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organic compounds
5-Chloroindoline-2,3-dione
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
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
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Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell 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
https://doi.org/10.1107/S1600536810042522/hb5688sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810042522/hb5688Isup2.hkl
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).
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.
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
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
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).
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell
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). ![]() | Fig. 1. View of the title compound with displacement ellipsoids for non-H atoms drawn at the 50% probability level. |
![]() | Fig. 2. Packing diagram. |
C8H4ClNO2 | Dx = 1.647 Mg m−3 |
Mr = 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 |
Enraf–Nonius CAD-4 diffractometer | 734 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.048 |
Graphite monochromator | θmax = 27.0°, θmin = 1.7° |
ω/2θ scans | h = −31→31 |
Absorption correction: ψ scan (North et al., 1968) | k = −7→0 |
Tmin = 0.955, Tmax = 0.977 | l = 0→6 |
1746 measured reflections | 3 standard reflections every 200 reflections |
884 independent reflections | intensity decay: 1% |
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(Fo2) + (0.065P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
884 reflections | Δρmax = 0.18 e Å−3 |
109 parameters | Δρmin = −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) |
C8H4ClNO2 | V = 732.1 (2) Å3 |
Mr = 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 |
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 = 0.977 | 3 standard reflections every 200 reflections |
1746 measured reflections | intensity decay: 1% |
884 independent reflections |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.102 | Δρmax = 0.18 e Å−3 |
S = 1.00 | Δρmin = −0.24 e Å−3 |
884 reflections | Absolute structure: Flack (1983), 862 Friedel pairs |
109 parameters | Absolute structure parameter: 0.11 (16) |
2 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
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) |
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) |
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) |
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 |
Mr | 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) |
Tmin, Tmax | 0.955, 0.977 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1746, 884, 734 |
Rint | 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 |
Δρmax, Δρmin (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).
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
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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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.