Ethyl (Z)-2-chloro-2-(2-phenyl­hydrazin-1-yl­idene)acetate

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

doi:10.1107/S1600536810032587

organic compounds

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ISSN: 2056-9890

Volume 66| Part 9| September 2010| Page o2374

https://doi.org/10.1107/S1600536810032587

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Ethyl (Z)-2-chloro-2-(2-phenylhydrazin-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, C₁₀H₁₁ClN₂O₂, features an almost planar C_ar—N(H)—N=C(Cl) unit [torsion angle = 0.8 (1)° whose phenyl substituent is almost coplanar with it [dihedral angle = 2.8 (2)°]; this unit is slightly twisted with respect to the carboxyl –CO₂ fragment [dihedral angle = 10.3 (2)°]. In the crystal, the amino group acts as a hydrogen-bond donor to the carbonyl O atom of an adjacent molecule; the hydrogen bond generates a helical chain 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 crystal structures, see: Xu (2006 ); Yin et al. (2006 ).

Experimental

Crystal data

C₁₀H₁₁ClN₂O₂
M_r = 226.66
Monoclinic, P 2₁ /c
a = 10.5091 (7) Å
b = 11.1813 (8) Å
c = 10.1190 (7) Å
β = 118.148 (1)°
V = 1048.41 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 100 K
0.30 × 0.30 × 0.10 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.904, T_max = 0.966
6532 measured reflections
2399 independent reflections
2191 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.076
S = 1.03
2399 reflections
140 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.85 (1)	2.18 (1)	2.969 (1)	153 (2)
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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/S1600536810032587/nk2054sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810032587/nk2054Isup2.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 parent compound (Scheme I) shows this characteristic linkage, whose torsion angle is 0.8 (1) °. 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 benzenediazonium chloride, prepared by diazotizing aniline (0.93 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 80% yield; m.p. 352–353 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 C₁₀H₁₁ClN₂O₂ at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
	Fig. 2. Part of the hydrogen-bonded helical chain structure (red dashed lines) which runs along the b-axis.

Ethyl (Z)-2-chloro-2-(2-phenylhydrazin-1-ylidene)acetate top

Crystal data top

C₁₀H₁₁ClN₂O₂	F(000) = 472
M_r = 226.66	D_x = 1.436 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4259 reflections
a = 10.5091 (7) Å	θ = 2.3–28.3°
b = 11.1813 (8) Å	µ = 0.35 mm⁻¹
c = 10.1190 (7) Å	T = 100 K
β = 118.148 (1)°	Irregular, yellow
V = 1048.41 (13) Å³	0.30 × 0.30 × 0.10 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	2399 independent reflections
Radiation source: fine-focus sealed tube	2191 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω scans	θ_max = 27.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→11
T_min = 0.904, T_max = 0.966	k = −14→12
6532 measured reflections	l = −13→13

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0409P)² + 0.389P] where P = (F_o² + 2F_c²)/3
2399 reflections	(Δ/σ)_max = 0.001
140 parameters	Δρ_max = 0.31 e Å⁻³
1 restraint	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₀H₁₁ClN₂O₂	V = 1048.41 (13) Å³
M_r = 226.66	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.5091 (7) Å	µ = 0.35 mm⁻¹
b = 11.1813 (8) Å	T = 100 K
c = 10.1190 (7) Å	0.30 × 0.30 × 0.10 mm
β = 118.148 (1)°

Data collection top

Bruker SMART APEX diffractometer	2399 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2191 reflections with I > 2σ(I)
T_min = 0.904, T_max = 0.966	R_int = 0.022
6532 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	1 restraint
wR(F²) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.31 e Å⁻³
2399 reflections	Δρ_min = −0.21 e Å⁻³
140 parameters

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

	x	y	z	U_iso*/U_eq
Cl1	0.52913 (3)	0.54445 (2)	0.33899 (3)	0.02076 (10)
O1	0.67383 (8)	0.38123 (7)	0.09626 (9)	0.01737 (18)
O2	0.49929 (9)	0.33068 (7)	0.15554 (9)	0.01943 (19)
N1	0.70432 (10)	0.70808 (8)	0.26261 (10)	0.0153 (2)
H1	0.6608 (17)	0.7284 (15)	0.3121 (17)	0.032 (4)*
N2	0.68722 (10)	0.59913 (8)	0.20434 (10)	0.01443 (19)
C1	0.78999 (11)	0.79127 (10)	0.23651 (11)	0.0143 (2)
C2	0.81229 (12)	0.90363 (10)	0.30391 (12)	0.0171 (2)
H2	0.7691	0.9232	0.3651	0.020*
C3	0.89810 (12)	0.98666 (11)	0.28081 (13)	0.0201 (2)
H3	0.9140	1.0629	0.3273	0.024*
C4	0.96101 (13)	0.95973 (11)	0.19073 (14)	0.0208 (2)
H4	1.0194	1.0170	0.1753	0.025*
C5	0.93736 (12)	0.84780 (11)	0.12342 (13)	0.0201 (2)
H5	0.9796	0.8289	0.0612	0.024*
C6	0.85275 (12)	0.76310 (10)	0.14599 (12)	0.0167 (2)
H6	0.8378	0.6866	0.1001	0.020*
C7	0.61141 (12)	0.52090 (10)	0.22737 (12)	0.0152 (2)
C8	0.58682 (11)	0.40102 (10)	0.15624 (12)	0.0147 (2)
C9	0.66715 (12)	0.26082 (10)	0.03770 (13)	0.0176 (2)
H9A	0.5698	0.2446	−0.0461	0.021*
H9B	0.6887	0.2006	0.1172	0.021*
C10	0.77830 (12)	0.25572 (12)	−0.01594 (13)	0.0213 (3)
H10A	0.7777	0.1760	−0.0566	0.032*
H10B	0.8740	0.2719	0.0681	0.032*
H10C	0.7557	0.3159	−0.0943	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.02594 (16)	0.01667 (16)	0.02897 (16)	−0.00155 (10)	0.02060 (13)	−0.00199 (10)
O1	0.0184 (4)	0.0141 (4)	0.0232 (4)	−0.0018 (3)	0.0128 (3)	−0.0032 (3)
O2	0.0200 (4)	0.0155 (4)	0.0260 (4)	−0.0020 (3)	0.0136 (3)	0.0007 (3)
N1	0.0167 (4)	0.0138 (5)	0.0185 (4)	−0.0005 (4)	0.0109 (4)	−0.0015 (3)
N2	0.0133 (4)	0.0130 (5)	0.0153 (4)	0.0013 (3)	0.0053 (3)	0.0007 (3)
C1	0.0109 (5)	0.0151 (5)	0.0148 (5)	0.0005 (4)	0.0043 (4)	0.0024 (4)
C2	0.0165 (5)	0.0163 (6)	0.0187 (5)	0.0016 (4)	0.0087 (4)	0.0002 (4)
C3	0.0187 (5)	0.0144 (5)	0.0249 (6)	−0.0006 (4)	0.0084 (5)	0.0001 (4)
C4	0.0164 (5)	0.0202 (6)	0.0247 (6)	−0.0026 (4)	0.0090 (5)	0.0044 (4)
C5	0.0172 (5)	0.0250 (6)	0.0201 (5)	0.0002 (5)	0.0105 (4)	0.0017 (4)
C6	0.0163 (5)	0.0169 (5)	0.0170 (5)	−0.0002 (4)	0.0078 (4)	−0.0007 (4)
C7	0.0144 (5)	0.0162 (5)	0.0166 (5)	0.0020 (4)	0.0087 (4)	0.0011 (4)
C8	0.0139 (5)	0.0149 (5)	0.0146 (5)	0.0018 (4)	0.0061 (4)	0.0025 (4)
C9	0.0184 (5)	0.0151 (5)	0.0200 (5)	0.0000 (4)	0.0098 (4)	−0.0022 (4)
C10	0.0189 (6)	0.0241 (6)	0.0221 (6)	−0.0015 (5)	0.0107 (5)	−0.0062 (5)

Geometric parameters (Å, º) top

Cl1—C7	1.7361 (11)	C3—H3	0.9500
O1—C8	1.3331 (13)	C4—C5	1.3900 (17)
O1—C9	1.4593 (13)	C4—H4	0.9500
O2—C8	1.2076 (14)	C5—C6	1.3897 (16)
N1—N2	1.3282 (13)	C5—H5	0.9500
N1—C1	1.4035 (14)	C6—H6	0.9500
N1—H1	0.853 (13)	C7—C8	1.4853 (15)
N2—C7	1.2765 (14)	C9—C10	1.5035 (15)
C1—C2	1.3957 (16)	C9—H9A	0.9900
C1—C6	1.3939 (15)	C9—H9B	0.9900
C2—C3	1.3888 (16)	C10—H10A	0.9800
C2—H2	0.9500	C10—H10B	0.9800
C3—C4	1.3883 (17)	C10—H10C	0.9800

C8—O1—C9	115.22 (8)	C5—C6—H6	120.3
N2—N1—C1	119.25 (9)	C1—C6—H6	120.3
N2—N1—H1	120.4 (11)	N2—C7—C8	120.72 (10)
C1—N1—H1	120.3 (11)	N2—C7—Cl1	124.07 (9)
C7—N2—N1	120.85 (9)	C8—C7—Cl1	115.21 (8)
C2—C1—C6	120.14 (10)	O2—C8—O1	124.99 (10)
C2—C1—N1	118.64 (10)	O2—C8—C7	123.26 (10)
C6—C1—N1	121.22 (10)	O1—C8—C7	111.74 (9)
C3—C2—C1	119.48 (10)	O1—C9—C10	106.55 (9)
C3—C2—H2	120.3	O1—C9—H9A	110.4
C1—C2—H2	120.3	C10—C9—H9A	110.4
C4—C3—C2	120.91 (11)	O1—C9—H9B	110.4
C4—C3—H3	119.5	C10—C9—H9B	110.4
C2—C3—H3	119.5	H9A—C9—H9B	108.6
C5—C4—C3	119.11 (11)	C9—C10—H10A	109.5
C5—C4—H4	120.4	C9—C10—H10B	109.5
C3—C4—H4	120.4	H10A—C10—H10B	109.5
C4—C5—C6	120.89 (11)	C9—C10—H10C	109.5
C4—C5—H5	119.6	H10A—C10—H10C	109.5
C6—C5—H5	119.6	H10B—C10—H10C	109.5
C5—C6—C1	119.46 (11)

C1—N1—N2—C7	179.17 (10)	N1—C1—C6—C5	−179.74 (10)
N2—N1—C1—C2	−177.17 (9)	N1—N2—C7—C8	177.11 (9)
N2—N1—C1—C6	2.49 (15)	N1—N2—C7—Cl1	−2.23 (15)
C6—C1—C2—C3	−0.40 (16)	C9—O1—C8—O2	−5.24 (15)
N1—C1—C2—C3	179.26 (10)	C9—O1—C8—C7	173.93 (9)
C1—C2—C3—C4	0.50 (17)	N2—C7—C8—O2	−168.44 (10)
C2—C3—C4—C5	−0.11 (17)	Cl1—C7—C8—O2	10.96 (14)
C3—C4—C5—C6	−0.38 (17)	N2—C7—C8—O1	12.38 (14)
C4—C5—C6—C1	0.47 (17)	Cl1—C7—C8—O1	−168.22 (7)
C2—C1—C6—C5	−0.08 (16)	C8—O1—C9—C10	−176.85 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.85 (1)	2.18 (1)	2.969 (1)	153 (2)

Symmetry code: (i) −x+1, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₁ClN₂O₂
M_r	226.66
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	10.5091 (7), 11.1813 (8), 10.1190 (7)
β (°)	118.148 (1)
V (Å³)	1048.41 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.35
Crystal size (mm)	0.30 × 0.30 × 0.10

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.904, 0.966
No. of measured, independent and observed [I > 2σ(I)] reflections	6532, 2399, 2191
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.076, 1.03
No. of reflections	2399
No. of parameters	140
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.21

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···O2ⁱ	0.85 (1)	2.18 (1)	2.969 (1)	153 (2)

Symmetry code: (i) −x+1, y+1/2, −z+1/2.

Acknowledgements

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

References

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