C1	120.4 (4)
O1—C8—C7	123.8 (4)	N2—N1—H1	122 (5)
O1—C8—C9	122.1 (4)	C1—N1—H1	118 (5)
C7—C8—C9	114.0 (3)	N1—N2—C7	122.4 (4)
C8—C9—Cl1	111.7 (3)	C10—O3—C11	116.1 (3)

C6—C1—C2—C3	0.2 (8)	O1—C8—C9—Cl1	−8.4 (7)
N1—C1—C2—C3	−179.2 (4)	C7—C8—C9—Cl1	175.5 (4)
C1—C2—C3—C4	−0.5 (7)	N2—C7—C10—O2	3.4 (8)
C2—C3—C4—C5	0.0 (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—C6	0.8 (8)	C8—C7—C10—O3	11.5 (7)
Cl2—C4—C5—C6	−179.8 (3)	C6—C1—N1—N2	162.5 (4)
C2—C1—C6—C5	0.6 (8)	C2—C1—N1—N2	−18.2 (8)
N1—C1—C6—C5	180.0 (4)	C1—N1—N2—C7	−179.3 (4)
C4—C5—C6—C1	−1.1 (8)	C8—C7—N2—N1	173.9 (4)
N2—C7—C8—O1	−170.5 (5)	C10—C7—N2—N1	−0.9 (7)
C10—C7—C8—O1	4.2 (8)	O2—C10—O3—C11	1.6 (7)
N2—C7—C8—C9	5.5 (6)	C7—C10—O3—C11	179.2 (4)
C10—C7—C8—C9	−179.8 (4)	C12—C11—O3—C10	178.6 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.89 (6)	1.96 (6)	2.608 (4)	129 (6)

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂Cl₂N₂O₃
M_r	303.14
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	8.6454 (10), 9.7251 (11), 9.9939 (11)
α, β, γ (°)	116.001 (8), 108.721 (8), 96.453 (9)
V (Å³)	682.91 (16)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.48
Crystal size (mm)	0.68 × 0.49 × 0.18

Data collection
Diffractometer	STOE IPDS-II diffractometer
Absorption correction	Integration (X-RED32; Stoe & Cie, 2002)
T_min, T_max	0.765, 0.916
No. of measured, independent and observed [I > 2σ(I)] reflections	5532, 1325, 991
R_int	0.068
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.138, 1.04
No. of reflections	1325
No. of parameters	146
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.20

Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia,1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.89 (6)	1.96 (6)	2.608 (4)	129 (6)

Acknowledgements

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

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Odabaşoğlu, M., Özdamar, O. & Büyükgüngör, O. (2005). Acta Cryst. E61, o2065–o2067. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Stoe & Cie (2002). X-AREA (Version 1.18) and X-RED32 (Version 1.04). Stoe & Cie, Darmstadt, Germany. Google Scholar