organic compounds
7-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 0.034 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 ). 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).
of 7-bromoisatin (Fig. 1In 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]. 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.
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 .
details are summarized in Table 2Structural data
CCDC reference: 1453500
https://doi.org/10.1107/S2414314616002686/vm4006sup1.cif
contains datablock I. DOI: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
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 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).C8H4BrNO2 | F(000) = 440 |
Mr = 226.03 | Dx = 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 |
Bruker D8 Venture CMOS diffractometer | 1374 independent reflections |
Radiation source: Mo | 1231 reflections with I > 2σ(I) |
TRIUMPH monochromator | Rint = 0.051 |
φ and ω scans | θmax = 25.3°, θmin = 3.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | h = −4→4 |
Tmin = 0.178, Tmax = 0.259 | k = −15→15 |
17212 measured reflections | l = −18→18 |
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(Fo2) + (0.0305P)2 + 1.3045P] where P = (Fo2 + 2Fc2)/3 |
S = 1.19 | (Δ/σ)max = 0.001 |
1374 reflections | Δρmax = 0.69 e Å−3 |
112 parameters | Δρmin = −0.37 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 | 0.78559 (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) |
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) |
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) |
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).
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