PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 September 1; 66(Pt 9): o2375.
Published online 2010 August 21. doi:  10.1107/S1600536810032599
PMCID: PMC3007972

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

Abstract

The title compound, C10H10Cl2N2O2, features a planar Car—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 [triangle]). For related structures, see: Xu (2006 [triangle]); Yin et al. (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2375-scheme1.jpg

Experimental

Crystal data

  • C10H10Cl2N2O2
  • M r = 261.10
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2375-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.072
  • wR(F 2) = 0.188
  • S = 1.03
  • 2518 reflections
  • 145 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.59 e Å−3
  • Δρmin = −0.34 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1123 Friedel pairs
  • Flack parameter: 0.03 (14)

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/S1600536810032599/nk2055sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810032599/nk2055Isup2.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 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).

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 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.

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 similarly positioned [N–H 0.86 Å, U(H) 1.2Ueq(N)]. The absolute structure parameter (Flack, 1983) was determined from 1123 Friedel pairs.

Figures

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.

Crystal data

C10H10Cl2N2O2F(000) = 268
Mr = 261.10Dx = 1.528 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 1574 reflections
a = 4.4611 (7) Åθ = 2.6–27.2°
b = 9.4546 (14) ŵ = 0.56 mm1
c = 13.464 (2) ÅT = 100 K
β = 91.642 (2)°Prism, colourless
V = 567.65 (15) Å30.35 × 0.10 × 0.05 mm
Z = 2

Data collection

Bruker SMART APEX diffractometer2518 independent reflections
Radiation source: fine-focus sealed tube2191 reflections with I > 2σ(I)
graphiteRint = 0.073
ω scansθmax = 27.5°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −5→5
Tmin = 0.829, Tmax = 0.973k = −12→11
5298 measured reflectionsl = −17→17

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.072H-atom parameters constrained
wR(F2) = 0.188w = 1/[σ2(Fo2) + (0.1216P)2 + 0.1253P] where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.001
2518 reflectionsΔρmax = 0.59 e Å3
145 parametersΔρmin = −0.34 e Å3
1 restraintAbsolute structure: Flack (1983), 1123 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.03 (14)

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

xyzUiso*/Ueq
Cl11.4745 (3)0.50000 (14)0.97204 (9)0.0301 (4)
Cl20.4463 (3)0.85685 (12)0.46296 (8)0.0226 (3)
N10.8095 (9)0.7704 (5)0.6374 (3)0.0203 (8)
H10.83760.74070.57800.024*
N20.6137 (9)0.8722 (4)0.6540 (3)0.0194 (8)
O10.0631 (7)1.0838 (4)0.5375 (2)0.0222 (7)
O20.2281 (8)1.0713 (4)0.6974 (2)0.0223 (7)
C10.9702 (11)0.7120 (5)0.7183 (4)0.0193 (10)
C20.9430 (11)0.7619 (5)0.8146 (4)0.0212 (10)
H2A0.81630.84030.82700.025*
C31.0993 (12)0.6981 (5)0.8922 (4)0.0240 (10)
H31.08040.73240.95810.029*
C41.2829 (11)0.5844 (6)0.8740 (4)0.0229 (10)
C51.3191 (11)0.5353 (5)0.7776 (4)0.0225 (10)
H51.45090.45870.76540.027*
C61.1616 (10)0.5990 (5)0.7000 (4)0.0207 (10)
H61.18360.56570.63400.025*
C70.4460 (10)0.9208 (5)0.5837 (3)0.0176 (9)
C80.2257 (10)1.0339 (5)0.6023 (3)0.0183 (9)
C90.0103 (11)1.1798 (5)0.7225 (4)0.0223 (10)
H9A−0.19451.15010.70120.027*
H9B0.05751.27000.68910.027*
C100.0316 (13)1.1969 (6)0.8335 (4)0.0282 (11)
H10A−0.11101.26940.85410.042*
H10B0.23561.22580.85340.042*
H10C−0.01591.10680.86540.042*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0349 (7)0.0288 (7)0.0262 (6)0.0030 (5)−0.0055 (5)0.0046 (5)
Cl20.0251 (6)0.0219 (6)0.0209 (5)−0.0002 (5)0.0003 (4)−0.0019 (5)
N10.0213 (19)0.021 (2)0.0193 (19)0.0011 (17)0.0023 (15)−0.0014 (15)
N20.0244 (19)0.0112 (18)0.0225 (19)−0.0033 (16)0.0012 (14)0.0034 (16)
O10.0253 (18)0.0156 (17)0.0253 (17)0.0035 (14)−0.0032 (13)0.0017 (13)
O20.0252 (18)0.0187 (17)0.0230 (17)0.0050 (14)−0.0007 (13)−0.0012 (13)
C10.019 (2)0.018 (3)0.022 (2)−0.0082 (19)−0.0025 (16)0.0008 (19)
C20.022 (2)0.015 (2)0.027 (3)−0.0014 (19)0.0028 (19)−0.0011 (18)
C30.029 (3)0.019 (3)0.023 (2)−0.004 (2)0.0002 (19)−0.0018 (19)
C40.020 (2)0.023 (2)0.025 (2)−0.0036 (19)−0.0055 (18)0.0060 (19)
C50.025 (2)0.015 (2)0.027 (2)−0.0026 (19)−0.0011 (18)−0.0014 (18)
C60.017 (2)0.022 (3)0.023 (2)0.0001 (19)0.0012 (17)−0.0020 (19)
C70.018 (2)0.018 (2)0.017 (2)−0.0054 (18)−0.0012 (16)−0.0019 (17)
C80.019 (2)0.016 (2)0.020 (2)−0.0081 (18)−0.0016 (16)0.0038 (17)
C90.025 (3)0.014 (2)0.028 (2)0.003 (2)0.000 (2)−0.0028 (18)
C100.038 (3)0.021 (3)0.026 (2)0.001 (2)0.002 (2)−0.003 (2)

Geometric parameters (Å, °)

Cl1—C41.745 (5)C3—C41.378 (7)
Cl2—C71.735 (5)C3—H30.9500
N1—N21.323 (6)C4—C51.392 (7)
N1—C11.400 (6)C5—C61.381 (7)
N1—H10.8600C5—H50.9500
N2—C71.275 (6)C6—H60.9500
O1—C81.214 (6)C7—C81.478 (7)
O2—C81.328 (6)C9—C101.504 (7)
O2—C91.459 (6)C9—H9A0.9900
C1—C21.388 (7)C9—H9B0.9900
C1—C61.394 (7)C10—H10A0.9800
C2—C31.379 (7)C10—H10B0.9800
C2—H2A0.9500C10—H10C0.9800
N2—N1—C1118.7 (4)C5—C6—H6120.0
N2—N1—H1120.6C1—C6—H6120.0
C1—N1—H1120.6N2—C7—C8120.9 (4)
C7—N2—N1120.8 (4)N2—C7—Cl2123.6 (4)
C8—O2—C9115.0 (4)C8—C7—Cl2115.4 (3)
C2—C1—C6119.7 (4)O1—C8—O2125.3 (4)
C2—C1—N1122.4 (5)O1—C8—C7123.1 (4)
C6—C1—N1117.9 (4)O2—C8—C7111.6 (4)
C3—C2—C1120.2 (5)O2—C9—C10106.4 (4)
C3—C2—H2A119.9O2—C9—H9A110.4
C1—C2—H2A119.9C10—C9—H9A110.4
C2—C3—C4119.8 (5)O2—C9—H9B110.4
C2—C3—H3120.1C10—C9—H9B110.4
C4—C3—H3120.1H9A—C9—H9B108.6
C3—C4—C5120.8 (4)C9—C10—H10A109.5
C3—C4—Cl1120.2 (4)C9—C10—H10B109.5
C5—C4—Cl1119.0 (4)H10A—C10—H10B109.5
C6—C5—C4119.3 (5)C9—C10—H10C109.5
C6—C5—H5120.3H10A—C10—H10C109.5
C4—C5—H5120.3H10B—C10—H10C109.5
C5—C6—C1120.1 (4)
C1—N1—N2—C7−174.5 (4)C2—C1—C6—C51.2 (7)
N2—N1—C1—C2−3.4 (7)N1—C1—C6—C5−178.3 (4)
N2—N1—C1—C6176.1 (4)N1—N2—C7—C8179.6 (4)
C6—C1—C2—C3−1.5 (7)N1—N2—C7—Cl22.3 (6)
N1—C1—C2—C3178.1 (4)C9—O2—C8—O11.1 (6)
C1—C2—C3—C40.0 (7)C9—O2—C8—C7−178.3 (4)
C2—C3—C4—C51.7 (7)N2—C7—C8—O1179.5 (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—C6178.2 (4)Cl2—C7—C8—O2176.4 (3)
C4—C5—C6—C10.5 (7)C8—O2—C9—C10175.2 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.862.203.009 (5)156

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NK2055).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2009). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • 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.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography