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

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

doi:10.1107/S2414314616002686

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 2| February 2016| x160268

https://doi.org/10.1107/S2414314616002686

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access

7-Bromo-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 L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 13 February 2016; accepted 15 February 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 0.034 Å. The molecules dimerize in the solid state through N—H⋯O hydrogen bonds. These dimers are further linked by intermolecular Br⋯O close contacts of 3.085 (2) Å to yield infinite chains along [20-1]. The nine-membered rings of the isatins stack along the a axis, with parallel slipped π–π interactions [intercentroid distance = 3.8320 (7) Å, interplanar distance = 3.341 (2) Å and slippage = 1.876 (4) Å].

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

CCDC reference: 1453500

Structure description

As part of a continuing study into the structure of halogenated isatins, we report, herein the crystal structure of 7-bromoisatin (Fig. 1). The structure exhibits a near planar molecule with the non-hydrogen atoms possessing a mean deviation from planarity of 0.034 Å, with similar bond lengths and angles as those observed in isatin (Goldschmidt et al., 1950 ). The structure of the title compound demonstrates intermolecular Br1⋯O2 close contacts of 3.085 (2) Å, which are also observed in the structures of 4-bromoisatin and 6-bromoisatin (Huang et al., 2016 ; Turbitt et al., 2016 ). No such halogen interactions were observed for 5-bromoisatin, 7-fluoroisatin or 7-chloroisatin (Gurung et al., 2016 ; Mohamed et al., 2007 , 2008 ; Shankland et al., 2007 ; Sun et al., 2010 ).

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 crystals, the molecules dimerize through N1—H1⋯O1 hydrogen bonds (Table 1). These couple with the Br⋯O interactions to form chains along [20 $[\overline{1}]$ ]. The nine-membered rings of the isatins stack along [100] with parallel slipped π-π- interactions [inter-centroid distance: 3.8320 (7) Å, inter-planar distance: 3.341 (2) Å, slippage: 1.876 (4) Å]. The packing of the title compound showing the hydrogen bonding is illustrated in Fig. 2.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.85 (2)	2.07 (2)	2.878 (4)	161 (4)
Symmetry code: (i) -x+1, -y+1, -z+1.

Figure 2
Molecular packing of the title compound along the a-axis with hydrogen bonding shown as dashed lines and Br⋯O interactions shown with thin solid lines.

Synthesis and crystallization

A commercial sample (Matrix Scientific) of 7-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 methylene chloride 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)	3.8320 (7), 13.072 (2), 15.004 (3)
β (°)	91.917 (7)
V (Å³)	751.1 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	5.42
Crystal size (mm)	0.18 × 0.14 × 0.08

Data collection
Diffractometer	Bruker D8 Venture CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.178, 0.259
No. of measured, independent and observed [I > 2σ(I)] reflections	17212, 1374, 1231
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.072, 1.19
No. of reflections	1374
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)	0.69, −0.37
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: 1453500

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314616002686/vm4006sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616002686/vm4006Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616002686/vm4006Isup3.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).

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

Crystal data top

C₈H₄BrNO₂	F(000) = 440
M_r = 226.03	D_x = 1.999 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7365 reflections
a = 3.8320 (7) Å	θ = 3.1–25.3°
b = 13.072 (2) Å	µ = 5.42 mm⁻¹
c = 15.004 (3) Å	T = 120 K
β = 91.917 (7)°	BLOCK, orange
V = 751.1 (2) Å³	0.18 × 0.14 × 0.08 mm
Z = 4

Data collection top

Bruker D8 Venture CMOS diffractometer	1374 independent reflections
Radiation source: Mo	1231 reflections with I > 2σ(I)
TRIUMPH monochromator	R_int = 0.051
φ and ω scans	θ_max = 25.3°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −4→4
T_min = 0.178, T_max = 0.259	k = −15→15
17212 measured reflections	l = −18→18

Refinement top

Refinement on F²	1 restraint
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.072	w = 1/[σ²(F_o²) + (0.0305P)² + 1.3045P] where P = (F_o² + 2F_c²)/3
S = 1.19	(Δ/σ)_max = 0.001
1374 reflections	Δρ_max = 0.69 e Å⁻³
112 parameters	Δρ_min = −0.37 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	0.78559 (9)	0.81463 (3)	0.42774 (2)	0.02233 (14)
O1	0.2403 (7)	0.47659 (19)	0.59756 (17)	0.0310 (6)
O2	0.0200 (7)	0.6053 (2)	0.74584 (16)	0.0261 (6)
N1	0.4553 (8)	0.6310 (2)	0.54806 (19)	0.0210 (6)
H1	0.553 (9)	0.614 (3)	0.5007 (18)	0.025*
C1	0.2953 (9)	0.5674 (3)	0.6052 (2)	0.0209 (7)
C2	0.1872 (9)	0.6353 (3)	0.6853 (2)	0.0196 (7)
C3	0.3267 (8)	0.7365 (3)	0.6663 (2)	0.0176 (7)
C4	0.3144 (9)	0.8280 (3)	0.7137 (2)	0.0216 (7)
H4	0.2105	0.8314	0.7703	0.026*
C5	0.4604 (9)	0.9145 (3)	0.6752 (2)	0.0241 (8)
H5	0.4629	0.9776	0.7067	0.029*
C6	0.6015 (9)	0.9095 (3)	0.5915 (2)	0.0211 (7)
H6	0.6955	0.9697	0.5661	0.025*
C7	0.6088 (9)	0.8177 (2)	0.5437 (2)	0.0180 (7)
C8	0.4733 (8)	0.7315 (2)	0.5823 (2)	0.0165 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0209 (2)	0.0246 (2)	0.0218 (2)	−0.00089 (15)	0.00512 (13)	0.00333 (14)
O1	0.0463 (17)	0.0174 (13)	0.0300 (14)	−0.0051 (12)	0.0133 (12)	−0.0004 (11)
O2	0.0329 (14)	0.0209 (13)	0.0251 (14)	0.0032 (11)	0.0116 (11)	0.0045 (10)
N1	0.0292 (16)	0.0165 (15)	0.0179 (15)	0.0000 (13)	0.0091 (12)	−0.0006 (12)
C1	0.0243 (18)	0.0176 (18)	0.0211 (17)	0.0046 (15)	0.0039 (14)	0.0002 (14)
C2	0.0164 (16)	0.0201 (18)	0.0224 (18)	0.0047 (14)	0.0023 (14)	0.0015 (14)
C3	0.0132 (16)	0.0196 (18)	0.0200 (17)	0.0035 (13)	−0.0003 (13)	0.0011 (13)
C4	0.0223 (17)	0.0226 (19)	0.0199 (17)	0.0044 (15)	−0.0006 (14)	−0.0022 (14)
C5	0.0233 (18)	0.0193 (17)	0.029 (2)	0.0017 (15)	−0.0053 (15)	−0.0053 (15)
C6	0.0159 (16)	0.0184 (17)	0.0288 (19)	−0.0015 (14)	−0.0023 (14)	0.0024 (14)
C7	0.0169 (15)	0.0209 (18)	0.0162 (16)	0.0014 (14)	−0.0002 (13)	0.0042 (13)
C8	0.0136 (15)	0.0159 (16)	0.0199 (17)	0.0019 (13)	−0.0014 (13)	−0.0011 (13)

Geometric parameters (Å, º) top

Br1—C7	1.888 (3)	C3—C8	1.399 (5)
O1—C1	1.210 (4)	C4—H4	0.9500
O2—C2	1.195 (4)	C4—C5	1.396 (5)
N1—H1	0.846 (19)	C5—H5	0.9500
N1—C1	1.356 (4)	C5—C6	1.385 (5)
N1—C8	1.411 (4)	C6—H6	0.9500
C1—C2	1.562 (5)	C6—C7	1.399 (5)
C2—C3	1.458 (5)	C7—C8	1.377 (5)
C3—C4	1.394 (5)

C1—N1—H1	126 (3)	C5—C4—H4	121.2
C1—N1—C8	111.0 (3)	C4—C5—H5	119.6
C8—N1—H1	123 (3)	C6—C5—C4	120.8 (3)
O1—C1—N1	128.6 (3)	C6—C5—H5	119.6
O1—C1—C2	125.5 (3)	C5—C6—H6	119.3
N1—C1—C2	106.0 (3)	C5—C6—C7	121.4 (3)
O2—C2—C1	124.1 (3)	C7—C6—H6	119.3
O2—C2—C3	131.0 (3)	C6—C7—Br1	120.3 (2)
C3—C2—C1	104.9 (3)	C8—C7—Br1	121.5 (3)
C4—C3—C2	131.3 (3)	C8—C7—C6	118.2 (3)
C4—C3—C8	121.4 (3)	C3—C8—N1	110.8 (3)
C8—C3—C2	107.1 (3)	C7—C8—N1	128.6 (3)
C3—C4—H4	121.2	C7—C8—C3	120.6 (3)
C3—C4—C5	117.6 (3)

Br1—C7—C8—N1	3.0 (5)	C2—C3—C8—N1	−3.5 (4)
Br1—C7—C8—C3	−176.6 (2)	C2—C3—C8—C7	176.1 (3)
O1—C1—C2—O2	−4.3 (6)	C3—C4—C5—C6	2.0 (5)
O1—C1—C2—C3	176.9 (4)	C4—C3—C8—N1	180.0 (3)
O2—C2—C3—C4	1.6 (6)	C4—C3—C8—C7	−0.4 (5)
O2—C2—C3—C8	−174.4 (4)	C4—C5—C6—C7	−1.2 (5)
N1—C1—C2—O2	175.1 (3)	C5—C6—C7—Br1	177.4 (3)
N1—C1—C2—C3	−3.7 (4)	C5—C6—C7—C8	−0.5 (5)
C1—N1—C8—C3	1.1 (4)	C6—C7—C8—N1	−179.1 (3)
C1—N1—C8—C7	−178.6 (3)	C6—C7—C8—C3	1.2 (5)
C1—C2—C3—C4	−179.7 (3)	C8—N1—C1—O1	−179.0 (4)
C1—C2—C3—C8	4.3 (3)	C8—N1—C1—C2	1.7 (4)
C2—C3—C4—C5	−176.8 (3)	C8—C3—C4—C5	−1.3 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.85 (2)	2.07 (2)	2.878 (4)	161 (4)

Symmetry code: (i) −x+1, −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| x160268

https://doi.org/10.1107/S2414314616002686

Open

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

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

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds