N-(4-Chloro­phen­yl)-2-(hydroxy­imino)acetamide

Jie Sun; Zaisheng Cai

doi:10.1107/S1600536809033315

. 2009 Aug 26;65(Pt 9):o2249. doi: 10.1107/S1600536809033315

N-(4-Chlorophenyl)-2-(hydroxyimino)acetamide

Jie Sun ^a,^*, Zaisheng Cai ^a

PMCID: PMC2969878 PMID: 21577646

Abstract

The title compound, C₈H₇ClN₂O₂, is an intermediate in the synthesis of 5-chloroisatin, which can be further transformed to 5-chloro-2-indolinone via a Wolff–Kishne reduction. The C₂N acetamide plane forms a dihedral angle of 6.3 (3)° with the benzene ring. An intramolecular C—H⋯O interaction results in the formation of a six-membered ring. In the crystal, intermolecular N—H⋯O, N—H⋯N and O—H⋯O hydrogen bonds link the molecules into multimers, forming sheets.

Related literature

For related structures, see: Miravitlles et al. (1974 ▶); Brianso et al. (1973 ▶); Liu et al. (2006 ▶). For the synthesis, see: Lai et al. (2003 ▶); Simon et al. (1997 ▶).

Experimental

Crystal data

C₈H₇ClN₂O₂
M _r = 198.61
Orthorhombic,
a = 10.101 (2) Å
b = 8.9150 (18) Å
c = 20.009 (4) Å
V = 1801.8 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.39 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.892, T _max = 0.962
3213 measured reflections
1639 independent reflections
1250 reflections with I > 2σ(I)
R _int = 0.031
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.153
S = 1.00
1639 reflections
119 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo,1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97 and PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809033315/fl2255sup1.cif

e-65-o2249-sup1.cif^{(15KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809033315/fl2255Isup2.hkl

e-65-o2249-Isup2.hkl^{(80.9KB, 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⋯O1ⁱ	0.86	2.52	3.115 (3)	127
N1—H1A⋯N2ⁱ	0.86	2.31	3.140 (3)	163
O2—H2A⋯O1ⁱⁱ	0.82	1.98	2.785 (3)	167
C5—H5A⋯O1	0.93	2.32	2.918 (3)	122

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

Acknowledgments

The authors thank the Center of Testing and Analysis of Nanjing University for support.

supplementary crystallographic information

Comment

The title compound is an important intermediate in the synthesis of 5-chloro-isatin,which can be further transformed to 5-chloro-2-indolinone via a Wolff-Kishne reduction.

As part of our ongoing studies on phenyl-substituted-2-indolinone(Lai et al., 2003; Simon et al.,1997), the crystal structure of (E)—N-(2-chlorophenyl)-2-(hydroxyimino)acetamide and (E)-2-(hydroxyimino)-N-phenylacetamide have been reported(Miravitlles et al.,1974; Brianso et al.,1973; Liu et al.,2006), we report herein the crystal structure of the title compound.

In the title compound (Fig 1), the bond lengths and angles are within normal ranges. The central acetamide plane N1/C7/O1/C8 forms a dihedral angle of 6.3 (3)° with the phenyl ring. An intramolecular C—H···O interaction results in the formation of a six-membered ring. In the crystal packiing, intermolecular N—H···O and N—H···N hydrogen bonds (Table 1) link the molecules into multimers (Fig. 2), ithat may be effective in the stabilization of the structure.

Experimental

85 g (0.06 mol) sodium sulfate and 300 ml water were added to a 1000 ml 3 mouthed flask, mixed until the sodium sulfate dissolved following which a saturated solution of 18 g (0.11 mol) chloral hydrate was added. While stirring, a mixture of 12.7 g(0.1 mol) p-chloroaniline, 12 ml hydrochloric acid and 100 ml water was added dropwise causing a white precipitate. Then 22 g(0.32 mol) hydroxylamine hydrochloride was added and the mixture was heated to 348k. After 5 h, a light yellow precipitate appeared which was filtered and washed with water, dried and recrystallized from ethanol (yield 90.2%). Crystals suitable for X-ray analysis were obtained by slow evaporation of an acetone solution (yield; 90%, m.p. 443 K).