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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810042522/hb5688sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536810042522/hb5688Isup2.hkl
Contains datablock I

CCDC reference: 799758

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.037
  • wR factor = 0.102
  • Data-to-parameter ratio = 16.0

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang .. 6 PLAT914_ALERT_3_C No Bijvoet Pairs in FCF for Non-centro Structure !
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 26.97 From the CIF: _reflns_number_total 1746 Count of symmetry unique reflns 884 Completeness (_total/calc) 197.51% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 862 Fraction of Friedel pairs measured 0.975 Are heavy atom types Z>Si present yes PLAT432_ALERT_2_G Short Inter X...Y Contact O1 .. C2 .. 2.81 Ang. PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 2 PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature 293 K PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels .......... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 6 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

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).

Refinement top

H atoms were positioned geometrically, with N—H = 0.86 Å (for NH) and C—H = 0.93 Å for aromatic, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C,N), where x = 1.5 for NH H and x = 1.2 for all other H atoms.

Structure description 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.

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
[Figure 1] Fig. 1. View of the title compound with displacement ellipsoids for non-H atoms drawn at the 50% probability level.
[Figure 2] Fig. 2. Packing diagram.
5-Chloroindoline-2,3-dione top
Crystal data top
C8H4ClNO2Dx = 1.647 Mg m3
Mr = 181.57Melting point: 520 K
Orthorhombic, Pna21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 25 reflections
a = 24.706 (5) Åθ = 9–13°
b = 5.6890 (11) ŵ = 0.47 mm1
c = 5.209 (1) ÅT = 293 K
V = 732.1 (2) Å3Block, red
Z = 40.10 × 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 tubeRint = 0.048
Graphite monochromatorθmax = 27.0°, θmin = 1.7°
ω/2θ scansh = 3131
Absorption correction: ψ scan
(North et al., 1968)
k = 70
Tmin = 0.955, Tmax = 0.977l = 06
1746 measured reflections3 standard reflections every 200 reflections
884 independent reflections intensity decay: 1%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.102 w = 1/[σ2(Fo2) + (0.065P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
884 reflectionsΔρmax = 0.18 e Å3
109 parametersΔρmin = 0.24 e Å3
2 restraintsAbsolute structure: Flack (1983), 862 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.11 (16)
Crystal data top
C8H4ClNO2V = 732.1 (2) Å3
Mr = 181.57Z = 4
Orthorhombic, Pna21Mo Kα radiation
a = 24.706 (5) ŵ = 0.47 mm1
b = 5.6890 (11) ÅT = 293 K
c = 5.209 (1) Å0.10 × 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)
Rint = 0.048
Tmin = 0.955, Tmax = 0.9773 standard reflections every 200 reflections
1746 measured reflections intensity decay: 1%
884 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.102Δρmax = 0.18 e Å3
S = 1.00Δρmin = 0.24 e Å3
884 reflectionsAbsolute structure: Flack (1983), 862 Friedel pairs
109 parametersAbsolute 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
xyzUiso*/Ueq
Cl0.26410 (4)0.6028 (2)0.2215 (3)0.0588 (4)
N0.45038 (11)0.1571 (5)0.7251 (9)0.0378 (8)
H0A0.46760.02910.69240.045*
O10.49964 (12)0.2818 (5)1.0752 (7)0.0441 (7)
C10.46351 (13)0.3075 (6)0.9153 (9)0.0335 (8)
O20.42293 (11)0.6781 (5)1.0449 (7)0.0446 (7)
C20.42335 (13)0.5098 (6)0.9018 (8)0.0332 (8)
C30.38713 (13)0.4525 (6)0.6867 (8)0.0321 (8)
C40.34278 (14)0.5650 (7)0.5820 (9)0.0351 (9)
H4A0.33000.70580.64970.042*
C50.31808 (13)0.4609 (7)0.3733 (8)0.0373 (9)
C60.33568 (15)0.2468 (7)0.2760 (8)0.0409 (10)
H6A0.31750.17930.13810.049*
C70.37976 (16)0.1329 (6)0.3811 (10)0.0390 (9)
H7A0.39200.00930.31480.047*
C80.40480 (13)0.2366 (6)0.5864 (9)0.0333 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl0.0493 (6)0.0757 (8)0.0512 (6)0.0147 (5)0.0117 (6)0.0048 (8)
N0.0425 (16)0.0279 (14)0.0430 (19)0.0100 (12)0.0008 (19)0.002 (2)
O10.0477 (13)0.0415 (14)0.0431 (17)0.0070 (13)0.0070 (15)0.0018 (16)
C10.0351 (18)0.0309 (18)0.034 (2)0.0025 (15)0.0050 (19)0.0035 (19)
O20.0524 (16)0.0387 (14)0.0427 (17)0.0069 (13)0.0030 (15)0.0108 (15)
C20.0398 (18)0.0263 (15)0.033 (2)0.0039 (15)0.0081 (18)0.0007 (18)
C30.0341 (16)0.0284 (15)0.034 (2)0.0043 (14)0.0069 (18)0.0027 (17)
C40.0402 (18)0.0330 (17)0.032 (2)0.0046 (15)0.0074 (18)0.0012 (18)
C50.0326 (16)0.045 (2)0.034 (2)0.0015 (16)0.0002 (18)0.006 (2)
C60.0439 (19)0.045 (2)0.033 (2)0.0096 (18)0.0013 (18)0.0013 (19)
C70.049 (2)0.0302 (17)0.038 (2)0.0020 (16)0.009 (2)0.0053 (18)
C80.0352 (17)0.0294 (17)0.035 (2)0.0004 (15)0.0059 (18)0.0018 (18)
Geometric parameters (Å, º) top
Cl—C51.748 (4)C3—C81.404 (5)
N—C11.349 (6)C4—C51.381 (6)
N—C81.412 (5)C4—H4A0.9300
N—H0A0.8600C5—C61.389 (6)
O1—C11.229 (5)C6—C71.380 (6)
C1—C21.521 (4)C6—H6A0.9300
O2—C21.213 (4)C7—C81.369 (6)
C2—C31.471 (5)C7—H7A0.9300
C3—C41.381 (5)
C1—N—C8111.4 (3)C3—C4—H4A121.2
C1—N—H0A124.3C4—C5—C6121.7 (4)
C8—N—H0A124.3C4—C5—Cl119.7 (3)
O1—C1—N126.7 (3)C6—C5—Cl118.6 (3)
O1—C1—C2126.5 (4)C7—C6—C5120.9 (4)
N—C1—C2106.8 (3)C7—C6—H6A119.5
O2—C2—C3129.6 (3)C5—C6—H6A119.5
O2—C2—C1125.1 (4)C8—C7—C6117.6 (4)
C3—C2—C1105.3 (3)C8—C7—H7A121.2
C4—C3—C8120.3 (4)C6—C7—H7A121.2
C4—C3—C2132.9 (3)C7—C8—C3121.8 (4)
C8—C3—C2106.7 (3)C7—C8—N128.5 (3)
C5—C4—C3117.6 (4)C3—C8—N109.7 (4)
C5—C4—H4A121.2
C8—N—C1—O1176.7 (4)C3—C4—C5—Cl176.5 (3)
C8—N—C1—C20.8 (4)C4—C5—C6—C71.8 (6)
O1—C1—C2—O22.4 (7)Cl—C5—C6—C7176.9 (3)
N—C1—C2—O2179.9 (4)C5—C6—C7—C81.0 (6)
O1—C1—C2—C3177.1 (4)C6—C7—C8—C30.7 (6)
N—C1—C2—C30.4 (4)C6—C7—C8—N179.5 (4)
O2—C2—C3—C40.2 (7)C4—C3—C8—C71.2 (6)
C1—C2—C3—C4179.2 (4)C2—C3—C8—C7179.6 (4)
O2—C2—C3—C8179.3 (4)C4—C3—C8—N179.8 (4)
C1—C2—C3—C80.2 (4)C2—C3—C8—N0.6 (4)
C8—C3—C4—C51.9 (6)C1—N—C8—C7179.8 (4)
C2—C3—C4—C5179.2 (4)C1—N—C8—C30.9 (5)
C3—C4—C5—C62.2 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N—H0A···O1i0.862.042.893 (4)172
C7—H7A···O2ii0.932.393.301 (5)166
Symmetry codes: (i) x+1, y, z1/2; (ii) x, y1, z1.

Experimental details

Crystal data
Chemical formulaC8H4ClNO2
Mr181.57
Crystal system, space groupOrthorhombic, Pna21
Temperature (K)293
a, b, c (Å)24.706 (5), 5.6890 (11), 5.209 (1)
V3)732.1 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.47
Crystal size (mm)0.10 × 0.05 × 0.05
Data collection
DiffractometerEnraf–Nonius CAD-4
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.955, 0.977
No. of measured, independent and
observed [I > 2σ(I)] reflections
1746, 884, 734
Rint0.048
(sin θ/λ)max1)0.638
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.102, 1.00
No. of reflections884
No. of parameters109
No. of restraints2
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.18, 0.24
Absolute structureFlack (1983), 862 Friedel pairs
Absolute structure parameter0.11 (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···AD—HH···AD···AD—H···A
N—H0A···O1i0.862.042.893 (4)172
C7—H7A···O2ii0.932.393.301 (5)166
Symmetry codes: (i) x+1, y, z1/2; (ii) x, y1, z1.
 

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