4-Bromo-1H-indole-2,3-dione

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

doi:10.1107/S2414314616000079

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 2| February 2016| x160007

https://doi.org/10.1107/S2414314616000079

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4-Bromo-1H-indole-2,3-dione

Haobo Huang,^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 L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 27 December 2015; accepted 3 January 2016; online 20 February 2016)

The title compound, C₈H₄BrNO₂, has a single planar molecule in the asymmetric unit with the non-H atoms possessing a mean deviation from planarity of 0.024 Å. The molecules dimerize in the solid state through N—H⋯O hydrogen bonds. There are intermolecular Br⋯O close contacts at 3.0430 (14) Å. The nine-membered rings of the isatins stack along [001] with parallel slipped π–π interactions [inter-centroid distance: 3.7173 (6) Å, inter-planar distance: 3.3110 (8) Å, slippage: 1.6898 (14) Å].

Keywords: crystal structure; hydrogen bonding; isatins; π–π interactions; halogen–oxygen interactions.

CCDC reference: 1445034

Structure description

Isatins are a class of compounds that are widely used in pharmaceuticals and organic synthesis. Herein we report the crystal structure of 4-bromoisatin as part of a study on the structure of halogenated isatin compounds. The structure exhibits a near planar molecule with the non-hydrogen atoms possessing a mean deviation from planarity of 0.024 Å (Fig. 1). The bond lengths and angles observed are similar to those seen in isatin (Goldschmidt et al., 1950 ). The structure of the title compound demonstrates an intermolecular Br1⋯O2ⁱⁱ close contact of 3.0430 (14) Å, symmetry code: (ii) −x + 2, −y, −z + 1. A similar bromo–oxygen interaction is observed in the structure of 6-bromoisatin (Turbitt et al. 2016 ), though no such halogen–oxygen interactions are observed for the derivatives of 4-chloroisatin (Hughes et al., 2010 ; Wang et al., 2012 ; Yu et al., 2012 )

Figure 1
Molecular structure of the title compound, showing the atom-labeling scheme. Displacement ellipsoids are 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). The nine-membered rings of the isatins stack along [001] with parallel slipped π–π interactions [inter-centroid distance: 3.7173 (6) Å, inter-planar distance: 3.3110 (8) Å, slippage: 1.6898 (14) Å]. The packing of the title compound indicating hydrogen bonding is shown in Fig. 2.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.91 (2)	2.01 (2)	2.874 (2)	159 (2)
Symmetry code: (i) -x+2, -y+1, -z+1.

Figure 2
View of the molecular packing of the title compound along the c axis with hydrogen bonding shown as dashed lines.

Synthesis and crystallization

A commercial sample (Matrix Scientific) of 4-bromo-1H-indole-2,3-dione was used for the crystallization. A sample suitable for single-crystal X-ray analysis was grown from the slow evaporation of an acetone/dimethylsulfoxide solution.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₈H₄BrNO₂
M_r	226.03
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	120
a, b, c (Å)	7.3655 (11), 13.689 (2), 7.2866 (12)
β (°)	93.378 (5)
V (Å³)	733.4 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	5.55
Crystal size (mm)	0.2 × 0.2 × 0.1

Data collection
Diffractometer	Bruker D8 Venture CMOS diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.174, 0.259
No. of measured, independent and observed [I > 2σ(I)] reflections	12353, 1381, 1285
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.609

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.019, 0.049, 1.08
No. of reflections	1381
No. of parameters	112
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)	0.46, −0.45
Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2014), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), OLEX2 (Dolomanov et al., 2009 ), publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1445034

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314616000079/vm4004sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616000079/vm4004Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616000079/vm4004Isup3.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 and publCIF (Westrip, 2010).

4-Bromo-1H-indole-2,3-dione top

Crystal data top

C₈H₄BrNO₂	F(000) = 440
M_r = 226.03	D_x = 2.047 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8354 reflections
a = 7.3655 (11) Å	θ = 3.0–25.6°
b = 13.689 (2) Å	µ = 5.55 mm⁻¹
c = 7.2866 (12) Å	T = 120 K
β = 93.378 (5)°	BLOCK, orange
V = 733.4 (2) Å³	0.2 × 0.2 × 0.1 mm
Z = 4

Data collection top

Bruker D8 Venture CMOS diffractometer	1381 independent reflections
Radiation source: Mo	1285 reflections with I > 2σ(I)
TRIUMPH monochromator	R_int = 0.034
φ and ω scans	θ_max = 25.6°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −8→8
T_min = 0.174, T_max = 0.259	k = −16→16
12353 measured reflections	l = −8→8

Refinement top

Refinement on F²	1 restraint
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.019	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.049	w = 1/[σ²(F_o²) + (0.0276P)² + 0.4818P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
1381 reflections	Δρ_max = 0.46 e Å⁻³
112 parameters	Δρ_min = −0.45 e Å⁻³

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
Br1	0.77232 (2)	0.02480 (2)	0.59115 (3)	0.01707 (9)
O1	1.14710 (19)	0.39227 (10)	0.4387 (2)	0.0203 (3)
O2	1.08320 (19)	0.18127 (10)	0.4576 (2)	0.0193 (3)
N1	0.8665 (2)	0.39792 (12)	0.5663 (2)	0.0154 (3)
H1	0.834 (3)	0.4616 (12)	0.575 (3)	0.018*
C1	1.0132 (3)	0.35425 (13)	0.4988 (2)	0.0152 (4)
C2	0.9784 (3)	0.24155 (13)	0.5103 (2)	0.0132 (4)
C3	0.8006 (2)	0.23315 (14)	0.5902 (2)	0.0121 (4)
C4	0.6908 (3)	0.15392 (14)	0.6301 (2)	0.0140 (4)
C5	0.5213 (3)	0.17041 (15)	0.6988 (3)	0.0167 (4)
H5	0.4463	0.1169	0.7285	0.020*
C6	0.4620 (3)	0.26585 (15)	0.7239 (2)	0.0170 (4)
H6	0.3457	0.2762	0.7704	0.020*
C7	0.5677 (3)	0.34683 (15)	0.6832 (3)	0.0160 (4)
H7	0.5253	0.4116	0.6999	0.019*
C8	0.7367 (3)	0.32875 (14)	0.6174 (2)	0.0126 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.01757 (13)	0.01081 (13)	0.02316 (13)	−0.00138 (7)	0.00398 (8)	0.00006 (7)
O1	0.0166 (7)	0.0146 (7)	0.0303 (8)	−0.0016 (6)	0.0073 (6)	0.0022 (6)
O2	0.0169 (7)	0.0139 (7)	0.0278 (8)	0.0028 (6)	0.0075 (6)	−0.0008 (6)
N1	0.0152 (8)	0.0096 (8)	0.0217 (8)	0.0017 (6)	0.0039 (6)	−0.0004 (7)
C1	0.0167 (10)	0.0128 (9)	0.0160 (9)	0.0004 (8)	0.0009 (7)	0.0006 (8)
C2	0.0136 (9)	0.0123 (9)	0.0138 (8)	0.0009 (7)	0.0000 (7)	0.0000 (7)
C3	0.0123 (9)	0.0124 (9)	0.0114 (8)	0.0010 (7)	0.0000 (7)	−0.0007 (7)
C4	0.0160 (9)	0.0128 (9)	0.0129 (8)	0.0001 (7)	−0.0001 (7)	−0.0004 (7)
C5	0.0148 (9)	0.0194 (10)	0.0160 (9)	−0.0026 (8)	0.0023 (7)	0.0008 (8)
C6	0.0121 (9)	0.0259 (11)	0.0134 (8)	0.0016 (8)	0.0026 (7)	−0.0017 (8)
C7	0.0165 (10)	0.0171 (10)	0.0144 (9)	0.0046 (8)	0.0003 (7)	−0.0016 (7)
C8	0.0146 (9)	0.0114 (9)	0.0116 (8)	−0.0004 (7)	0.0002 (7)	−0.0007 (7)

Geometric parameters (Å, º) top

Br1—C4	1.8933 (19)	C3—C8	1.409 (3)
O1—C1	1.219 (2)	C4—C5	1.391 (3)
O2—C2	1.208 (2)	C5—H5	0.9500
N1—H1	0.908 (16)	C5—C6	1.393 (3)
N1—C1	1.352 (3)	C6—H6	0.9500
N1—C8	1.411 (3)	C6—C7	1.396 (3)
C1—C2	1.567 (3)	C7—H7	0.9500
C2—C3	1.468 (3)	C7—C8	1.382 (3)
C3—C4	1.394 (3)

C1—N1—H1	132.2 (17)	C5—C4—C3	119.55 (18)
C1—N1—C8	111.58 (16)	C4—C5—H5	120.2
C8—N1—H1	116.0 (17)	C4—C5—C6	119.62 (18)
O1—C1—N1	128.50 (17)	C6—C5—H5	120.2
O1—C1—C2	125.29 (17)	C5—C6—H6	118.9
N1—C1—C2	106.20 (15)	C5—C6—C7	122.26 (18)
O2—C2—C1	123.09 (17)	C7—C6—H6	118.9
O2—C2—C3	132.38 (18)	C6—C7—H7	121.4
C3—C2—C1	104.52 (15)	C8—C7—C6	117.14 (18)
C4—C3—C2	133.28 (18)	C8—C7—H7	121.4
C4—C3—C8	119.37 (17)	C3—C8—N1	110.39 (16)
C8—C3—C2	107.25 (16)	C7—C8—N1	127.55 (18)
C3—C4—Br1	120.15 (14)	C7—C8—C3	122.05 (18)
C5—C4—Br1	120.30 (15)

Br1—C4—C5—C6	−178.98 (14)	C2—C3—C8—N1	−2.3 (2)
O1—C1—C2—O2	−0.8 (3)	C2—C3—C8—C7	176.91 (16)
O1—C1—C2—C3	−179.57 (18)	C3—C4—C5—C6	1.1 (3)
O2—C2—C3—C4	−1.0 (4)	C4—C3—C8—N1	−179.08 (16)
O2—C2—C3—C8	−177.2 (2)	C4—C3—C8—C7	0.1 (3)
N1—C1—C2—O2	178.72 (18)	C4—C5—C6—C7	−0.3 (3)
N1—C1—C2—C3	−0.04 (19)	C5—C6—C7—C8	−0.5 (3)
C1—N1—C8—C3	2.4 (2)	C6—C7—C8—N1	179.71 (17)
C1—N1—C8—C7	−176.77 (18)	C6—C7—C8—C3	0.6 (3)
C1—C2—C3—C4	177.55 (18)	C8—N1—C1—O1	178.14 (19)
C1—C2—C3—C8	1.40 (18)	C8—N1—C1—C2	−1.4 (2)
C2—C3—C4—Br1	3.3 (3)	C8—C3—C4—Br1	179.07 (13)
C2—C3—C4—C5	−176.79 (18)	C8—C3—C4—C5	−1.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.91 (2)	2.01 (2)	2.874 (2)	159 (2)

Symmetry code: (i) −x+2, −y+1, −z+1.

Acknowledgements

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

References

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IUCrDATA

ISSN: 2414-3146

Volume 1| Part 2| February 2016| x160007

https://doi.org/10.1107/S2414314616000079

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

4-Bromo-1H-indole-2,3-dione

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds