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Acta Crystallogr Sect E Struct Rep Online. 2010 September 1; 66(Pt 9): o2374.
Published online 2010 August 21. doi:  10.1107/S1600536810032587
PMCID: PMC3007979

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

Abstract

The title compound, C10H11ClN2O2, features an almost planar Car—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 [triangle]). For related crystal structures, see: Xu (2006 [triangle]); Yin et al. (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2374-scheme1.jpg

Experimental

Crystal data

  • C10H11ClN2O2
  • M r = 226.66
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2374-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.026
  • wR(F 2) = 0.076
  • S = 1.03
  • 2399 reflections
  • 140 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.31 e Å−3
  • Δρmin = −0.21 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810032587/nk2054sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810032587/nk2054Isup2.hkl

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

Acknowledgments

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

supplementary crystallographic information

Comment

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 Caryl–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).

Experimental

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.

Refinement

Carbon-bound H-atoms were placed in calculated positions [C–H 0.95 to 0.99 Å, U(H) 1.2 to 1.5Ueq(C)] and were included in the refinement in the riding model approximation. The amino H-atom was located in a difference Fourier map, and was refined with a distance restraint [N–H 0.86±0.01 Å]; its temperature factor was freely refined.

Figures

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.

Crystal data

C10H11ClN2O2F(000) = 472
Mr = 226.66Dx = 1.436 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4259 reflections
a = 10.5091 (7) Åθ = 2.3–28.3°
b = 11.1813 (8) ŵ = 0.35 mm1
c = 10.1190 (7) ÅT = 100 K
β = 118.148 (1)°Irregular, yellow
V = 1048.41 (13) Å30.30 × 0.30 × 0.10 mm
Z = 4

Data collection

Bruker SMART APEX diffractometer2399 independent reflections
Radiation source: fine-focus sealed tube2191 reflections with I > 2σ(I)
graphiteRint = 0.022
ω scansθmax = 27.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −13→11
Tmin = 0.904, Tmax = 0.966k = −14→12
6532 measured reflectionsl = −13→13

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)] = 0.026Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.076H atoms treated by a mixture of independent and constrained refinement
S = 1.03w = 1/[σ2(Fo2) + (0.0409P)2 + 0.389P] where P = (Fo2 + 2Fc2)/3
2399 reflections(Δ/σ)max = 0.001
140 parametersΔρmax = 0.31 e Å3
1 restraintΔρmin = −0.21 e Å3

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

xyzUiso*/Ueq
Cl10.52913 (3)0.54445 (2)0.33899 (3)0.02076 (10)
O10.67383 (8)0.38123 (7)0.09626 (9)0.01737 (18)
O20.49929 (9)0.33068 (7)0.15554 (9)0.01943 (19)
N10.70432 (10)0.70808 (8)0.26261 (10)0.0153 (2)
H10.6608 (17)0.7284 (15)0.3121 (17)0.032 (4)*
N20.68722 (10)0.59913 (8)0.20434 (10)0.01443 (19)
C10.78999 (11)0.79127 (10)0.23651 (11)0.0143 (2)
C20.81229 (12)0.90363 (10)0.30391 (12)0.0171 (2)
H20.76910.92320.36510.020*
C30.89810 (12)0.98666 (11)0.28081 (13)0.0201 (2)
H30.91401.06290.32730.024*
C40.96101 (13)0.95973 (11)0.19073 (14)0.0208 (2)
H41.01941.01700.17530.025*
C50.93736 (12)0.84780 (11)0.12342 (13)0.0201 (2)
H50.97960.82890.06120.024*
C60.85275 (12)0.76310 (10)0.14599 (12)0.0167 (2)
H60.83780.68660.10010.020*
C70.61141 (12)0.52090 (10)0.22737 (12)0.0152 (2)
C80.58682 (11)0.40102 (10)0.15624 (12)0.0147 (2)
C90.66715 (12)0.26082 (10)0.03770 (13)0.0176 (2)
H9A0.56980.2446−0.04610.021*
H9B0.68870.20060.11720.021*
C100.77830 (12)0.25572 (12)−0.01594 (13)0.0213 (3)
H10A0.77770.1760−0.05660.032*
H10B0.87400.27190.06810.032*
H10C0.75570.3159−0.09430.032*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.02594 (16)0.01667 (16)0.02897 (16)−0.00155 (10)0.02060 (13)−0.00199 (10)
O10.0184 (4)0.0141 (4)0.0232 (4)−0.0018 (3)0.0128 (3)−0.0032 (3)
O20.0200 (4)0.0155 (4)0.0260 (4)−0.0020 (3)0.0136 (3)0.0007 (3)
N10.0167 (4)0.0138 (5)0.0185 (4)−0.0005 (4)0.0109 (4)−0.0015 (3)
N20.0133 (4)0.0130 (5)0.0153 (4)0.0013 (3)0.0053 (3)0.0007 (3)
C10.0109 (5)0.0151 (5)0.0148 (5)0.0005 (4)0.0043 (4)0.0024 (4)
C20.0165 (5)0.0163 (6)0.0187 (5)0.0016 (4)0.0087 (4)0.0002 (4)
C30.0187 (5)0.0144 (5)0.0249 (6)−0.0006 (4)0.0084 (5)0.0001 (4)
C40.0164 (5)0.0202 (6)0.0247 (6)−0.0026 (4)0.0090 (5)0.0044 (4)
C50.0172 (5)0.0250 (6)0.0201 (5)0.0002 (5)0.0105 (4)0.0017 (4)
C60.0163 (5)0.0169 (5)0.0170 (5)−0.0002 (4)0.0078 (4)−0.0007 (4)
C70.0144 (5)0.0162 (5)0.0166 (5)0.0020 (4)0.0087 (4)0.0011 (4)
C80.0139 (5)0.0149 (5)0.0146 (5)0.0018 (4)0.0061 (4)0.0025 (4)
C90.0184 (5)0.0151 (5)0.0200 (5)0.0000 (4)0.0098 (4)−0.0022 (4)
C100.0189 (6)0.0241 (6)0.0221 (6)−0.0015 (5)0.0107 (5)−0.0062 (5)

Geometric parameters (Å, °)

Cl1—C71.7361 (11)C3—H30.9500
O1—C81.3331 (13)C4—C51.3900 (17)
O1—C91.4593 (13)C4—H40.9500
O2—C81.2076 (14)C5—C61.3897 (16)
N1—N21.3282 (13)C5—H50.9500
N1—C11.4035 (14)C6—H60.9500
N1—H10.853 (13)C7—C81.4853 (15)
N2—C71.2765 (14)C9—C101.5035 (15)
C1—C21.3957 (16)C9—H9A0.9900
C1—C61.3939 (15)C9—H9B0.9900
C2—C31.3888 (16)C10—H10A0.9800
C2—H20.9500C10—H10B0.9800
C3—C41.3883 (17)C10—H10C0.9800
C8—O1—C9115.22 (8)C5—C6—H6120.3
N2—N1—C1119.25 (9)C1—C6—H6120.3
N2—N1—H1120.4 (11)N2—C7—C8120.72 (10)
C1—N1—H1120.3 (11)N2—C7—Cl1124.07 (9)
C7—N2—N1120.85 (9)C8—C7—Cl1115.21 (8)
C2—C1—C6120.14 (10)O2—C8—O1124.99 (10)
C2—C1—N1118.64 (10)O2—C8—C7123.26 (10)
C6—C1—N1121.22 (10)O1—C8—C7111.74 (9)
C3—C2—C1119.48 (10)O1—C9—C10106.55 (9)
C3—C2—H2120.3O1—C9—H9A110.4
C1—C2—H2120.3C10—C9—H9A110.4
C4—C3—C2120.91 (11)O1—C9—H9B110.4
C4—C3—H3119.5C10—C9—H9B110.4
C2—C3—H3119.5H9A—C9—H9B108.6
C5—C4—C3119.11 (11)C9—C10—H10A109.5
C5—C4—H4120.4C9—C10—H10B109.5
C3—C4—H4120.4H10A—C10—H10B109.5
C4—C5—C6120.89 (11)C9—C10—H10C109.5
C4—C5—H5119.6H10A—C10—H10C109.5
C6—C5—H5119.6H10B—C10—H10C109.5
C5—C6—C1119.46 (11)
C1—N1—N2—C7179.17 (10)N1—C1—C6—C5−179.74 (10)
N2—N1—C1—C2−177.17 (9)N1—N2—C7—C8177.11 (9)
N2—N1—C1—C62.49 (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—C3179.26 (10)C9—O1—C8—C7173.93 (9)
C1—C2—C3—C40.50 (17)N2—C7—C8—O2−168.44 (10)
C2—C3—C4—C5−0.11 (17)Cl1—C7—C8—O210.96 (14)
C3—C4—C5—C6−0.38 (17)N2—C7—C8—O112.38 (14)
C4—C5—C6—C10.47 (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, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O2i0.85 (1)2.18 (1)2.969 (1)153 (2)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NK2054).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2009). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Shawali, A. S. & Farghaly, T. A. (2008). ARKIVOC, i, 18–64.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2010). J. Appl. Cryst.43, 920–925.
  • Xu, J. (2006). Acta Cryst. E62, o5317–o5318.
  • Yin, Z.-G., Du, Y.-J., Zhang, J.-S., Qian, H.-Y. & Wang, Q.-L. (2006). Acta Cryst. E62, o4807–o4808.

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