5,7-Di­chloro-1H-indole-2,3-dione

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

doi:10.1107/S2414314616015108

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 9| September 2016| x161510

doi:10.1107/S2414314616015108

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5,7-Dichloro-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 J. Simpson, University of Otago, New Zealand (Received 23 September 2016; accepted 24 September 2016; online 30 September 2016)

The title compound, C₈H₃Cl₂NO₂, has a single molecule in the asymmetric unit that is close to planar, with the non-H atoms having a mean deviation from planarity of 0.035 Å. The molecules dimerize through two N—H⋯O hydrogen bonds. A weak intermolecular offset π–π interaction is also observed between the five- and six-membered rings, with a centroid–centroid separation of 3.8444 (16) Å.

Keywords: crystal structure; isatins; hydrogen bonding.

CCDC reference: 1506169

Structure description

Herein we report the crystal structure of 5,7-dichloroisatin (Fig. 1). There is a single, near-planar molecule in the asymmetric unit that has a mean deviation from planarity for the non-H atoms of 0.035 Å. The bond distances and angles observed for the title compound are consistent with those observed in 1H-indole-2,3-dione (Goldschmidt & Llewellyn, 1950 ).

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 dimerize through N1—H1⋯O1 hydrogen bonds (Table 1) and these dimers are stacked along the b-axis direction by a weak π–π contact between the N1/C1–C3/C8 and C3–C8 rings with an inter-centroid distance of 3.8444 (16) Å (Fig. 2). The monosubstituted 5-chloroisatin and 7-chloroisatin demonstrate C—H⋯O interactions in the solid state (Sun & Cai, 2010 ; Wei et al., 2010 ), while no such interaction is observed for the 5,7-disubstituted complex reported here. The 4,7-dichloro isomer of the title compound dimerizes through N—H⋯O hydrogen bonds in a similar fashion to 5,7-dichloroisatin, but unlike the title compound, it also has C—H⋯O as well as π–π interactions (Golen & Manke, 2016 ). The 4,6-dichloro isomer only has N—H⋯O intermolecular interactions, though these form chains rather than dimers (Mastrolia et al., 2016 ).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86 (2)	1.98 (2)	2.832 (2)	167 (3)
Symmetry code: (i) -x+1, -y, -z+1.

Figure 2
The molecular packing of the title compound along the b axis, with hydrogen bonds shown as dashed lines.

Synthesis and crystallization

A commercial sample (Matrix Scientific) of 5,7-dichloroisatin was recrystallized from the slow evaporation of an acetone solution to yield orange blocks suitable for single-crystal diffraction analysis.

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	Monoclinic, P2₁/c
Temperature (K)	120
a, b, c (Å)	11.0789 (17), 4.9866 (8), 15.049 (2)
β (°)	108.041 (7)
V (Å³)	790.5 (2)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	7.08
Crystal size (mm)	0.24 × 0.16 × 0.05

Data collection
Diffractometer	Bruker D8 Venture CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.288, 0.468
No. of measured, independent and observed [I > 2σ(I)] reflections	10168, 1496, 1356
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.611

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.086, 1.06
No. of reflections	1496
No. of parameters	121
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)	0.31, −0.34
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: 1506169

Crystal structure: contains datablock I. DOI: 10.1107/S2414314616015108/sj4060sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616015108/sj4060Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616015108/sj4060Isup3.cml

checkCIF report

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).

5,7-Dichloro-1H-indole-2,3-dione top

Crystal data top

C₈H₃Cl₂NO₂	F(000) = 432
M_r = 216.01	D_x = 1.815 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 6137 reflections
a = 11.0789 (17) Å	θ = 4.2–70.4°
b = 4.9866 (8) Å	µ = 7.08 mm⁻¹
c = 15.049 (2) Å	T = 120 K
β = 108.041 (7)°	Block, orange
V = 790.5 (2) Å³	0.24 × 0.16 × 0.05 mm
Z = 4

Data collection top

Bruker D8 Venture CMOS diffractometer	1496 independent reflections
Radiation source: Cu	1356 reflections with I > 2σ(I)
HELIOS MX monochromator	R_int = 0.059
φ and ω scans	θ_max = 70.4°, θ_min = 4.2°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −13→13
T_min = 0.288, T_max = 0.468	k = −5→6
10168 measured reflections	l = −18→18

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.086	w = 1/[σ²(F_o²) + (0.0359P)² + 0.9613P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
1496 reflections	Δρ_max = 0.31 e Å⁻³
121 parameters	Δρ_min = −0.34 e Å⁻³
1 restraint

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	0.97776 (5)	0.75293 (13)	0.90244 (4)	0.02880 (18)
Cl2	0.74527 (5)	0.65413 (12)	0.53083 (4)	0.02535 (17)
O1	0.46893 (16)	−0.1568 (3)	0.60119 (11)	0.0238 (4)
O2	0.60384 (15)	−0.1147 (3)	0.80286 (11)	0.0220 (4)
N1	0.59860 (19)	0.2023 (4)	0.59574 (13)	0.0199 (4)
H1	0.582 (3)	0.213 (6)	0.5359 (12)	0.024*
C1	0.5484 (2)	0.0101 (5)	0.63789 (15)	0.0196 (5)
C2	0.6184 (2)	0.0373 (5)	0.74484 (15)	0.0191 (5)
C3	0.7063 (2)	0.2649 (5)	0.75254 (15)	0.0186 (5)
C4	0.7939 (2)	0.3839 (5)	0.82884 (16)	0.0207 (5)
H4	0.8036	0.3267	0.8909	0.025*
C5	0.8670 (2)	0.5915 (5)	0.81031 (16)	0.0210 (5)
C6	0.8533 (2)	0.6781 (5)	0.71998 (16)	0.0226 (5)
H6	0.9047	0.8202	0.7098	0.027*
C7	0.7645 (2)	0.5570 (5)	0.64436 (15)	0.0203 (5)
C8	0.6913 (2)	0.3505 (5)	0.66125 (15)	0.0184 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0247 (3)	0.0351 (4)	0.0249 (3)	−0.0087 (2)	0.0053 (2)	−0.0035 (2)
Cl2	0.0295 (3)	0.0284 (3)	0.0214 (3)	0.0001 (2)	0.0126 (2)	0.0049 (2)
O1	0.0273 (9)	0.0232 (9)	0.0213 (8)	−0.0055 (7)	0.0082 (7)	−0.0017 (7)
O2	0.0268 (8)	0.0213 (9)	0.0203 (8)	0.0003 (7)	0.0109 (7)	0.0018 (7)
N1	0.0227 (10)	0.0218 (11)	0.0164 (9)	−0.0020 (8)	0.0079 (8)	0.0001 (8)
C1	0.0206 (11)	0.0201 (12)	0.0203 (11)	0.0016 (9)	0.0096 (9)	−0.0003 (9)
C2	0.0186 (10)	0.0199 (12)	0.0207 (11)	0.0019 (9)	0.0090 (9)	−0.0003 (9)
C3	0.0205 (11)	0.0177 (11)	0.0191 (11)	0.0020 (9)	0.0083 (9)	0.0010 (8)
C4	0.0200 (11)	0.0229 (12)	0.0208 (11)	0.0014 (9)	0.0086 (9)	0.0005 (9)
C5	0.0166 (10)	0.0241 (13)	0.0221 (11)	0.0004 (9)	0.0058 (9)	−0.0024 (9)
C6	0.0207 (11)	0.0227 (13)	0.0277 (12)	−0.0002 (9)	0.0124 (10)	0.0000 (10)
C7	0.0206 (11)	0.0228 (12)	0.0200 (10)	0.0035 (9)	0.0102 (9)	0.0030 (9)
C8	0.0173 (10)	0.0192 (11)	0.0199 (10)	0.0028 (9)	0.0077 (9)	−0.0017 (9)

Geometric parameters (Å, º) top

Cl1—C5	1.738 (2)	C3—C4	1.386 (3)
Cl2—C7	1.724 (2)	C3—C8	1.399 (3)
O1—C1	1.213 (3)	C4—H4	0.9500
O2—C2	1.204 (3)	C4—C5	1.395 (3)
N1—H1	0.864 (17)	C5—C6	1.389 (3)
N1—C1	1.360 (3)	C6—H6	0.9500
N1—C8	1.395 (3)	C6—C7	1.391 (3)
C1—C2	1.561 (3)	C7—C8	1.382 (3)
C2—C3	1.477 (3)

C1—N1—H1	123.2 (19)	C5—C4—H4	121.5
C1—N1—C8	111.21 (19)	C4—C5—Cl1	119.63 (17)
C8—N1—H1	125.0 (19)	C6—C5—Cl1	118.20 (18)
O1—C1—N1	128.0 (2)	C6—C5—C4	122.2 (2)
O1—C1—C2	126.0 (2)	C5—C6—H6	120.0
N1—C1—C2	105.96 (19)	C5—C6—C7	120.0 (2)
O2—C2—C1	123.9 (2)	C7—C6—H6	120.0
O2—C2—C3	131.3 (2)	C6—C7—Cl2	121.84 (18)
C3—C2—C1	104.65 (18)	C8—C7—Cl2	119.48 (18)
C4—C3—C2	132.0 (2)	C8—C7—C6	118.7 (2)
C4—C3—C8	121.5 (2)	N1—C8—C3	111.7 (2)
C8—C3—C2	106.41 (19)	C7—C8—N1	127.6 (2)
C3—C4—H4	121.5	C7—C8—C3	120.7 (2)
C3—C4—C5	116.9 (2)

Cl1—C5—C6—C7	−179.08 (18)	C2—C3—C8—N1	1.7 (3)
Cl2—C7—C8—N1	−0.3 (3)	C2—C3—C8—C7	−177.7 (2)
Cl2—C7—C8—C3	179.01 (17)	C3—C4—C5—Cl1	179.36 (17)
O1—C1—C2—O2	3.1 (4)	C3—C4—C5—C6	0.3 (3)
O1—C1—C2—C3	178.8 (2)	C4—C3—C8—N1	179.8 (2)
O2—C2—C3—C4	−4.3 (4)	C4—C3—C8—C7	0.3 (3)
O2—C2—C3—C8	173.5 (2)	C4—C5—C6—C7	0.0 (4)
N1—C1—C2—O2	−174.5 (2)	C5—C6—C7—Cl2	−179.15 (18)
N1—C1—C2—C3	1.2 (2)	C5—C6—C7—C8	−0.1 (3)
C1—N1—C8—C3	−1.0 (3)	C6—C7—C8—N1	−179.4 (2)
C1—N1—C8—C7	178.4 (2)	C6—C7—C8—C3	0.0 (3)
C1—C2—C3—C4	−179.5 (2)	C8—N1—C1—O1	−177.7 (2)
C1—C2—C3—C8	−1.7 (2)	C8—N1—C1—C2	−0.2 (2)
C2—C3—C4—C5	177.0 (2)	C8—C3—C4—C5	−0.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86 (2)	1.98 (2)	2.832 (2)	167 (3)

Symmetry code: (i) −x+1, −y, −z+1.

Acknowledgements

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

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