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

Sun, J.; Cai, Z.

doi:10.1107/S1600536809033315

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2249

doi:10.1107/S1600536809033315

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

Jie Sun ^a ^* and Zaisheng Cai ^a

^aCollege of Chemistry, Chemical Engineering and Biotechnology, Donghua University, North Renmin Road No. 2999 Songjiang, Shanghai 201620, People's Republic of China
^*Correspondence e-mail: sunjie5516@126.com

(Received 8 July 2009; accepted 21 August 2009; online 26 August 2009)

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, P b c a
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[F² > 2σ(F²)] = 0.047
wR(F²) = 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

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
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) $[x+{\script{1\over 2}}, -y-{\script{1\over 2}}, -z+1]$ .

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.

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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 top

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).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); 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 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bond is shown as dashed line.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

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

Crystal data top

C₈H₇ClN₂O₂	D_x = 1.464 Mg m⁻³
M_r = 198.61	Melting point: 443 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 25 reflections
a = 10.101 (2) Å	θ = 10–14°
b = 8.9150 (18) Å	µ = 0.39 mm⁻¹
c = 20.009 (4) Å	T = 293 K
V = 1801.8 (6) Å³	Block, yellow
Z = 8	0.30 × 0.20 × 0.10 mm
F(000) = 816

Data collection top

Enraf–Nonius CAD-4 diffractometer	1250 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.031
Graphite monochromator	θ_max = 25.3°, θ_min = 2.0°
ω/2θ scans	h = 0→12
Absorption correction: ψ scan (North et al., 1968)	k = 0→10
T_min = 0.892, T_max = 0.962	l = −24→24
3213 measured reflections	3 standard reflections every 200 reflections
1639 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.047	H-atom parameters constrained
wR(F²) = 0.153	w = 1/[σ²(F_o²) + (0.1P)² + 0.25P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
1639 reflections	Δρ_max = 0.40 e Å⁻³
119 parameters	Δρ_min = −0.36 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.013 (3)

Crystal data top

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

Data collection top

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

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.153	H-atom parameters constrained
S = 1.00	Δρ_max = 0.40 e Å⁻³
1639 reflections	Δρ_min = −0.36 e Å⁻³
119 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Cl	0.26935 (10)	0.17533 (11)	0.78148 (5)	0.0896 (4)
O1	0.65722 (17)	−0.19066 (16)	0.54941 (10)	0.0497 (5)
N1	0.62352 (19)	0.0637 (2)	0.55162 (10)	0.0425 (5)
H1A	0.6442	0.1442	0.5304	0.051*
C1	0.3696 (3)	0.1410 (3)	0.71252 (15)	0.0565 (7)
O2	0.96195 (19)	−0.0993 (2)	0.42075 (9)	0.0572 (6)
H2A	1.0264	−0.1546	0.4246	0.086*
N2	0.86646 (19)	−0.1394 (2)	0.46737 (10)	0.0435 (5)
C2	0.4060 (3)	0.2563 (3)	0.67015 (13)	0.0571 (7)
H2C	0.3749	0.3531	0.6775	0.068*
C3	0.4883 (2)	0.2267 (3)	0.61720 (13)	0.0473 (6)
H3A	0.5137	0.3044	0.5889	0.057*
C4	0.5342 (2)	0.0825 (2)	0.60529 (12)	0.0392 (6)
C5	0.4961 (3)	−0.0326 (3)	0.64785 (13)	0.0572 (8)
H5A	0.5260	−0.1298	0.6405	0.069*
C6	0.4138 (3)	−0.0022 (3)	0.70111 (15)	0.0610 (8)
H6A	0.3881	−0.0794	0.7295	0.073*
C7	0.6807 (2)	−0.0630 (2)	0.52908 (12)	0.0393 (6)
C8	0.7835 (2)	−0.0349 (3)	0.47759 (12)	0.0415 (6)
H8A	0.7870	0.0549	0.4540	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.0956 (7)	0.0920 (7)	0.0814 (6)	0.0178 (5)	0.0434 (5)	0.0147 (5)
O1	0.0536 (11)	0.0290 (9)	0.0667 (11)	−0.0014 (7)	0.0034 (9)	0.0062 (8)
N1	0.0494 (11)	0.0265 (9)	0.0518 (12)	−0.0012 (8)	0.0038 (10)	0.0060 (8)
C1	0.0499 (15)	0.0637 (17)	0.0559 (16)	0.0043 (13)	0.0082 (12)	0.0062 (13)
O2	0.0517 (11)	0.0475 (10)	0.0725 (13)	0.0092 (9)	0.0147 (10)	0.0054 (9)
N2	0.0431 (11)	0.0347 (10)	0.0526 (12)	−0.0002 (9)	0.0000 (9)	0.0023 (9)
C2	0.0609 (17)	0.0482 (14)	0.0621 (17)	0.0131 (13)	0.0106 (14)	0.0045 (13)
C3	0.0477 (14)	0.0404 (13)	0.0538 (14)	0.0021 (11)	0.0040 (12)	0.0088 (11)
C4	0.0387 (12)	0.0340 (12)	0.0449 (12)	−0.0032 (10)	−0.0013 (10)	0.0016 (10)
C5	0.0754 (19)	0.0340 (13)	0.0621 (16)	−0.0052 (13)	0.0115 (15)	0.0025 (12)
C6	0.0713 (19)	0.0507 (15)	0.0611 (16)	−0.0100 (14)	0.0161 (14)	0.0107 (14)
C7	0.0394 (12)	0.0311 (11)	0.0472 (13)	0.0000 (10)	−0.0072 (11)	0.0024 (9)
C8	0.0453 (13)	0.0303 (11)	0.0491 (13)	0.0018 (10)	−0.0003 (10)	0.0048 (10)

Geometric parameters (Å, º) top

Cl—C1	1.739 (3)	C2—C3	1.373 (3)
O1—C7	1.232 (3)	C2—H2C	0.9300
N1—C7	1.346 (3)	C3—C4	1.387 (3)
N1—C4	1.412 (3)	C3—H3A	0.9300
N1—H1A	0.8600	C4—C5	1.388 (3)
C1—C6	1.371 (4)	C5—C6	1.378 (4)
C1—C2	1.382 (4)	C5—H5A	0.9300
O2—N2	1.389 (3)	C6—H6A	0.9300
O2—H2A	0.8200	C7—C8	1.484 (3)
N2—C8	1.270 (3)	C8—H8A	0.9300

C7—N1—C4	128.95 (19)	C3—C4—N1	117.01 (19)
C7—N1—H1A	115.5	C5—C4—N1	123.8 (2)
C4—N1—H1A	115.5	C6—C5—C4	119.8 (2)
C6—C1—C2	120.2 (3)	C6—C5—H5A	120.1
C6—C1—Cl	119.1 (2)	C4—C5—H5A	120.1
C2—C1—Cl	120.7 (2)	C1—C6—C5	120.5 (2)
N2—O2—H2A	109.5	C1—C6—H6A	119.7
C8—N2—O2	112.20 (19)	C5—C6—H6A	119.7
C3—C2—C1	119.5 (3)	O1—C7—N1	125.6 (2)
C3—C2—H2C	120.3	O1—C7—C8	121.3 (2)
C1—C2—H2C	120.3	N1—C7—C8	113.04 (19)
C2—C3—C4	120.9 (2)	N2—C8—C7	116.7 (2)
C2—C3—H3A	119.6	N2—C8—H8A	121.6
C4—C3—H3A	119.6	C7—C8—H8A	121.6
C3—C4—C5	119.1 (2)

C6—C1—C2—C3	−1.0 (4)	C2—C1—C6—C5	0.8 (5)
Cl—C1—C2—C3	178.1 (2)	Cl—C1—C6—C5	−178.4 (2)
C1—C2—C3—C4	0.7 (4)	C4—C5—C6—C1	−0.2 (4)
C2—C3—C4—C5	−0.2 (4)	C4—N1—C7—O1	5.3 (4)
C2—C3—C4—N1	−177.1 (2)	C4—N1—C7—C8	−171.9 (2)
C7—N1—C4—C3	−179.0 (2)	O2—N2—C8—C7	−177.10 (19)
C7—N1—C4—C5	4.3 (4)	O1—C7—C8—N2	−16.5 (3)
C3—C4—C5—C6	−0.1 (4)	N1—C7—C8—N2	160.9 (2)
N1—C4—C5—C6	176.6 (2)

Hydrogen-bond geometry (Å, º) top

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

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

Experimental details

Crystal data
Chemical formula	C₈H₇ClN₂O₂
M_r	198.61
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	10.101 (2), 8.9150 (18), 20.009 (4)
V (Å³)	1801.8 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.39
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.892, 0.962
No. of measured, independent and observed [I > 2σ(I)] reflections	3213, 1639, 1250
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.153, 1.00
No. of reflections	1639
No. of parameters	119
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.36

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4(Harms & Wocadlo,1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.8600	2.5200	3.115 (3)	127.00
N1—H1A···N2ⁱ	0.8600	2.3100	3.140 (3)	163.00
O2—H2A···O1ⁱⁱ	0.8200	1.9800	2.785 (3)	167.00
C5—H5A···O1	0.9300	2.3200	2.918 (3)	122.00

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

Acknowledgements

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

References

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