2-(4-Chloro­phen­oxy)acetohydrazide

Grzegorz Dutkiewicz; C S Chidan Kumar; B Narayana; H S Yathirajan; Maciej Kubicki

doi:10.1107/S1600536809049538

. 2009 Nov 25;65(Pt 12):o3189. doi: 10.1107/S1600536809049538

2-(4-Chlorophenoxy)acetohydrazide

Grzegorz Dutkiewicz ^a, C S Chidan Kumar ^b, B Narayana ^c, H S Yathirajan ^b, Maciej Kubicki ^a,^*

PMCID: PMC2972103 PMID: 21578901

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 ▶); Liu et al. (2006 ▶); Narayana et al. (2005 ▶). For related structures, see: Akhtar et al. (2009 ▶); Lokanath et al. (1998 ▶); Mahendra et al. (2004 ▶); Podyachev et al. (2007 ▶). For graph-set symbols, see: Bernstein et al. (1995 ▶). For halogen–halogen interactions, see: Pedireddi et al. (1994 ▶). graphic file with name e-65-o3189-scheme1.jpg

Experimental

Crystal data

C₈H₉ClN₂O₂
M _r = 200.62
Monoclinic,
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 ▶) 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
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.28 e Å⁻³

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

Supplementary Material

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

e-65-o3189-sup1.cif^{(15.2KB, cif)}

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

e-65-o3189-Isup2.hkl^{(85KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4ⁱ	0.93 (4)	2.51 (4)	3.160 (3)	127 (3)
N1—H1B⋯O4ⁱⁱ	0.89 (4)	2.15 (4)	3.020 (3)	165 (3)
N2—H2⋯N1ⁱⁱⁱ	0.86 (3)	2.23 (3)	2.997 (3)	149 (3)
C8—H8⋯O4^iv	0.94 (3)	2.51 (3)	3.376 (3)	153 (2)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

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%).