Ethyl 2-chloro-[2-(4-chloro­phen­yl)hydrazin-1-yl­idene]acetate

Asiri, A.M.; Zayed, M.E.M.; Ng, S.W.

doi:10.1107/S1600536810032599

organic compounds

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ISSN: 2056-9890

Volume 66| Part 9| September 2010| Page o2375

https://doi.org/10.1107/S1600536810032599

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Ethyl 2-chloro-[2-(4-chlorophenyl)hydrazin-1-ylidene]acetate

Abdullah M. Asiri,^a Mohie E. M. Zayed ^a and Seik Weng Ng ^b ^*

^aChemistry Department, Faculty of Science, King Abdul Aziz University, PO Box 80203, Jeddah 21589, Saudi Arabia, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 11 August 2010; accepted 13 August 2010; online 21 August 2010)

The title compound, C₁₀H₁₀Cl₂N₂O₂, features a planar C_ar—N(H)—N=C(Cl) unit [torsion angle = 5.5 (4)°] whose benzene substituent is coplanar with it [dihedral angle = 4.7 (4)°]; this unit is slightly twisted with respect to the carboxyl –CO₂ fragment [dihedral angle = 2.2 (52)°]. The amino group acts as a hydrogen-bond donor to the carbonyl O atom of an adjacent molecule; the hydrogen bond generates a helical polymer that runs along the b axis of the monoclinic unit cell.

Related literature

For a review of the reactions of hydrazonyl halides with heterocyclic thiones for heteroannulation, the synthesis of spiroheterocycles and heterocyclic ring formation, see: Shawali & Farghaly (2008 ). For related structures, see: Xu (2006 ); Yin et al. (2006 ).

Experimental

Crystal data

C₁₀H₁₀Cl₂N₂O₂
M_r = 261.10
Monoclinic, P 2₁
a = 4.4611 (7) Å
b = 9.4546 (14) Å
c = 13.464 (2) Å
β = 91.642 (2)°
V = 567.65 (15) Å³
Z = 2
Mo Kα radiation
μ = 0.56 mm⁻¹
T = 100 K
0.35 × 0.10 × 0.05 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.829, T_max = 0.973
5298 measured reflections
2518 independent reflections
2191 reflections with I > 2σ(I)
R_int = 0.073

Refinement

R[F² > 2σ(F²)] = 0.072
wR(F²) = 0.188
S = 1.03
2518 reflections
145 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.34 e Å⁻³
Absolute structure: Flack (1983 ), 1123 Friedel pairs
Flack parameter: 0.03 (14)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	2.20	3.009 (5)	156
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+1]$ .

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810032599/nk2055sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810032599/nk2055Isup2.hkl

checkCIF report

Comment top

Ethyl 2-chloro(phenylhydrazono)acetate belongs to the class of of hydrazonyl halides that undergo heteroannulation, and are used for the synthesis of spiroheterocycles and other heterocyclic compounds. The utility in some aspects of heterocyclic chemistry has recently been reviewed (Shawali & Farghaly (2008). The central structural feature is an planar C_aryl–NH–N═C unit, as noted in the crystal structures of other substituted derivatives (Xu, 2006; Yin et al., 2006). The chlorine-substituted compound (Scheme I) shows this characteristic linkage, whose torsion angle is 5.5?(41) °. The carbon-nitrogen double bond is of a Z-configuration (Fig. 1). Such a configuration allows the amino site to form a hydrogen bond to the double-bond carbonyl oxygen atom of an adjacent molecule, this hydrogen bond giving rise to a helical chain that runs along the b axis of the unit cell (Fig. 2).

Related literature top

For a review of the reactions of hydrazonyl halides with heterocyclic thiones for heteroannulation, the synthesis of spiroheterocycles and heterocyclic ring formation, see: Shawali & Farghaly (2008). For related crystal structures, see: Xu (2006); Yin et al. (2006).

Experimental top

The synthesis works with either 3-chloropentane-2,4-dione or ethyl 2-chloro-3-oxobutanoate. To a solution of either 3-chloropentane-2,4-dione (1.34 g, 10 mmol) or ethyl 2-chloro-3-oxobutanoate (1.64 g, 10 mmol) in ethanol (100 ml) was added sodium acetate trihydrate (1.3 g, 10 mmol). The mixture was chilled to 273 K. To the mixture was added a cold solution of p-chlorobenzenediazonium chloride, prepared by diazotizing p-chloroaniline (1.20 g, 10 mmol) dissolved in 6M hydrochloricacid (6 ml) with a solution of sodium nitrite (0.7 g, 10 mmol) dissolved in water (10 ml). The diazonium salt was added over a period of 20 min. The reaction mixture was stirred for another 15 min. and then left for 3 h in a refrigerator. The resulting solid was collected and washed with water. The crude product was recrystallized from ethanol to give the hydrazone in 85% yield; m.p. 428–431 K.

Structure description top

For a review of the reactions of hydrazonyl halides with heterocyclic thiones for heteroannulation, the synthesis of spiroheterocycles and heterocyclic ring formation, see: Shawali & Farghaly (2008). For related crystal structures, see: Xu (2006); Yin et al. (2006).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Displacement ellipsoid plot of C₁₀H₁₀Cl₂N₂O₂ at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
	Fig. 2. The hydrogen bonded chain structure (red dashed lines) forming a helical chain that runs along the b axis.

Ethyl 2-chloro-[2-(4-chlorophenyl)hydrazin-1-ylidene]acetate top

Crystal data top

C₁₀H₁₀Cl₂N₂O₂	F(000) = 268
M_r = 261.10	D_x = 1.528 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1574 reflections
a = 4.4611 (7) Å	θ = 2.6–27.2°
b = 9.4546 (14) Å	µ = 0.56 mm⁻¹
c = 13.464 (2) Å	T = 100 K
β = 91.642 (2)°	Prism, colourless
V = 567.65 (15) Å³	0.35 × 0.10 × 0.05 mm
Z = 2

Data collection top

Bruker SMART APEX diffractometer	2518 independent reflections
Radiation source: fine-focus sealed tube	2191 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.073
ω scans	θ_max = 27.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −5→5
T_min = 0.829, T_max = 0.973	k = −12→11
5298 measured reflections	l = −17→17

Refinement top

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)] = 0.072	H-atom parameters constrained
wR(F²) = 0.188	w = 1/[σ²(F_o²) + (0.1216P)² + 0.1253P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
2518 reflections	Δρ_max = 0.59 e Å⁻³
145 parameters	Δρ_min = −0.34 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1123 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (14)

Crystal data top

C₁₀H₁₀Cl₂N₂O₂	V = 567.65 (15) Å³
M_r = 261.10	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 4.4611 (7) Å	µ = 0.56 mm⁻¹
b = 9.4546 (14) Å	T = 100 K
c = 13.464 (2) Å	0.35 × 0.10 × 0.05 mm
β = 91.642 (2)°

Data collection top

Bruker SMART APEX diffractometer	2518 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2191 reflections with I > 2σ(I)
T_min = 0.829, T_max = 0.973	R_int = 0.073
5298 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.072	H-atom parameters constrained
wR(F²) = 0.188	Δρ_max = 0.59 e Å⁻³
S = 1.03	Δρ_min = −0.34 e Å⁻³
2518 reflections	Absolute structure: Flack (1983), 1123 Friedel pairs
145 parameters	Absolute structure parameter: 0.03 (14)
1 restraint

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	1.4745 (3)	0.50000 (14)	0.97204 (9)	0.0301 (4)
Cl2	0.4463 (3)	0.85685 (12)	0.46296 (8)	0.0226 (3)
N1	0.8095 (9)	0.7704 (5)	0.6374 (3)	0.0203 (8)
H1	0.8376	0.7407	0.5780	0.024*
N2	0.6137 (9)	0.8722 (4)	0.6540 (3)	0.0194 (8)
O1	0.0631 (7)	1.0838 (4)	0.5375 (2)	0.0222 (7)
O2	0.2281 (8)	1.0713 (4)	0.6974 (2)	0.0223 (7)
C1	0.9702 (11)	0.7120 (5)	0.7183 (4)	0.0193 (10)
C2	0.9430 (11)	0.7619 (5)	0.8146 (4)	0.0212 (10)
H2A	0.8163	0.8403	0.8270	0.025*
C3	1.0993 (12)	0.6981 (5)	0.8922 (4)	0.0240 (10)
H3	1.0804	0.7324	0.9581	0.029*
C4	1.2829 (11)	0.5844 (6)	0.8740 (4)	0.0229 (10)
C5	1.3191 (11)	0.5353 (5)	0.7776 (4)	0.0225 (10)
H5	1.4509	0.4587	0.7654	0.027*
C6	1.1616 (10)	0.5990 (5)	0.7000 (4)	0.0207 (10)
H6	1.1836	0.5657	0.6340	0.025*
C7	0.4460 (10)	0.9208 (5)	0.5837 (3)	0.0176 (9)
C8	0.2257 (10)	1.0339 (5)	0.6023 (3)	0.0183 (9)
C9	0.0103 (11)	1.1798 (5)	0.7225 (4)	0.0223 (10)
H9A	−0.1945	1.1501	0.7012	0.027*
H9B	0.0575	1.2700	0.6891	0.027*
C10	0.0316 (13)	1.1969 (6)	0.8335 (4)	0.0282 (11)
H10A	−0.1110	1.2694	0.8541	0.042*
H10B	0.2356	1.2258	0.8534	0.042*
H10C	−0.0159	1.1068	0.8654	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0349 (7)	0.0288 (7)	0.0262 (6)	0.0030 (5)	−0.0055 (5)	0.0046 (5)
Cl2	0.0251 (6)	0.0219 (6)	0.0209 (5)	−0.0002 (5)	0.0003 (4)	−0.0019 (5)
N1	0.0213 (19)	0.021 (2)	0.0193 (19)	0.0011 (17)	0.0023 (15)	−0.0014 (15)
N2	0.0244 (19)	0.0112 (18)	0.0225 (19)	−0.0033 (16)	0.0012 (14)	0.0034 (16)
O1	0.0253 (18)	0.0156 (17)	0.0253 (17)	0.0035 (14)	−0.0032 (13)	0.0017 (13)
O2	0.0252 (18)	0.0187 (17)	0.0230 (17)	0.0050 (14)	−0.0007 (13)	−0.0012 (13)
C1	0.019 (2)	0.018 (3)	0.022 (2)	−0.0082 (19)	−0.0025 (16)	0.0008 (19)
C2	0.022 (2)	0.015 (2)	0.027 (3)	−0.0014 (19)	0.0028 (19)	−0.0011 (18)
C3	0.029 (3)	0.019 (3)	0.023 (2)	−0.004 (2)	0.0002 (19)	−0.0018 (19)
C4	0.020 (2)	0.023 (2)	0.025 (2)	−0.0036 (19)	−0.0055 (18)	0.0060 (19)
C5	0.025 (2)	0.015 (2)	0.027 (2)	−0.0026 (19)	−0.0011 (18)	−0.0014 (18)
C6	0.017 (2)	0.022 (3)	0.023 (2)	0.0001 (19)	0.0012 (17)	−0.0020 (19)
C7	0.018 (2)	0.018 (2)	0.017 (2)	−0.0054 (18)	−0.0012 (16)	−0.0019 (17)
C8	0.019 (2)	0.016 (2)	0.020 (2)	−0.0081 (18)	−0.0016 (16)	0.0038 (17)
C9	0.025 (3)	0.014 (2)	0.028 (2)	0.003 (2)	0.000 (2)	−0.0028 (18)
C10	0.038 (3)	0.021 (3)	0.026 (2)	0.001 (2)	0.002 (2)	−0.003 (2)

Geometric parameters (Å, º) top

Cl1—C4	1.745 (5)	C3—C4	1.378 (7)
Cl2—C7	1.735 (5)	C3—H3	0.9500
N1—N2	1.323 (6)	C4—C5	1.392 (7)
N1—C1	1.400 (6)	C5—C6	1.381 (7)
N1—H1	0.8600	C5—H5	0.9500
N2—C7	1.275 (6)	C6—H6	0.9500
O1—C8	1.214 (6)	C7—C8	1.478 (7)
O2—C8	1.328 (6)	C9—C10	1.504 (7)
O2—C9	1.459 (6)	C9—H9A	0.9900
C1—C2	1.388 (7)	C9—H9B	0.9900
C1—C6	1.394 (7)	C10—H10A	0.9800
C2—C3	1.379 (7)	C10—H10B	0.9800
C2—H2A	0.9500	C10—H10C	0.9800

N2—N1—C1	118.7 (4)	C5—C6—H6	120.0
N2—N1—H1	120.6	C1—C6—H6	120.0
C1—N1—H1	120.6	N2—C7—C8	120.9 (4)
C7—N2—N1	120.8 (4)	N2—C7—Cl2	123.6 (4)
C8—O2—C9	115.0 (4)	C8—C7—Cl2	115.4 (3)
C2—C1—C6	119.7 (4)	O1—C8—O2	125.3 (4)
C2—C1—N1	122.4 (5)	O1—C8—C7	123.1 (4)
C6—C1—N1	117.9 (4)	O2—C8—C7	111.6 (4)
C3—C2—C1	120.2 (5)	O2—C9—C10	106.4 (4)
C3—C2—H2A	119.9	O2—C9—H9A	110.4
C1—C2—H2A	119.9	C10—C9—H9A	110.4
C2—C3—C4	119.8 (5)	O2—C9—H9B	110.4
C2—C3—H3	120.1	C10—C9—H9B	110.4
C4—C3—H3	120.1	H9A—C9—H9B	108.6
C3—C4—C5	120.8 (4)	C9—C10—H10A	109.5
C3—C4—Cl1	120.2 (4)	C9—C10—H10B	109.5
C5—C4—Cl1	119.0 (4)	H10A—C10—H10B	109.5
C6—C5—C4	119.3 (5)	C9—C10—H10C	109.5
C6—C5—H5	120.3	H10A—C10—H10C	109.5
C4—C5—H5	120.3	H10B—C10—H10C	109.5
C5—C6—C1	120.1 (4)

C1—N1—N2—C7	−174.5 (4)	C2—C1—C6—C5	1.2 (7)
N2—N1—C1—C2	−3.4 (7)	N1—C1—C6—C5	−178.3 (4)
N2—N1—C1—C6	176.1 (4)	N1—N2—C7—C8	179.6 (4)
C6—C1—C2—C3	−1.5 (7)	N1—N2—C7—Cl2	2.3 (6)
N1—C1—C2—C3	178.1 (4)	C9—O2—C8—O1	1.1 (6)
C1—C2—C3—C4	0.0 (7)	C9—O2—C8—C7	−178.3 (4)
C2—C3—C4—C5	1.7 (7)	N2—C7—C8—O1	179.5 (4)
C2—C3—C4—Cl1	−178.4 (4)	Cl2—C7—C8—O1	−3.0 (6)
C3—C4—C5—C6	−1.9 (7)	N2—C7—C8—O2	−1.1 (6)
Cl1—C4—C5—C6	178.2 (4)	Cl2—C7—C8—O2	176.4 (3)
C4—C5—C6—C1	0.5 (7)	C8—O2—C9—C10	175.2 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.20	3.009 (5)	156

Symmetry code: (i) −x+1, y−1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₀Cl₂N₂O₂
M_r	261.10
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	100
a, b, c (Å)	4.4611 (7), 9.4546 (14), 13.464 (2)
β (°)	91.642 (2)
V (Å³)	567.65 (15)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.56
Crystal size (mm)	0.35 × 0.10 × 0.05

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.829, 0.973
No. of measured, independent and observed [I > 2σ(I)] reflections	5298, 2518, 2191
R_int	0.073
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.072, 0.188, 1.03
No. of reflections	2518
No. of parameters	145
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.34
Absolute structure	Flack (1983), 1123 Friedel pairs
Absolute structure parameter	0.03 (14)

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.20	3.009 (5)	156

Symmetry code: (i) −x+1, y−1/2, −z+1.

Acknowledgements

The authors thank King Abdul Aziz University and the University of Malaya for supporting this study.

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