organic compounds
4-Bromo-1H-indole-2,3-dione
aDepartment of Chemistry and Biochemistry, University of Massachusetts Dartmouth, 285 Old Westport Road, North Dartmouth, MA 02747, USA
*Correspondence e-mail: dmanke@umassd.edu
The title compound, C8H4BrNO2, has a single planar molecule in the 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 ). 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)
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. 1In 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.
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 .
details are summarized in Table 2Structural data
CCDC reference: 1445034
https://doi.org/10.1107/S2414314616000079/vm4004sup1.cif
contains datablock I. DOI: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
Data collection: APEX2 (Bruker, 2014); cell
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).C8H4BrNO2 | F(000) = 440 |
Mr = 226.03 | Dx = 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 |
Bruker D8 Venture CMOS diffractometer | 1381 independent reflections |
Radiation source: Mo | 1285 reflections with I > 2σ(I) |
TRIUMPH monochromator | Rint = 0.034 |
φ and ω scans | θmax = 25.6°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | h = −8→8 |
Tmin = 0.174, Tmax = 0.259 | k = −16→16 |
12353 measured reflections | l = −8→8 |
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(Fo2) + (0.0276P)2 + 0.4818P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.001 |
1381 reflections | Δρmax = 0.46 e Å−3 |
112 parameters | Δρmin = −0.45 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
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) |
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) |
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) |
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).
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