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

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

doi:10.1107/S2414314616001772

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 2| February 2016| x160177

https://doi.org/10.1107/S2414314616001772

Open

access

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

Sita Gurung,^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 K. Fejfarova, Institute of Macromolecular Chemistry, AS CR, v.v.i, Czech Republic (Received 20 January 2016; accepted 28 January 2016; online 6 February 2016)

The title compound, C₈H₄BrNO₂, has a single, almost planar, planar molecule in the asymmetric unit, with the non-H atoms having a mean deviation from planarity of 0.024 Å. In the crystal, N—H⋯O hydrogen bonds link the molecules into [001] C(4) chains. C—H⋯O interactions form [0-11] chains. These interactions combine to generate sheets along (100). No π–π interactions are observed in the structure.

Keywords: crystal structure; hydrogen bonding; isatins.

CCDC reference: 1450609

Structure description

Herein, we report the crystal structure of 5-bromoisatin (Fig. 1), as part of a continuing study on halogenated isatins. The structure exhibits a near planar molecule with the non-hydrogen atoms possessing a mean deviation from planarity of 0.024 Å, with similar bond lengths and angles to those observed in isatin (Goldschmidt et al., 1950 ). The structure of other bromoisatins report short Br⋯O contacts (Huang et al., 2016 ; Turbitt et al., 2016 ), which are not observed in 5-bromoisatin. The structures of N-subsistuted derivatives of 5-bromoisatin have been reported (Kurkin et al., 2008 ; Maamri et al., 2012 ) with only one instance of a Br⋯O interaction being observed (Kharbach et al., 2015 ).

Figure 1
The 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 crystals, the molecules form [001] C(4) chains through N1—H1⋯O1 hydrogen bonds (Table 1). C7—H7⋯O2 interactions form [0 $[\overline1]$ 1] chains. The combination of these two interactions results i sheets along (100). No π–π interactions are observed in the structure. 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	0.86 (1)	2.05 (3)	2.886 (6)	166 (9)
C7—H7⋯O2ⁱⁱ	0.95	2.38	3.312 (7)	167
Symmetry codes: (i) $[-x+1, -y, z+{\script{1\over 2}}]$ ; (ii) x, y-1, z+1.

Figure 2
The molecular packing of the title compound along the b axis with N—H⋯O hydrogen bonds shown as dashed lines.

Synthesis and crystallization

A commercial sample (Matrix Scientific) of 5-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 its acetonitrile 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	Orthorhombic, Pna2₁
Temperature (K)	120
a, b, c (Å)	25.1411 (18), 5.6851 (4), 5.1593 (3)
V (Å³)	737.42 (9)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	5.52
Crystal size (mm)	0.2 × 0.12 × 0.1

Data collection
Diffractometer	Bruker D8 Venture CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.109, 0.148
No. of measured, independent and observed [I > 2σ(I)] reflections	8877, 1334, 1232
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.054, 1.12
No. of reflections	1334
No. of parameters	113
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)	0.45, −0.79
Absolute structure	Refined as an inversion twin
Absolute structure parameter	0.02 (2)
Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2014), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), OLEX2 (Dolomanov et al., 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1450609

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314616001772/ff4002sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616001772/ff4002Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616001772/ff4002Isup3.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-Bromo-1H-indole-2,3-dione top

Crystal data top

C₈H₄BrNO₂	F(000) = 440
M_r = 226.03	D_x = 2.036 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 5354 reflections
a = 25.1411 (18) Å	θ = 3.2–25.4°
b = 5.6851 (4) Å	µ = 5.52 mm⁻¹
c = 5.1593 (3) Å	T = 120 K
V = 737.42 (9) Å³	Block, orange
Z = 4	0.2 × 0.12 × 0.1 mm

Data collection top

Bruker D8 Venture CMOS diffractometer	1334 independent reflections
Radiation source: Mo	1232 reflections with I > 2σ(I)
TRIUMPH monochromator	R_int = 0.035
φ and ω scans	θ_max = 25.4°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −30→30
T_min = 0.109, T_max = 0.148	k = −6→6
8877 measured reflections	l = −6→6

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)] = 0.025	w = 1/[σ²(F_o²) + 1.6735P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.054	(Δ/σ)_max < 0.001
S = 1.12	Δρ_max = 0.45 e Å⁻³
1334 reflections	Δρ_min = −0.79 e Å⁻³
113 parameters	Absolute structure: Refined as an inversion twin
2 restraints	Absolute structure parameter: 0.02 (2)

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
Br1	0.26549 (2)	0.64837 (9)	0.99780 (18)	0.02277 (16)
O1	0.50004 (16)	0.2784 (7)	0.1243 (9)	0.0188 (9)
O2	0.42674 (16)	0.6864 (6)	0.1519 (8)	0.0185 (9)
N1	0.45090 (16)	0.1622 (7)	0.4830 (18)	0.0185 (10)
H1	0.4664 (18)	0.028 (5)	0.496 (19)	0.022*
C1	0.4649 (2)	0.3068 (9)	0.2839 (11)	0.0151 (12)
C2	0.4258 (2)	0.5187 (9)	0.2971 (12)	0.0144 (12)
C3	0.38981 (18)	0.4647 (8)	0.5154 (17)	0.0146 (11)
C4	0.3472 (2)	0.5867 (10)	0.6209 (12)	0.0156 (12)
H4	0.3359	0.7335	0.5523	0.019*
C5	0.3218 (2)	0.4844 (10)	0.8311 (11)	0.0148 (12)
C6	0.3381 (2)	0.2689 (10)	0.9336 (10)	0.0151 (14)
H6	0.3195	0.2040	1.0771	0.018*
C7	0.3812 (2)	0.1476 (11)	0.8286 (11)	0.0176 (13)
H7	0.3925	0.0011	0.8980	0.021*
C8	0.4068 (2)	0.2485 (10)	0.6199 (11)	0.0138 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0220 (3)	0.0254 (3)	0.0210 (3)	0.0056 (2)	0.0035 (5)	−0.0021 (5)
O1	0.021 (2)	0.016 (2)	0.020 (2)	0.0018 (17)	0.0033 (18)	−0.0030 (17)
O2	0.026 (2)	0.012 (2)	0.017 (2)	0.0028 (17)	−0.0013 (18)	0.0046 (18)
N1	0.020 (2)	0.0111 (19)	0.024 (3)	0.0047 (18)	−0.002 (4)	0.003 (3)
C1	0.018 (3)	0.009 (3)	0.018 (3)	0.002 (2)	−0.003 (3)	−0.002 (2)
C2	0.016 (3)	0.013 (3)	0.014 (3)	−0.001 (2)	−0.004 (2)	−0.003 (2)
C3	0.017 (2)	0.015 (2)	0.012 (3)	0.0009 (19)	−0.004 (4)	0.004 (4)
C4	0.018 (3)	0.013 (3)	0.016 (3)	0.002 (2)	−0.006 (2)	−0.001 (2)
C5	0.016 (3)	0.019 (3)	0.010 (3)	0.001 (2)	0.000 (2)	−0.004 (2)
C6	0.020 (3)	0.016 (3)	0.009 (4)	−0.005 (2)	−0.002 (2)	0.000 (2)
C7	0.021 (3)	0.014 (3)	0.018 (3)	−0.001 (3)	−0.004 (2)	0.004 (3)
C8	0.017 (3)	0.011 (3)	0.013 (3)	0.001 (2)	−0.004 (2)	−0.003 (3)

Geometric parameters (Å, º) top

Br1—C5	1.901 (5)	C3—C8	1.409 (8)
O1—C1	1.219 (7)	C4—H4	0.9500
O2—C2	1.213 (7)	C4—C5	1.386 (8)
N1—H1	0.858 (14)	C5—C6	1.396 (8)
N1—C1	1.362 (9)	C6—H6	0.9500
N1—C8	1.403 (8)	C6—C7	1.394 (8)
C1—C2	1.555 (7)	C7—H7	0.9500
C2—C3	1.478 (9)	C7—C8	1.380 (8)
C3—C4	1.387 (8)

C1—N1—H1	119 (6)	C5—C4—H4	121.5
C1—N1—C8	111.9 (4)	C4—C5—Br1	119.4 (4)
C8—N1—H1	129 (5)	C4—C5—C6	122.0 (5)
O1—C1—N1	128.1 (5)	C6—C5—Br1	118.5 (4)
O1—C1—C2	126.2 (5)	C5—C6—H6	119.5
N1—C1—C2	105.8 (5)	C7—C6—C5	121.0 (5)
O2—C2—C1	124.7 (5)	C7—C6—H6	119.5
O2—C2—C3	130.2 (5)	C6—C7—H7	121.3
C3—C2—C1	105.0 (4)	C8—C7—C6	117.4 (5)
C4—C3—C2	132.0 (5)	C8—C7—H7	121.3
C4—C3—C8	121.3 (6)	N1—C8—C3	110.6 (5)
C8—C3—C2	106.7 (5)	C7—C8—N1	128.1 (5)
C3—C4—H4	121.5	C7—C8—C3	121.3 (5)
C5—C4—C3	116.9 (5)

Br1—C5—C6—C7	−176.2 (4)	C2—C3—C8—C7	−180.0 (5)
O1—C1—C2—O2	−2.1 (9)	C3—C4—C5—Br1	176.7 (5)
O1—C1—C2—C3	177.5 (6)	C3—C4—C5—C6	0.1 (8)
O2—C2—C3—C4	−0.6 (11)	C4—C3—C8—N1	−179.0 (6)
O2—C2—C3—C8	−179.4 (6)	C4—C3—C8—C7	1.1 (9)
N1—C1—C2—O2	178.7 (6)	C4—C5—C6—C7	0.4 (8)
N1—C1—C2—C3	−1.7 (6)	C5—C6—C7—C8	−0.2 (8)
C1—N1—C8—C3	−1.2 (7)	C6—C7—C8—N1	179.6 (6)
C1—N1—C8—C7	178.7 (6)	C6—C7—C8—C3	−0.6 (8)
C1—C2—C3—C4	179.9 (7)	C8—N1—C1—O1	−177.4 (6)
C1—C2—C3—C8	1.1 (6)	C8—N1—C1—C2	1.8 (7)
C2—C3—C4—C5	−179.5 (6)	C8—C3—C4—C5	−0.8 (9)
C2—C3—C8—N1	−0.1 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86 (1)	2.05 (3)	2.886 (6)	166 (9)
C7—H7···O2ⁱⁱ	0.95	2.38	3.312 (7)	167

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

Acknowledgements

We gratefully 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
Huang, H., Golen, J. A. & Manke, D. R. (2016). IUCrData, 1, x160007. Google Scholar
Kharbach, Y., Haoudi, A., Capet, F., Mazzah, A. & El Ammari, L. (2015). Acta Cryst. E71, o1024–o1025. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kurkin, A. V., Bernovskaya, A. A., Yurovskaya, M. A. & Rybakov, V. B. (2008). Acta Cryst. E64, o1448. Web of Science CSD CrossRef IUCr Journals Google Scholar
Maamri, K., Zouihri, H., Essassi, E. M. & Ng, S. W. (2012). Acta Cryst. E68, o240. Web of Science CSD CrossRef IUCr Journals 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
Turbitt, J. R., Golen, J. A. & Manke, D. R. (2016). IUCrData, 1, x152434. Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 2| February 2016| x160177

https://doi.org/10.1107/S2414314616001772

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

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

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

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds