6-Chloro-1H-indole-2,3-dione

Golen, J.A.; Manke, D.R.

doi:10.1107/S2414314616006908

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 4| April 2016| x160690

doi:10.1107/S2414314616006908

Open

access

6-Chloro-1H-indole-2,3-dione

James A. Golen ^a and David R. Manke ^a ^*

^aDepartment of Chemistry and Biochemistry, University of Massachusetts Dartmouth, 285 Old Westport Road, North Dartmouth, MA 02747, USA
^*Correspondence e-mail: dmanke@umassd.edu

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 19 April 2016; accepted 23 April 2016; online 29 April 2016)

The molecule of the title compound, C₈H₄ClNO₂, is planar, with the non-H atoms possessing an r.m.s. deviation from planarity of 0.062 Å. In the crystal, molecules are linked through N—H⋯O hydrogen bonds, forming chains along [010]. The chains are further linked through C—H⋯O hydrogen bonds, forming layers parallel to (001).

Keywords: crystal structure; isatins; 6-chloroisatin; hydrogen bonding.

CCDC reference: 1476175

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Chemical scheme

Structure description

Herein, we report on the crystal structure of 6-chloroisatin (Fig. 1). The molecule is almost planar with the non-H atoms possessing an r.m.s. deviation from planarity of 0.062 Å. The bond distances and angles are similar to those reported for 1H-indole-2,3-dione (Goldschmidt & Llewellyn, 1950 ).

Figure 1
The molecular structure of the title compound, showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level.

In the crystal, molecules are linked together through N1—H1⋯O1 hydrogen bonds, forming chains along [010]. The chains are connected through C7—H7⋯O2 hydrogen bonds, forming layers parallel to the ab plane (Table 1 and Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86 (1)	2.03 (2)	2.885 (4)	172 (4)
C7—H7⋯O2ⁱⁱ	0.95	2.32	3.260 (4)	170
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+1]$ ; (ii) x-1, y-1, z.

Figure 2
The molecular packing of the title compound viewed along the b axis, with the hydrogen bonds shown as dashed lines (see Table 1

The two reported structures of 6-chloroisatin derivatives also demonstrate C—H⋯O interactions from the carbon on the 7 position of the isatin ring with the oxygen on the 2 position of an isatin ring (Liu et al., 2011 , 2012 ). In contrast, the other reported 6-haloisatins possess intermolecular interactions through their halogen atoms, with 6-fluoroisatin possessing C—H⋯F close contacts (Golen & Manke, 2016 ) and 6-bromoisatin possessing Br⋯O interactions (Turbitt et al., 2016 ). Both 4-chloroisatin (Juma et al., 2016 ) and 7-chloroisatin (Sun & Cai, 2010 ) demonstrate C—H⋯Cl interactions which are not present in the crystal of the title isomer.

Synthesis and crystallization

A commercial sample (Matrix Scientific) of 6-chloro-1H-indole-2,3-dione was used for crystallization. A sample suitable for single-crystal X-ray difffraction analysis was grown by slow evaporation from a dimethylsulfoxide solution.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₈H₄ClNO₂
M_r	181.57
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	120
a, b, c (Å)	5.6231 (6), 4.9930 (6), 12.5145 (14)
β (°)	91.916 (7)
V (Å³)	351.16 (7)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	4.41
Crystal size (mm)	0.22 × 0.06 × 0.04

Data collection
Diffractometer	Bruker Venture D8 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.349, 0.467
No. of measured, independent and observed [I > 2σ(I)] reflections	4219, 1262, 1183
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.070, 1.12
No. of reflections	1262
No. of parameters	114
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.20
Absolute structure	Refined as an inversion twin.
Absolute structure parameter	0.09 (3)
Computer programs: APEX2 and SAINT (Bruker, 2014), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), OLEX2 (Dolomanov et al., 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1476175

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2414314616006908/su4040sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616006908/su4040Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616006908/su4040Isup3.cml

checkCIF report

Experimental top

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1.

Results and discussion top

Experimental top

Structure description top

In the crystal, molecules are linked together through N1—H1···O1 hydrogen bonds, forming chains along [010]. The chains are connected through C7—H7···O2 hydrogen bonds, forming layers parallel to the ab plane (Table 1 and Fig. 2).

The two reported structures of 6-chloroisatin derivatives also demonstrate C—H···O interactions from the carbon on the 7 position of the isatin ring with the oxygen on the 2 position of an isatin ring (Liu et al., 2011, 2012). In contrast, the other reported 6-haloisatins possess intermolecular interactions through their halogen atoms, with 6-fluoroisatin possessing C—H···F close contacts (Golen & Manke, 2016) and 6-bromoisatin possessing Br···O interactions (Turbitt et al., 2016). Both 4-chloroisatin (Juma et al., 2016) and 7-chloroisatin (Sun & Cai, 2010) demonstrate C—H···Cl interactions which are not present in the crystal of the title isomer.

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The molecular packing of the title compound viewed along the b axis, with the hydrogen bonds shown as dashed lines (see Table 1).

6-Chloro-1H-indole-2,3-dione top

Crystal data top

C₈H₄ClNO₂	F(000) = 184
M_r = 181.57	D_x = 1.717 Mg m⁻³
Monoclinic, P2₁	Cu Kα radiation, λ = 1.54178 Å
a = 5.6231 (6) Å	Cell parameters from 3414 reflections
b = 4.9930 (6) Å	θ = 3.5–68.5°
c = 12.5145 (14) Å	µ = 4.41 mm⁻¹
β = 91.916 (7)°	T = 120 K
V = 351.16 (7) Å³	Block, orange
Z = 2	0.22 × 0.06 × 0.04 mm

Data collection top

Bruker Venture D8 CMOS diffractometer	1183 reflections with I > 2σ(I)
Radiation source: Cu	R_int = 0.052
φ and ω scans	θ_max = 68.5°, θ_min = 3.5°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −6→6
T_min = 0.349, T_max = 0.467	k = −6→6
4219 measured reflections	l = −15→14
1262 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.070	w = 1/[σ²(F_o²) + (0.0176P)² + 0.0693P] where P = (F_o² + 2F_c²)/3
S = 1.12	(Δ/σ)_max < 0.001
1262 reflections	Δρ_max = 0.22 e Å⁻³
114 parameters	Δρ_min = −0.20 e Å⁻³
2 restraints	Absolute structure: Refined as an inversion twin.
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.09 (3)

Crystal data top

C₈H₄ClNO₂	V = 351.16 (7) Å³
M_r = 181.57	Z = 2
Monoclinic, P2₁	Cu Kα radiation
a = 5.6231 (6) Å	µ = 4.41 mm⁻¹
b = 4.9930 (6) Å	T = 120 K
c = 12.5145 (14) Å	0.22 × 0.06 × 0.04 mm
β = 91.916 (7)°

Data collection top

Bruker Venture D8 CMOS diffractometer	1262 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2014)	1183 reflections with I > 2σ(I)
T_min = 0.349, T_max = 0.467	R_int = 0.052
4219 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.070	Δρ_max = 0.22 e Å⁻³
S = 1.12	Δρ_min = −0.20 e Å⁻³
1262 reflections	Absolute structure: Refined as an inversion twin.
114 parameters	Absolute structure parameter: 0.09 (3)
2 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refined as a 2-component inversion twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.09834 (14)	−0.01835 (18)	0.08160 (7)	0.0243 (2)
O1	0.2777 (4)	1.0175 (6)	0.49908 (19)	0.0232 (6)
O2	0.6762 (4)	1.0073 (6)	0.35185 (18)	0.0235 (5)
N1	0.1575 (5)	0.6515 (6)	0.3975 (2)	0.0202 (7)
H1	0.035 (5)	0.614 (9)	0.434 (3)	0.035 (13)*
C1	0.3027 (6)	0.8549 (8)	0.4278 (3)	0.0192 (7)
C2	0.5114 (6)	0.8531 (8)	0.3481 (3)	0.0190 (7)
C3	0.4503 (6)	0.6351 (7)	0.2732 (3)	0.0185 (7)
C4	0.5569 (6)	0.5441 (7)	0.1822 (3)	0.0206 (8)
H4	0.7019	0.6208	0.1602	0.025*
C5	0.4494 (6)	0.3391 (8)	0.1233 (3)	0.0229 (8)
H5	0.5195	0.2729	0.0605	0.027*
C6	0.2363 (6)	0.2324 (7)	0.1582 (3)	0.0198 (8)
C7	0.1259 (6)	0.3158 (7)	0.2494 (3)	0.0196 (8)
H7	−0.0174	0.2362	0.2721	0.024*
C8	0.2363 (5)	0.5226 (8)	0.3059 (3)	0.0169 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0281 (4)	0.0218 (4)	0.0229 (4)	−0.0025 (4)	−0.0018 (3)	−0.0020 (5)
O1	0.0223 (11)	0.0237 (15)	0.0238 (13)	0.0034 (12)	0.0045 (9)	−0.0029 (13)
O2	0.0222 (11)	0.0225 (13)	0.0257 (13)	−0.0039 (13)	0.0009 (9)	0.0017 (14)
N1	0.0180 (15)	0.0224 (16)	0.0204 (17)	−0.0005 (12)	0.0066 (12)	0.0002 (13)
C1	0.0207 (17)	0.0178 (16)	0.019 (2)	0.0042 (15)	0.0005 (14)	0.0035 (17)
C2	0.0189 (16)	0.0183 (16)	0.0198 (19)	0.0035 (15)	−0.0002 (13)	0.0044 (16)
C3	0.0171 (16)	0.0171 (18)	0.0213 (19)	0.0015 (13)	0.0001 (13)	0.0012 (14)
C4	0.0189 (15)	0.023 (2)	0.0204 (18)	0.0001 (13)	0.0034 (12)	0.0039 (14)
C5	0.0238 (18)	0.0235 (19)	0.022 (2)	0.0046 (15)	0.0050 (14)	0.0011 (17)
C6	0.0217 (17)	0.0165 (17)	0.0209 (19)	0.0015 (13)	−0.0035 (14)	0.0025 (14)
C7	0.0165 (16)	0.019 (2)	0.024 (2)	0.0008 (13)	0.0010 (13)	0.0058 (15)
C8	0.0181 (15)	0.018 (2)	0.0141 (15)	0.0013 (15)	0.0014 (11)	0.0031 (15)

Geometric parameters (Å, º) top

Cl1—C6	1.743 (4)	C3—C8	1.401 (5)
O1—C1	1.218 (4)	C4—H4	0.9500
O2—C2	1.204 (4)	C4—C5	1.388 (5)
N1—H1	0.859 (14)	C5—H5	0.9500
N1—C1	1.350 (5)	C5—C6	1.395 (5)
N1—C8	1.400 (5)	C6—C7	1.382 (5)
C1—C2	1.565 (5)	C7—H7	0.9500
C2—C3	1.470 (5)	C7—C8	1.386 (5)
C3—C4	1.382 (5)

C1—N1—H1	120 (3)	C5—C4—H4	120.4
C1—N1—C8	111.8 (3)	C4—C5—H5	120.7
C8—N1—H1	128 (3)	C4—C5—C6	118.6 (3)
O1—C1—N1	128.6 (3)	C6—C5—H5	120.7
O1—C1—C2	125.3 (3)	C5—C6—Cl1	118.3 (3)
N1—C1—C2	106.1 (3)	C7—C6—Cl1	117.8 (3)
O2—C2—C1	124.4 (3)	C7—C6—C5	123.9 (3)
O2—C2—C3	131.4 (3)	C6—C7—H7	122.0
C3—C2—C1	104.3 (3)	C6—C7—C8	116.1 (3)
C4—C3—C2	132.1 (3)	C8—C7—H7	122.0
C4—C3—C8	120.6 (3)	N1—C8—C3	110.7 (3)
C8—C3—C2	107.2 (3)	C7—C8—N1	127.7 (3)
C3—C4—H4	120.4	C7—C8—C3	121.6 (3)
C3—C4—C5	119.2 (3)

Cl1—C6—C7—C8	−177.6 (3)	C2—C3—C8—C7	177.9 (3)
O1—C1—C2—O2	3.3 (6)	C3—C4—C5—C6	0.2 (5)
O1—C1—C2—C3	−175.3 (3)	C4—C3—C8—N1	−177.9 (3)
O2—C2—C3—C4	−2.5 (7)	C4—C3—C8—C7	0.7 (5)
O2—C2—C3—C8	−179.3 (4)	C4—C5—C6—Cl1	178.2 (3)
N1—C1—C2—O2	−179.4 (3)	C4—C5—C6—C7	−1.0 (5)
N1—C1—C2—C3	2.0 (4)	C5—C6—C7—C8	1.6 (5)
C1—N1—C8—C3	2.2 (4)	C6—C7—C8—N1	177.0 (3)
C1—N1—C8—C7	−176.4 (3)	C6—C7—C8—C3	−1.4 (5)
C1—C2—C3—C4	176.0 (3)	C8—N1—C1—O1	174.7 (4)
C1—C2—C3—C8	−0.7 (4)	C8—N1—C1—C2	−2.5 (4)
C2—C3—C4—C5	−176.4 (4)	C8—C3—C4—C5	0.0 (5)
C2—C3—C8—N1	−0.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86 (1)	2.03 (2)	2.885 (4)	172 (4)
C7—H7···O2ⁱⁱ	0.95	2.32	3.260 (4)	170

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.859 (14)	2.031 (16)	2.885 (4)	172 (4)
C7—H7···O2ⁱⁱ	0.95	2.32	3.260 (4)	170

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

Experimental details

Crystal data
Chemical formula	C₈H₄ClNO₂
M_r	181.57
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	120
a, b, c (Å)	5.6231 (6), 4.9930 (6), 12.5145 (14)
β (°)	91.916 (7)
V (Å³)	351.16 (7)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	4.41
Crystal size (mm)	0.22 × 0.06 × 0.04

Data collection
Diffractometer	Bruker Venture D8 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2014)
T_min, T_max	0.349, 0.467
No. of measured, independent and observed [I > 2σ(I)] reflections	4219, 1262, 1183
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.070, 1.12
No. of reflections	1262
No. of parameters	114
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.20
Absolute structure	Refined as an inversion twin.
Absolute structure parameter	0.09 (3)

Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2014), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

Acknowledgements

We gratefully acknowledge support from the National Science Foundation (CHE-1429086).

References

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IUCrDATA

ISSN: 2414-3146

Volume 1| Part 4| April 2016| x160690

doi:10.1107/S2414314616006908

Open

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

6-Chloro-1H-indole-2,3-dione

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds