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

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ISSN: 2414-3146

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

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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 ππ inter­actions [inter­centroid distance = 3.8320 (7) Å, inter­planar distance = 3.341 (2) Å and slippage = 1.876 (4) Å].

3D view (loading...)
[Scheme 3D1]
Chemical scheme
[Scheme 1]

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[link]). 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[Goldschmidt, G. H. & Llewellyn, F. J. (1950). Acta Cryst. 3, 294-305.]). 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[Huang, H., Golen, J. A. & Manke, D. R. (2016). IUCrData, 1, x160007.]; Turbitt et al., 2016[Turbitt, J. R., Golen, J. A. & Manke, D. R. (2016). IUCrData, 1, x152434.]). No such halogen inter­actions were observed for 5-bromo­isatin, 7-fluoro­isatin or 7-chloro­isatin (Gurung et al., 2016[Gurung, S., Golen, J. A. & Manke, D. R. (2016). IUCrData, 1, x160177.]; Mohamed et al., 2007[Mohamed, S., Barnett, S. A. & Tocher, D. A. (2007). Acta Cryst. E63, o3575.], 2008[Mohamed, S., Barnett, S. A., Tocher, D. A., Price, S. L., Shankland, K. & Leech, C. K. (2008). CrystEngComm, 10, 399-404.]; Shankland et al., 2007[Shankland, K., Leech, C. K., Mohamed, S., Barnett, S. A. & Tocher, D. A. (2007). Acta Cryst. E63, o3574.]; Sun et al., 2010[Sun, J. & Cai, Z.-S. (2010). Acta Cryst. E66, o25.]).

[Figure 1]
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[link]). 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[link].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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]
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[link].

Table 2
Experimental details

Crystal data
Chemical formula C8H4BrNO2
Mr 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)
V3) 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[Bruker (2014). APEX2, SAINT, and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.178, 0.259
No. of measured, independent and observed [I > 2σ(I)] reflections 17212, 1374, 1231
Rint 0.051
(sin θ/λ)max−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
Δρmax, Δρmin (e Å−3) 0.69, −0.37
Computer programs: APEX2 (Bruker, 2014[Bruker (2014). APEX2, SAINT, and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SAINT (Bruker, 2014[Bruker (2014). APEX2, SAINT, and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Structural data


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
C8H4BrNO2F(000) = 440
Mr = 226.03Dx = 1.999 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 7365 reflections
a = 3.8320 (7) Åθ = 3.1–25.3°
b = 13.072 (2) ŵ = 5.42 mm1
c = 15.004 (3) ÅT = 120 K
β = 91.917 (7)°BLOCK, orange
V = 751.1 (2) Å30.18 × 0.14 × 0.08 mm
Z = 4
Data collection top
Bruker D8 Venture CMOS
diffractometer
1374 independent reflections
Radiation source: Mo1231 reflections with I > 2σ(I)
TRIUMPH monochromatorRint = 0.051
φ and ω scansθmax = 25.3°, θmin = 3.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2014)
h = 44
Tmin = 0.178, Tmax = 0.259k = 1515
17212 measured reflectionsl = 1818
Refinement top
Refinement on F21 restraint
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.029H 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 reflectionsΔρmax = 0.69 e Å3
112 parametersΔρmin = 0.37 e Å3
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
xyzUiso*/Ueq
Br10.78559 (9)0.81463 (3)0.42774 (2)0.02233 (14)
O10.2403 (7)0.47659 (19)0.59756 (17)0.0310 (6)
O20.0200 (7)0.6053 (2)0.74584 (16)0.0261 (6)
N10.4553 (8)0.6310 (2)0.54806 (19)0.0210 (6)
H10.553 (9)0.614 (3)0.5007 (18)0.025*
C10.2953 (9)0.5674 (3)0.6052 (2)0.0209 (7)
C20.1872 (9)0.6353 (3)0.6853 (2)0.0196 (7)
C30.3267 (8)0.7365 (3)0.6663 (2)0.0176 (7)
C40.3144 (9)0.8280 (3)0.7137 (2)0.0216 (7)
H40.21050.83140.77030.026*
C50.4604 (9)0.9145 (3)0.6752 (2)0.0241 (8)
H50.46290.97760.70670.029*
C60.6015 (9)0.9095 (3)0.5915 (2)0.0211 (7)
H60.69550.96970.56610.025*
C70.6088 (9)0.8177 (2)0.5437 (2)0.0180 (7)
C80.4733 (8)0.7315 (2)0.5823 (2)0.0165 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0209 (2)0.0246 (2)0.0218 (2)0.00089 (15)0.00512 (13)0.00333 (14)
O10.0463 (17)0.0174 (13)0.0300 (14)0.0051 (12)0.0133 (12)0.0004 (11)
O20.0329 (14)0.0209 (13)0.0251 (14)0.0032 (11)0.0116 (11)0.0045 (10)
N10.0292 (16)0.0165 (15)0.0179 (15)0.0000 (13)0.0091 (12)0.0006 (12)
C10.0243 (18)0.0176 (18)0.0211 (17)0.0046 (15)0.0039 (14)0.0002 (14)
C20.0164 (16)0.0201 (18)0.0224 (18)0.0047 (14)0.0023 (14)0.0015 (14)
C30.0132 (16)0.0196 (18)0.0200 (17)0.0035 (13)0.0003 (13)0.0011 (13)
C40.0223 (17)0.0226 (19)0.0199 (17)0.0044 (15)0.0006 (14)0.0022 (14)
C50.0233 (18)0.0193 (17)0.029 (2)0.0017 (15)0.0053 (15)0.0053 (15)
C60.0159 (16)0.0184 (17)0.0288 (19)0.0015 (14)0.0023 (14)0.0024 (14)
C70.0169 (15)0.0209 (18)0.0162 (16)0.0014 (14)0.0002 (13)0.0042 (13)
C80.0136 (15)0.0159 (16)0.0199 (17)0.0019 (13)0.0014 (13)0.0011 (13)
Geometric parameters (Å, º) top
Br1—C71.888 (3)C3—C81.399 (5)
O1—C11.210 (4)C4—H40.9500
O2—C21.195 (4)C4—C51.396 (5)
N1—H10.846 (19)C5—H50.9500
N1—C11.356 (4)C5—C61.385 (5)
N1—C81.411 (4)C6—H60.9500
C1—C21.562 (5)C6—C71.399 (5)
C2—C31.458 (5)C7—C81.377 (5)
C3—C41.394 (5)
C1—N1—H1126 (3)C5—C4—H4121.2
C1—N1—C8111.0 (3)C4—C5—H5119.6
C8—N1—H1123 (3)C6—C5—C4120.8 (3)
O1—C1—N1128.6 (3)C6—C5—H5119.6
O1—C1—C2125.5 (3)C5—C6—H6119.3
N1—C1—C2106.0 (3)C5—C6—C7121.4 (3)
O2—C2—C1124.1 (3)C7—C6—H6119.3
O2—C2—C3131.0 (3)C6—C7—Br1120.3 (2)
C3—C2—C1104.9 (3)C8—C7—Br1121.5 (3)
C4—C3—C2131.3 (3)C8—C7—C6118.2 (3)
C4—C3—C8121.4 (3)C3—C8—N1110.8 (3)
C8—C3—C2107.1 (3)C7—C8—N1128.6 (3)
C3—C4—H4121.2C7—C8—C3120.6 (3)
C3—C4—C5117.6 (3)
Br1—C7—C8—N13.0 (5)C2—C3—C8—N13.5 (4)
Br1—C7—C8—C3176.6 (2)C2—C3—C8—C7176.1 (3)
O1—C1—C2—O24.3 (6)C3—C4—C5—C62.0 (5)
O1—C1—C2—C3176.9 (4)C4—C3—C8—N1180.0 (3)
O2—C2—C3—C41.6 (6)C4—C3—C8—C70.4 (5)
O2—C2—C3—C8174.4 (4)C4—C5—C6—C71.2 (5)
N1—C1—C2—O2175.1 (3)C5—C6—C7—Br1177.4 (3)
N1—C1—C2—C33.7 (4)C5—C6—C7—C80.5 (5)
C1—N1—C8—C31.1 (4)C6—C7—C8—N1179.1 (3)
C1—N1—C8—C7178.6 (3)C6—C7—C8—C31.2 (5)
C1—C2—C3—C4179.7 (3)C8—N1—C1—O1179.0 (4)
C1—C2—C3—C84.3 (3)C8—N1—C1—C21.7 (4)
C2—C3—C4—C5176.8 (3)C8—C3—C4—C51.3 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.85 (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

First citationBruker (2014). APEX2, SAINT, and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationDolomanov, 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
First citationGoldschmidt, G. H. & Llewellyn, F. J. (1950). Acta Cryst. 3, 294–305.  CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
First citationGurung, S., Golen, J. A. & Manke, D. R. (2016). IUCrData, 1, x160177.  Google Scholar
First citationHuang, H., Golen, J. A. & Manke, D. R. (2016). IUCrData, 1, x160007.  Google Scholar
First citationMohamed, S., Barnett, S. A. & Tocher, D. A. (2007). Acta Cryst. E63, o3575.  CSD CrossRef IUCr Journals Google Scholar
First citationMohamed, S., Barnett, S. A., Tocher, D. A., Price, S. L., Shankland, K. & Leech, C. K. (2008). CrystEngComm, 10, 399–404.  CAS Google Scholar
First citationShankland, K., Leech, C. K., Mohamed, S., Barnett, S. A. & Tocher, D. A. (2007). Acta Cryst. E63, o3574.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2015). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
First citationSun, J. & Cai, Z.-S. (2010). Acta Cryst. E66, o25.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationTurbitt, J. R., Golen, J. A. & Manke, D. R. (2016). IUCrData, 1, x152434.  Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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