4,6-Di­chloro-1H-indole-2,3-dione

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

doi:10.1107/S2414314616006957

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 5| May 2016| x160695

doi:10.1107/S2414314616006957

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access

4,6-Dichloro-1H-indole-2,3-dione

Ronald J. Mastrolia,^a 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 W. T. A. Harrison, University of Aberdeen, Scotland (Received 24 April 2016; accepted 24 April 2016; online 4 May 2016)

The title compound, C₈H₃Cl₂NO₂, has a single, almost planar, molecule in the asymmetric unit, with the non-H atoms having a mean deviation from planarity of 0.027 Å. In the crystal, N—H⋯O hydrogen bonds form infinite C(4) chains along [100]. No π–π interactions were observed in the structure.

Keywords: crystal structure; hydrogen bonding; isatins.

CCDC reference: 1476205

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Chemical scheme

Structure description

Figure 1
The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level. H atoms are drawn as spheres of arbitrary radius

In the crystal, the molecules are linked through N1—H1⋯O1 hydrogen bonds (Table 1) to form infinite chains along [100] (Fig. 2). No other intermolecular hydrogen bonding or π–π interactions are observed. In addition to N—H⋯O hydrogen bonding, the monosubstituted 4-chloroisatin possesses C—H⋯Cl close contacts (Juma et al., 2016 ) and 6-chloroisatin possesses C—H⋯O interactions (Golen & Manke, 2016 ), neither of which are observed in the title compound.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.87 (2)	1.98 (2)	2.809 (3)	161 (3)
Symmetry code: (i) $[x+{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ .

Figure 2
Molecular packing of the title compound along the b axis, with hydrogen bonding shown as dashed lines.

Synthesis and crystallization

A commercial sample (Matrix Scientific) of 4,6-dichloro-1H-indole-2,3-dione was used for the crystallization. Orange blocks were grown from the slow evaporation of an acetone solution.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₈H₃Cl₂NO₂
M_r	216.01
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	120
a, b, c (Å)	8.6253 (19), 7.1250 (16), 26.289 (6)
V (Å³)	1615.6 (6)
Z	8
Radiation type	Cu Kα
μ (mm⁻¹)	6.92
Crystal size (mm)	0.25 × 0.2 × 0.1

Data collection
Diffractometer	Bruker Venture D8 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.190, 0.386
No. of measured, independent and observed [I > 2σ(I)] reflections	13414, 1604, 1531
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.619

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.098, 1.10
No. of reflections	1604
No. of parameters	122
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.26
Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2014), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), OLEX2 (Dolomanov et al., 2009 ), OLEX2 and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1476205

Crystal structure: contains datablock I. DOI: 10.1107/S2414314616006957/hb4042sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616006957/hb4042Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616006957/hb4042Isup3.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

A commercial sample (Matrix Scientific) of 4,6-dichloro-1H-indole-2,3-dione was used for the crystallization. Orange blocks were grown from the slow evaporation of an acetone solution.

Structure description top

Herein we report the crystal structure of 4,6-dichloroisatin (Fig. 1), which has a near planar molecule in the asymmetric unit, with non-H atoms possessing a mean deviation from planarity of 0.027 Å. The distances and angles are consistent with those reported for 1H-indole-2,3-dione (Goldschmidt & Llewellyn, 1950). In the crystal, the molecules are linked through N1—H1···O1 hydrogen bonds to form infinite chains along [100] (Fig. 2). No other intermolecular hydrogen bonding or π–π interactions are observed. In addition to N—H···O hydrogen bonding, the monosubstituted 4-chloroisatin possesses C—H···Cl close contacts (Juma et al., 2016) and 6-chloroisatin possesses C—H···O interactions (Golen & Manke, 2016), neither of which are observed in the title compound.

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 and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level. H atoms are drawn as spheres of arbitrary radius
	Fig. 2. Molecular packing of the title compound along the b axis, with hydrogen bonding shown as dashed lines.

4,6-Dichloro-1H-indole-2,3-dione top

Crystal data top

C₈H₃Cl₂NO₂	F(000) = 864
M_r = 216.01	D_x = 1.776 Mg m⁻³
Orthorhombic, Pbca	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 8528 reflections
a = 8.6253 (19) Å	θ = 3.4–72.4°
b = 7.1250 (16) Å	µ = 6.92 mm⁻¹
c = 26.289 (6) Å	T = 120 K
V = 1615.6 (6) Å³	Block, orange
Z = 8	0.25 × 0.2 × 0.1 mm

Data collection top

Bruker Venture D8 CMOS diffractometer	1604 independent reflections
Radiation source: Cu	1531 reflections with I > 2σ(I)
HELIOS MX monochromator	R_int = 0.057
φ and ω scans	θ_max = 72.7°, θ_min = 3.4°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −10→10
T_min = 0.190, T_max = 0.386	k = −8→8
13414 measured reflections	l = −32→32

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.038	w = 1/[σ²(F_o²) + (0.0427P)² + 2.2094P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.098	(Δ/σ)_max < 0.001
S = 1.10	Δρ_max = 0.34 e Å⁻³
1604 reflections	Δρ_min = −0.26 e Å⁻³
122 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0017 (3)

Crystal data top

C₈H₃Cl₂NO₂	V = 1615.6 (6) Å³
M_r = 216.01	Z = 8
Orthorhombic, Pbca	Cu Kα radiation
a = 8.6253 (19) Å	µ = 6.92 mm⁻¹
b = 7.1250 (16) Å	T = 120 K
c = 26.289 (6) Å	0.25 × 0.2 × 0.1 mm

Data collection top

Bruker Venture D8 CMOS diffractometer	1604 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2014)	1531 reflections with I > 2σ(I)
T_min = 0.190, T_max = 0.386	R_int = 0.057
13414 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	1 restraint
wR(F²) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.34 e Å⁻³
1604 reflections	Δρ_min = −0.26 e Å⁻³
122 parameters

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.

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

	x	y	z	U_iso*/U_eq
Cl1	0.29514 (7)	0.91432 (9)	0.57109 (2)	0.0280 (2)
Cl2	0.90946 (7)	0.85524 (8)	0.54527 (2)	0.0266 (2)
O1	0.4268 (2)	0.5417 (3)	0.76169 (6)	0.0307 (4)
O2	0.2373 (2)	0.7287 (3)	0.68422 (6)	0.0340 (5)
N1	0.6227 (2)	0.6103 (3)	0.70490 (7)	0.0233 (4)
H1	0.706 (2)	0.586 (4)	0.7219 (10)	0.028*
C8	0.6327 (3)	0.6988 (3)	0.65726 (8)	0.0199 (5)
C4	0.4730 (3)	0.8391 (3)	0.59277 (9)	0.0211 (5)
C3	0.4861 (3)	0.7546 (3)	0.64011 (8)	0.0216 (5)
C7	0.7662 (3)	0.7288 (3)	0.62975 (8)	0.0219 (5)
H7	0.8654	0.6946	0.6424	0.026*
C6	0.7471 (3)	0.8124 (3)	0.58219 (8)	0.0208 (5)
C5	0.6037 (3)	0.8662 (3)	0.56284 (9)	0.0225 (5)
H5	0.5954	0.9202	0.5299	0.027*
C2	0.3748 (3)	0.7047 (4)	0.68032 (9)	0.0240 (5)
C1	0.4750 (3)	0.6071 (4)	0.72214 (9)	0.0255 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0227 (3)	0.0336 (4)	0.0277 (3)	0.0046 (2)	−0.0042 (2)	0.0030 (2)
Cl2	0.0233 (3)	0.0291 (3)	0.0273 (3)	−0.0025 (2)	0.0057 (2)	0.0015 (2)
O1	0.0293 (9)	0.0422 (11)	0.0205 (8)	0.0017 (8)	0.0032 (7)	0.0037 (8)
O2	0.0229 (9)	0.0498 (12)	0.0291 (9)	0.0048 (8)	0.0039 (7)	0.0043 (8)
N1	0.0212 (10)	0.0314 (11)	0.0172 (9)	0.0039 (8)	−0.0006 (7)	0.0013 (8)
C8	0.0226 (11)	0.0206 (11)	0.0165 (10)	−0.0002 (9)	−0.0002 (8)	−0.0037 (8)
C4	0.0211 (11)	0.0206 (11)	0.0215 (11)	0.0019 (9)	−0.0024 (9)	−0.0029 (9)
C3	0.0223 (11)	0.0226 (11)	0.0198 (10)	−0.0017 (9)	0.0013 (9)	−0.0030 (9)
C7	0.0210 (11)	0.0227 (11)	0.0220 (10)	−0.0005 (9)	−0.0005 (9)	−0.0041 (9)
C6	0.0217 (11)	0.0198 (11)	0.0210 (10)	−0.0020 (9)	0.0036 (9)	−0.0034 (8)
C5	0.0307 (13)	0.0187 (11)	0.0181 (10)	−0.0037 (10)	−0.0028 (9)	−0.0006 (8)
C2	0.0225 (12)	0.0286 (12)	0.0208 (11)	0.0019 (10)	0.0014 (9)	−0.0022 (9)
C1	0.0273 (12)	0.0296 (13)	0.0195 (11)	0.0030 (10)	0.0010 (9)	−0.0023 (9)

Geometric parameters (Å, º) top

Cl1—C4	1.722 (2)	C4—C3	1.387 (3)
Cl2—C6	1.731 (2)	C4—C5	1.388 (3)
O1—C1	1.213 (3)	C3—C2	1.471 (3)
O2—C2	1.202 (3)	C7—H7	0.9500
N1—H1	0.865 (17)	C7—C6	1.395 (3)
N1—C8	1.405 (3)	C6—C5	1.391 (3)
N1—C1	1.352 (3)	C5—H5	0.9500
C8—C3	1.400 (3)	C2—C1	1.562 (3)
C8—C7	1.377 (3)

C8—N1—H1	120 (2)	C6—C7—H7	122.0
C1—N1—H1	127.4 (19)	C7—C6—Cl2	118.82 (19)
C1—N1—C8	111.3 (2)	C5—C6—Cl2	117.76 (17)
C3—C8—N1	111.1 (2)	C5—C6—C7	123.4 (2)
C7—C8—N1	126.1 (2)	C4—C5—C6	118.4 (2)
C7—C8—C3	122.8 (2)	C4—C5—H5	120.8
C3—C4—Cl1	120.31 (18)	C6—C5—H5	120.8
C3—C4—C5	120.2 (2)	O2—C2—C3	132.1 (2)
C5—C4—Cl1	119.49 (18)	O2—C2—C1	123.3 (2)
C8—C3—C2	106.8 (2)	C3—C2—C1	104.6 (2)
C4—C3—C8	119.1 (2)	O1—C1—N1	128.1 (2)
C4—C3—C2	134.1 (2)	O1—C1—C2	125.8 (2)
C8—C7—H7	122.0	N1—C1—C2	106.14 (19)
C8—C7—C6	116.0 (2)

Cl1—C4—C3—C8	−178.52 (17)	C8—C7—C6—C5	0.8 (3)
Cl1—C4—C3—C2	1.4 (4)	C4—C3—C2—O2	−2.5 (5)
Cl1—C4—C5—C6	176.95 (17)	C4—C3—C2—C1	178.3 (3)
Cl2—C6—C5—C4	−177.68 (17)	C3—C8—C7—C6	−2.5 (3)
O2—C2—C1—O1	1.9 (4)	C3—C4—C5—C6	−2.1 (3)
O2—C2—C1—N1	−178.5 (3)	C3—C2—C1—O1	−178.7 (2)
N1—C8—C3—C4	−177.9 (2)	C3—C2—C1—N1	0.8 (3)
N1—C8—C3—C2	2.2 (3)	C7—C8—C3—C4	1.9 (4)
N1—C8—C7—C6	177.3 (2)	C7—C8—C3—C2	−178.0 (2)
C8—N1—C1—O1	−180.0 (2)	C7—C6—C5—C4	1.5 (4)
C8—N1—C1—C2	0.5 (3)	C5—C4—C3—C8	0.5 (3)
C8—C3—C2—O2	177.5 (3)	C5—C4—C3—C2	−179.6 (2)
C8—C3—C2—C1	−1.8 (3)	C1—N1—C8—C3	−1.7 (3)
C8—C7—C6—Cl2	179.91 (17)	C1—N1—C8—C7	178.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.87 (2)	1.98 (2)	2.809 (3)	161 (3)

Symmetry code: (i) x+1/2, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.865 (17)	1.977 (19)	2.809 (3)	161 (3)

Symmetry code: (i) x+1/2, y, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₈H₃Cl₂NO₂
M_r	216.01
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	120
a, b, c (Å)	8.6253 (19), 7.1250 (16), 26.289 (6)
V (Å³)	1615.6 (6)
Z	8
Radiation type	Cu Kα
µ (mm⁻¹)	6.92
Crystal size (mm)	0.25 × 0.2 × 0.1

Data collection
Diffractometer	Bruker Venture D8 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2014)
T_min, T_max	0.190, 0.386
No. of measured, independent and observed [I > 2σ(I)] reflections	13414, 1604, 1531
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.619

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.098, 1.10
No. of reflections	1604
No. of parameters	122
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.26

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

Acknowledgements

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

References

Bruker (2014). APEX2, SAINT, and SADABS. Bruker AXS Inc., Madison Wisconsin, USA. Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Goldschmidt, G. H. & Llewellyn, F. J. (1950). Acta Cryst. 3, 294–305. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Golen, J. A. & Manke, D. R. (2016). IUCrData, 1, x160690. Google Scholar
Juma, R. M., Golen, J. A. & Manke, D. R. (2016). IUCrData, 1, x160689. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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IUCrDATA

ISSN: 2414-3146

Volume 1| Part 5| May 2016| x160695

doi:10.1107/S2414314616006957

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

4,6-Di­chloro-1H-indole-2,3-dione

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds

4,6-Dichloro-1H-indole-2,3-dione