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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): o3189.
Published online 2009 November 25. doi:  10.1107/S1600536809049538
PMCID: PMC2972103

2-(4-Chloro­phen­oxy)acetohydrazide

Abstract

In the title compound, C8H9ClN2O2, the two planar fragments, i.e. the chloro­phenyl and C—C(=O)—N groups, are inclined at 14.93 (17)°. In the crystal, relatively weak inter­molecular N—H(...)N, C—H(...)O and N—H(...)O hydrogen bonds connect the mol­ecules into layers. The hydro­phobic parts of mol­ecules stick outside these layers and are connected with the neighbouring layers only by van der Waals contacts and Cl(...)Cl inter­actions [3.406 (2) Å].

Related literature

For background to hydrazides, see: Cajocorius et al. (1977 [triangle]); Liu et al. (2006 [triangle]); Narayana et al. (2005 [triangle]). For related structures, see: Akhtar et al. (2009 [triangle]); Lokanath et al. (1998 [triangle]); Mahendra et al. (2004 [triangle]); Podyachev et al. (2007 [triangle]). For graph-set symbols, see: Bernstein et al. (1995 [triangle]). For halogen–halogen inter­actions, see: Pedireddi et al. (1994 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o3189-scheme1.jpg

Experimental

Crystal data

  • C8H9ClN2O2
  • M r = 200.62
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o3189-efi13.jpg
  • a = 6.444 (1) Å
  • b = 4.011 (1) Å
  • c = 35.369 (4) Å
  • β = 91.89 (1)°
  • V = 913.7 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.39 mm−1
  • T = 295 K
  • 0.4 × 0.4 × 0.15 mm

Data collection

  • Oxford Diffraction Xcalibur (Sapphire2, large Be window) diffractometer
  • Absorption correction: multi-scan (CrysAlis Pro; Oxford Diffraction, 2009 [triangle]) T min = 0.678, T max = 0.944
  • 2864 measured reflections
  • 1761 independent reflections
  • 1448 reflections with I > 2σ(I)
  • R int = 0.022

Refinement

  • R[F 2 > 2σ(F 2)] = 0.058
  • wR(F 2) = 0.118
  • S = 1.15
  • 1761 reflections
  • 154 parameters
  • All H-atom parameters refined
  • Δρmax = 0.22 e Å−3
  • Δρmin = −0.28 e Å−3

Data collection: CrysAlis Pro (Oxford Diffraction, 2009 [triangle]); cell refinement: CrysAlis Pro; data reduction: CrysAlis Pro; program(s) used to solve structure: SIR92 (Altomare et al., 1993 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: Stereochemical Workstation Operation Manual (Siemens, 1989 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809049538/is2496sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809049538/is2496Isup2.hkl

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

Acknowledgments

CSC thanks the University of Mysore for research facilities.

supplementary crystallographic information

Comment

Hydrazides are useful precursors in the synthesis of several heterocyclic systems (e.g., Narayana et al., 2005). Some substituted hydrazides are reported to exhibit carcinostatic activity against several types of tumors and also possess antimicrobial activity (e.g., Cajocorius et al., 1977). They are also used as intermediates in many pharmaceutically important compounds (Liu et al., 2006). A new hydrazide, 2-(4-chlorophenoxy)acetohydrazide (I, Scheme 1), C8H9ClN2O2 was synthesized and its crystal structure is reported.

The molecule of I consists of two planar fragments (Fig. 1): the phenyl ring [maximum deviation of 0.014 (2) Å] and the N—C(=O)—C group, which is planar within 0.008 (2) Å. The N1 and O6 atoms deviate significantly (by ca 0.11 Å), and in the opposite directions, from this latter plane. Overall, the molecule is only slightly bent as the dihedral angle between the planes described above is 14.93 (17)°. Even smaller values of this angle were observed in similar compounds: 5.0° in [2-methyl-4-(2-methylbenzoyl)-phenoxy]acetohydrazide (Mahendra et al., 2004), 3.6° in (2,4-dichlorophenoxy)acetohydrazide (Lokanath et al., 1998) or 5.7° in 4-tert-butylphenoxyacetohydrazide (Podyachev et al., 2007). This planar and (Z)-NCCO conformation was sometimes ascribed to the doubtful intramolecular N—H···O hydrogen bond. When the steric hindrance is present, as for instance in the structure of 2-(4-bromophenoxy)propanohydrazide (Akhtar et al., 2009), the two planar fragments become almost perpendicular, dihedral angle between them is 84.9°.

In the crystal structure rather long intermolecular hydrogen bonds connect molecules into three-dimensional network (Table 1). The N—H···N hydrogen bonds, for which the terminal nitrogen atom of NH2 group acts as an acceptor, make a C(3) graph-set motif (Bernstein et al., 1995) - the chain of molecules along the b axis. Two N—H···O hydrogen bonds between the NH2 group and carbonyl oxygen atoms from neighbouring molecules make antiparallel C(5) chains that are interwoven into subsequent R22(10) rings. In the crystal structure there are layers of molecules connected by these hydrogen bonded hydrophilic fragments and the hydrophobic chlorophenyl fragments stick outside the layers. There are relatively short and linear Cl···Cl contacts between these layers [Cl13···Cl13(3 - x,-1 - y,1 - z) 3.406 (2) Å, C10—Cl13···Cl13(3 - x,-1 - y,1 - z) 155.14 (13)°], suggesting that there is a possibility for "dihalogen" interactions (e.g. Pedireddi et al., 1994).

Experimental

A mixture of ethyl(4-chlorophenoxy)acetate (21.4 g, 0.1 mol) and 6.0 ml of hydrazine hydrate in 90 ml of ethanol was refluxed over water bath for 6 h. The precipitate formed was filtered and recrystallized from ethanol (m.p.: 425 K). Analysis for C8H9ClN2O2: Found (Calculated): C 47.89 (47.81), H 4.52 (4.48), N 13.96% (13.88%).

Refinement

All hydrogen atoms were freely refined.

Figures

Fig. 1.
Anisotropic ellipsoid representation of the compound I together with atom labelling scheme. The ellipsoids are drawn at the 50% probability level and hydrogen atoms are depicted as spheres with arbitrary radii.
Fig. 2.
The hydrogen bonded motifs in the crystal structure of I. Hydrogen bonds are shown as dashed lines. (a) the N—H···N chain. [Symmetry codes: (i) x, y, z; (ii) x, -3/2 + y, 3/2 - z; (iii) 2 - x, 1/2 + y, 3/2 - z; (iv) 2 - ...
Fig. 3.
Crystal packing as seen along the a axis. Hydrogen bonds and Cl···Cl contacts are shown as dashed lines.

Crystal data

C8H9ClN2O2F(000) = 416
Mr = 200.62Dx = 1.458 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1266 reflections
a = 6.444 (1) Åθ = 2.3–26.8°
b = 4.011 (1) ŵ = 0.39 mm1
c = 35.369 (4) ÅT = 295 K
β = 91.89 (1)°Plate, colourless
V = 913.7 (3) Å30.4 × 0.4 × 0.15 mm
Z = 4

Data collection

Oxford Diffraction Xcalibur (Sapphire2, large Be window) diffractometer1761 independent reflections
Radiation source: Enhance (Mo) X-ray Source1448 reflections with I > 2σ(I)
graphiteRint = 0.022
Detector resolution: 8.1929 pixels mm-1θmax = 26.8°, θmin = 2.3°
ω–scanh = −8→6
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)k = −3→4
Tmin = 0.678, Tmax = 0.944l = −31→43
2864 measured reflections

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)] = 0.058Hydrogen site location: difference Fourier map
wR(F2) = 0.118All H-atom parameters refined
S = 1.15w = 1/[σ2(Fo2) + (0.0271P)2 + 1.1206P] where P = (Fo2 + 2Fc2)/3
1761 reflections(Δ/σ)max = 0.002
154 parametersΔρmax = 0.22 e Å3
0 restraintsΔρmin = −0.28 e Å3

Special details

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)

xyzUiso*/Ueq
N10.7883 (4)0.5362 (7)0.75916 (7)0.0346 (6)
H1A0.717 (5)0.733 (11)0.7541 (10)0.066 (11)*
H1B0.711 (5)0.417 (9)0.7747 (9)0.054 (10)*
N20.8013 (3)0.3650 (6)0.72417 (6)0.0317 (5)
H20.909 (4)0.247 (8)0.7201 (8)0.039 (8)*
C30.6568 (4)0.4000 (7)0.69716 (7)0.0300 (6)
O40.4957 (3)0.5630 (6)0.70086 (5)0.0425 (5)
C50.6937 (4)0.2401 (8)0.65965 (8)0.0341 (6)
H5A0.573 (5)0.103 (8)0.6525 (8)0.047 (9)*
H5B0.709 (4)0.412 (8)0.6420 (8)0.043 (8)*
O60.8781 (3)0.0467 (5)0.66140 (5)0.0398 (5)
C70.9615 (4)−0.0520 (8)0.62801 (7)0.0342 (6)
C81.1514 (4)−0.2151 (8)0.63137 (8)0.0412 (7)
H81.213 (5)−0.241 (8)0.6556 (8)0.050 (9)*
C91.2501 (5)−0.3162 (9)0.59971 (9)0.0478 (8)
H91.374 (5)−0.431 (9)0.6008 (9)0.062 (10)*
C101.1589 (5)−0.2639 (9)0.56450 (8)0.0473 (8)
C110.9690 (5)−0.1103 (10)0.56080 (8)0.0514 (9)
H110.902 (5)−0.092 (9)0.5362 (9)0.063 (10)*
C120.8682 (5)−0.0049 (8)0.59270 (8)0.0417 (7)
H120.742 (5)0.108 (9)0.5893 (8)0.052 (9)*
Cl131.28833 (18)−0.3900 (3)0.52474 (3)0.0838 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0321 (12)0.0390 (16)0.0327 (12)−0.0020 (11)0.0021 (10)−0.0013 (11)
N20.0264 (11)0.0380 (15)0.0307 (11)0.0052 (11)−0.0004 (9)−0.0004 (10)
C30.0266 (12)0.0283 (15)0.0352 (13)−0.0003 (12)0.0016 (10)0.0043 (12)
O40.0316 (10)0.0512 (14)0.0445 (11)0.0149 (10)−0.0025 (8)0.0003 (10)
C50.0307 (14)0.0371 (17)0.0342 (14)0.0034 (13)−0.0026 (11)0.0025 (13)
O60.0404 (10)0.0479 (13)0.0307 (9)0.0165 (10)−0.0024 (8)−0.0001 (9)
C70.0363 (14)0.0361 (17)0.0301 (13)−0.0001 (13)0.0013 (11)−0.0013 (12)
C80.0369 (15)0.049 (2)0.0379 (15)0.0075 (14)−0.0049 (12)−0.0007 (14)
C90.0384 (16)0.051 (2)0.0537 (18)0.0085 (16)0.0029 (14)−0.0046 (16)
C100.0562 (19)0.046 (2)0.0406 (16)0.0091 (16)0.0109 (14)−0.0036 (14)
C110.063 (2)0.061 (2)0.0305 (14)0.0130 (19)−0.0030 (14)0.0010 (16)
C120.0418 (16)0.045 (2)0.0375 (15)0.0105 (14)−0.0040 (12)0.0009 (13)
Cl130.0958 (8)0.1032 (9)0.0543 (5)0.0323 (7)0.0293 (5)−0.0067 (6)

Geometric parameters (Å, °)

N1—N21.420 (3)C7—C121.381 (4)
N1—H1A0.93 (4)C7—C81.389 (4)
N1—H1B0.89 (4)C8—C91.367 (4)
N2—C31.319 (3)C8—H80.94 (3)
N2—H20.86 (3)C9—C101.376 (4)
C3—O41.237 (3)C9—H90.92 (4)
C3—C51.499 (4)C10—C111.372 (4)
C5—O61.419 (3)C10—Cl131.734 (3)
C5—H5A0.98 (3)C11—C121.387 (4)
C5—H5B0.94 (3)C11—H110.96 (3)
O6—C71.372 (3)C12—H120.93 (3)
N2—N1—H1A107 (2)O6—C7—C8115.6 (2)
N2—N1—H1B109 (2)C12—C7—C8119.8 (3)
H1A—N1—H1B107 (3)C9—C8—C7120.1 (3)
C3—N2—N1121.3 (2)C9—C8—H8121.4 (19)
C3—N2—H2119.6 (19)C7—C8—H8118.4 (19)
N1—N2—H2119.0 (19)C8—C9—C10120.0 (3)
O4—C3—N2123.6 (2)C8—C9—H9123 (2)
O4—C3—C5118.5 (2)C10—C9—H9117 (2)
N2—C3—C5117.8 (2)C11—C10—C9120.5 (3)
O6—C5—C3110.6 (2)C11—C10—Cl13120.3 (2)
O6—C5—H5A111.3 (19)C9—C10—Cl13119.1 (3)
C3—C5—H5A108.6 (17)C10—C11—C12120.0 (3)
O6—C5—H5B108.7 (18)C10—C11—H11120 (2)
C3—C5—H5B107.4 (19)C12—C11—H11120 (2)
H5A—C5—H5B110 (3)C7—C12—C11119.5 (3)
C7—O6—C5118.1 (2)C7—C12—H12122.2 (19)
O6—C7—C12124.6 (3)C11—C12—H12118.1 (19)
N1—N2—C3—O4−4.8 (4)C7—C8—C9—C10−1.6 (5)
N1—N2—C3—C5173.5 (2)C8—C9—C10—C110.1 (6)
O4—C3—C5—O6−176.2 (3)C8—C9—C10—Cl13179.3 (3)
N2—C3—C5—O65.4 (4)C9—C10—C11—C120.4 (6)
C3—C5—O6—C7−164.9 (2)Cl13—C10—C11—C12−178.9 (3)
C5—O6—C7—C12−6.7 (4)O6—C7—C12—C11178.9 (3)
C5—O6—C7—C8174.5 (3)C8—C7—C12—C11−2.4 (5)
O6—C7—C8—C9−178.4 (3)C10—C11—C12—C70.8 (6)
C12—C7—C8—C92.8 (5)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···O4i0.93 (4)2.51 (4)3.160 (3)127 (3)
N1—H1B···O4ii0.89 (4)2.15 (4)3.020 (3)165 (3)
N2—H2···N1iii0.86 (3)2.23 (3)2.997 (3)149 (3)
C8—H8···O4iv0.94 (3)2.51 (3)3.376 (3)153 (2)

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) −x+1, y−1/2, −z+3/2; (iii) −x+2, y−1/2, −z+3/2; (iv) x+1, y−1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IS2496).

References

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