5-Chloro­indoline-2,3-dione

Wei, W.-B.; Tian, S.; Zhou, H.; Sun, J.; Wang, H.-B.

doi:10.1107/S1600536810042522

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o3024

https://doi.org/10.1107/S1600536810042522

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5-Chloroindoline-2,3-dione

Wen-Bin Wei,^a,^b Shuo Tian,^b Hao Zhou,^b Jie Sun ^a and Hai-Bo Wang ^a ^*

^aCollege of Light Industry and Food Science, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China, and ^bCollege of Science, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: wanghaibo@njut.edu.cn

(Received 15 October 2010; accepted 20 October 2010; online 31 October 2010)

The title compound, C₈H₄ClNO₂, is almost planar (r.m.s. deviation for the non-H atoms = 0.023 Å). In the crystal, N—H⋯O hydrogen bonds link the molecules into C(4) chains propagating in [001] and C—H⋯O interactions cross-link the chains.

Related literature

For further synthetic details, see: Silva et al. (2001 ). For reference bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₈H₄ClNO₂
M_r = 181.57
Orthorhombic, P n a 2₁
a = 24.706 (5) Å
b = 5.6890 (11) Å
c = 5.209 (1) Å
V = 732.1 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.47 mm⁻¹
T = 293 K
0.10 × 0.05 × 0.05 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.955, T_max = 0.977
1746 measured reflections
884 independent reflections
734 reflections with I > 2σ(I)
R_int = 0.048
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.102
S = 1.00
884 reflections
109 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.24 e Å⁻³
Absolute structure: Flack (1983 ), 862 Friedel pairs
Flack parameter: 0.11 (16)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N—H0A⋯O1ⁱ	0.86	2.04	2.893 (4)	172
C7—H7A⋯O2ⁱⁱ	0.93	2.39	3.301 (5)	166
Symmetry codes: (i) $[-x+1, -y, z-{\script{1\over 2}}]$ ; (ii) x, y-1, z-1.

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; 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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810042522/hb5688sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810042522/hb5688Isup2.hkl

checkCIF report

Comment top

5-Chloroindoline-2,3-dione is an important pharmaceutical intermediate for synthesizing 5-chlorooxindole and tenidap which was evaluated as novel nonsteroidal anti-inflammatory agents. We report herein the crystal structure of the title compound.

In the molecule of the title compound (Fig 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (N/C1—C3/C8) and B (C3—C8) are nearly coplanar, and they are oriented at dihedral angles of A/B = 0.30 (3).

In the crystal structure, intermolecular N—H···O interaction may be effective in the stabilization of the structure.

Related literature top

For further synthetic details, see: Silva et al. (2001). For reference bond lengths, see: Allen et al. (1987).

Experimental top

For the preparation of the title compound, the method developed by Sandmeyer is the oldest and the most frequently used. It consists in the reaction of 4-chloroaniline with chloral hydrate and hydroxylamine hydrochloride in aqueous sodium sulfate to form an 4-chloroisonitrosoacetanilide, which after isolation, when treated with concentrated sulfuric acid, furnishes the title compound in 75% overall yield (Silva et al., 2001). Red blocks of (I) were obtained by slow evaporation of a methanol solution (m.p. 520 K).

Structure description top

In the crystal structure, intermolecular N—H···O interaction may be effective in the stabilization of the structure.

For further synthetic details, see: Silva et al. (2001). For reference bond lengths, see: Allen et al. (1987).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); 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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. View of the title compound with displacement ellipsoids for non-H atoms drawn at the 50% probability level.
	Fig. 2. Packing diagram.

5-Chloroindoline-2,3-dione top

Crystal data top

C₈H₄ClNO₂	D_x = 1.647 Mg m⁻³
M_r = 181.57	Melting point: 520 K
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 25 reflections
a = 24.706 (5) Å	θ = 9–13°
b = 5.6890 (11) Å	µ = 0.47 mm⁻¹
c = 5.209 (1) Å	T = 293 K
V = 732.1 (2) Å³	Block, red
Z = 4	0.10 × 0.05 × 0.05 mm
F(000) = 368

Data collection top

Enraf–Nonius CAD-4 diffractometer	734 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.048
Graphite monochromator	θ_max = 27.0°, θ_min = 1.7°
ω/2θ scans	h = −31→31
Absorption correction: ψ scan (North et al., 1968)	k = −7→0
T_min = 0.955, T_max = 0.977	l = 0→6
1746 measured reflections	3 standard reflections every 200 reflections
884 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)] = 0.037	H-atom parameters constrained
wR(F²) = 0.102	w = 1/[σ²(F_o²) + (0.065P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
884 reflections	Δρ_max = 0.18 e Å⁻³
109 parameters	Δρ_min = −0.24 e Å⁻³
2 restraints	Absolute structure: Flack (1983), 862 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.11 (16)

Crystal data top

C₈H₄ClNO₂	V = 732.1 (2) Å³
M_r = 181.57	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 24.706 (5) Å	µ = 0.47 mm⁻¹
b = 5.6890 (11) Å	T = 293 K
c = 5.209 (1) Å	0.10 × 0.05 × 0.05 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	734 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.048
T_min = 0.955, T_max = 0.977	3 standard reflections every 200 reflections
1746 measured reflections	intensity decay: 1%
884 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.102	Δρ_max = 0.18 e Å⁻³
S = 1.00	Δρ_min = −0.24 e Å⁻³
884 reflections	Absolute structure: Flack (1983), 862 Friedel pairs
109 parameters	Absolute structure parameter: 0.11 (16)
2 restraints

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	0.26410 (4)	0.6028 (2)	0.2215 (3)	0.0588 (4)
N	0.45038 (11)	0.1571 (5)	0.7251 (9)	0.0378 (8)
H0A	0.4676	0.0291	0.6924	0.045*
O1	0.49964 (12)	0.2818 (5)	1.0752 (7)	0.0441 (7)
C1	0.46351 (13)	0.3075 (6)	0.9153 (9)	0.0335 (8)
O2	0.42293 (11)	0.6781 (5)	1.0449 (7)	0.0446 (7)
C2	0.42335 (13)	0.5098 (6)	0.9018 (8)	0.0332 (8)
C3	0.38713 (13)	0.4525 (6)	0.6867 (8)	0.0321 (8)
C4	0.34278 (14)	0.5650 (7)	0.5820 (9)	0.0351 (9)
H4A	0.3300	0.7058	0.6497	0.042*
C5	0.31808 (13)	0.4609 (7)	0.3733 (8)	0.0373 (9)
C6	0.33568 (15)	0.2468 (7)	0.2760 (8)	0.0409 (10)
H6A	0.3175	0.1793	0.1381	0.049*
C7	0.37976 (16)	0.1329 (6)	0.3811 (10)	0.0390 (9)
H7A	0.3920	−0.0093	0.3148	0.047*
C8	0.40480 (13)	0.2366 (6)	0.5864 (9)	0.0333 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.0493 (6)	0.0757 (8)	0.0512 (6)	0.0147 (5)	−0.0117 (6)	0.0048 (8)
N	0.0425 (16)	0.0279 (14)	0.0430 (19)	0.0100 (12)	−0.0008 (19)	−0.002 (2)
O1	0.0477 (13)	0.0415 (14)	0.0431 (17)	0.0070 (13)	−0.0070 (15)	0.0018 (16)
C1	0.0351 (18)	0.0309 (18)	0.034 (2)	0.0025 (15)	0.0050 (19)	0.0035 (19)
O2	0.0524 (16)	0.0387 (14)	0.0427 (17)	0.0069 (13)	0.0030 (15)	−0.0108 (15)
C2	0.0398 (18)	0.0263 (15)	0.033 (2)	0.0039 (15)	0.0081 (18)	−0.0007 (18)
C3	0.0341 (16)	0.0284 (15)	0.034 (2)	0.0043 (14)	0.0069 (18)	0.0027 (17)
C4	0.0402 (18)	0.0330 (17)	0.032 (2)	0.0046 (15)	0.0074 (18)	−0.0012 (18)
C5	0.0326 (16)	0.045 (2)	0.034 (2)	0.0015 (16)	0.0002 (18)	0.006 (2)
C6	0.0439 (19)	0.045 (2)	0.033 (2)	−0.0096 (18)	0.0013 (18)	−0.0013 (19)
C7	0.049 (2)	0.0302 (17)	0.038 (2)	−0.0020 (16)	0.009 (2)	−0.0053 (18)
C8	0.0352 (17)	0.0294 (17)	0.035 (2)	−0.0004 (15)	0.0059 (18)	−0.0018 (18)

Geometric parameters (Å, º) top

Cl—C5	1.748 (4)	C3—C8	1.404 (5)
N—C1	1.349 (6)	C4—C5	1.381 (6)
N—C8	1.412 (5)	C4—H4A	0.9300
N—H0A	0.8600	C5—C6	1.389 (6)
O1—C1	1.229 (5)	C6—C7	1.380 (6)
C1—C2	1.521 (4)	C6—H6A	0.9300
O2—C2	1.213 (4)	C7—C8	1.369 (6)
C2—C3	1.471 (5)	C7—H7A	0.9300
C3—C4	1.381 (5)

C1—N—C8	111.4 (3)	C3—C4—H4A	121.2
C1—N—H0A	124.3	C4—C5—C6	121.7 (4)
C8—N—H0A	124.3	C4—C5—Cl	119.7 (3)
O1—C1—N	126.7 (3)	C6—C5—Cl	118.6 (3)
O1—C1—C2	126.5 (4)	C7—C6—C5	120.9 (4)
N—C1—C2	106.8 (3)	C7—C6—H6A	119.5
O2—C2—C3	129.6 (3)	C5—C6—H6A	119.5
O2—C2—C1	125.1 (4)	C8—C7—C6	117.6 (4)
C3—C2—C1	105.3 (3)	C8—C7—H7A	121.2
C4—C3—C8	120.3 (4)	C6—C7—H7A	121.2
C4—C3—C2	132.9 (3)	C7—C8—C3	121.8 (4)
C8—C3—C2	106.7 (3)	C7—C8—N	128.5 (3)
C5—C4—C3	117.6 (4)	C3—C8—N	109.7 (4)
C5—C4—H4A	121.2

C8—N—C1—O1	176.7 (4)	C3—C4—C5—Cl	−176.5 (3)
C8—N—C1—C2	−0.8 (4)	C4—C5—C6—C7	−1.8 (6)
O1—C1—C2—O2	2.4 (7)	Cl—C5—C6—C7	176.9 (3)
N—C1—C2—O2	179.9 (4)	C5—C6—C7—C8	1.0 (6)
O1—C1—C2—C3	−177.1 (4)	C6—C7—C8—C3	−0.7 (6)
N—C1—C2—C3	0.4 (4)	C6—C7—C8—N	−179.5 (4)
O2—C2—C3—C4	−0.2 (7)	C4—C3—C8—C7	1.2 (6)
C1—C2—C3—C4	179.2 (4)	C2—C3—C8—C7	−179.6 (4)
O2—C2—C3—C8	−179.3 (4)	C4—C3—C8—N	−179.8 (4)
C1—C2—C3—C8	0.2 (4)	C2—C3—C8—N	−0.6 (4)
C8—C3—C4—C5	−1.9 (6)	C1—N—C8—C7	179.8 (4)
C2—C3—C4—C5	179.2 (4)	C1—N—C8—C3	0.9 (5)
C3—C4—C5—C6	2.2 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H0A···O1ⁱ	0.86	2.04	2.893 (4)	172
C7—H7A···O2ⁱⁱ	0.93	2.39	3.301 (5)	166

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

Experimental details

Crystal data
Chemical formula	C₈H₄ClNO₂
M_r	181.57
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	293
a, b, c (Å)	24.706 (5), 5.6890 (11), 5.209 (1)
V (Å³)	732.1 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.47
Crystal size (mm)	0.10 × 0.05 × 0.05

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.955, 0.977
No. of measured, independent and observed [I > 2σ(I)] reflections	1746, 884, 734
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.102, 1.00
No. of reflections	884
No. of parameters	109
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.24
Absolute structure	Flack (1983), 862 Friedel pairs
Absolute structure parameter	0.11 (16)

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H0A···O1ⁱ	0.86	2.04	2.893 (4)	172
C7—H7A···O2ⁱⁱ	0.93	2.39	3.301 (5)	166

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

Acknowledgements

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

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
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