organic compounds
6-Bromo-1H-indole-2,3-dione hemihydrate
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, C8H4BrNO2·0.5H2O, has a single planar molecule in the with the non-H atoms having a mean deviation from planarity of 0.028 Å. There is also a half of a water molecule (twofold symmetry) present in the which hydrogen bonds with the isatin molecules through O—H⋯O and N—H⋯O hydrogen bonds to form a two-dimensional framework in the ab plane. There are close Br⋯O contacts of 2.999 (2) Å to link the layers. The nine-membered rings of the isatin molecules stack along the a axis with parallel slipped π–π interactions [inter-centroid distances = 3.6989 (19) and 4.1227 (19) Å].
Keywords: crystal structure; isatins; hydrogen bonding; π–π interactions; halogen–oxygen interactions.
CCDC reference: 1443113
Structure description
Isatins are a class of compounds that have a wide use in organic synthesis and in pharmaceuticals. We have begun a study on the structure of halogenated isatin compounds, and herein report the . The structure exhibits a nearly planar molecule with the non-hydrogen atoms having a mean deviation from planarity of 0.028 Å. The bond lengths and angles observed are similar to those seen in isatin (Goldschmidt et al., 1950). The structure also demonstrates an intermolecular Br1⋯O1 close contact of 2.999 (2) Å. A related I⋯O interaction is observed in the structure of 6-iodoisatin (Garden et al., 2006), though no such halogen-oxygen interactions are observed for the derivatives of 6-bromoisatin (Ji et al., 2009; Zhao et al., 2012).
of 6-bromoisatin, Fig. 1In the crystal, there is a half of a water molecule present in the , to form a two-dimensional framework parallel to to the ab plane. The nine-membered rings of the isatins stack along a with parallel slipped π–π interactions [inter-centroid distances: 3.6989 (19) and 4.1227 (19) Å, inter-planar distances: 3.345 (2) and 3.341 (3) Å, slippage: 1.579 (4) and 2.415 (3) Å]. Halogen bonding of the type Br⋯O links layers along the c axis. The packing of the title compound indicating hydrogen bonding is shown in Fig. 2.
along with the organic molecule. The water molecule hydrogen bonds with isatin molecules through N1—H1⋯O3 and O3—H3⋯O2 hydrogen bonds, Table 1Synthesis and crystallization
A commercial sample (Matrix Scientific) of 6-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 acetone solution.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1443113
10.1107/S2414314615024347/tk4001sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314615024347/tk4001Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314615024347/tk4001Isup3.cml
Isatins are a class of compounds that have a wide use in organic synthesis and in pharmaceuticals. We have begun a study on the structure of halogenated isatin compounds, and herein report the
of 6-bromoisatin, Fig. 1. The structure exhibits a nearly planar molecule with the non-hydrogen atoms having a mean deviation from planarity of 0.028 Å. The bond lengths and angles observed are similar to those seen in isatin (Goldschmidt et al., 1950). The structure also demonstrates an intermolecular Br1···O1 close contact of 2.999 (2) Å. A related I···O interaction is observed in the structure of 6-iodoisatin (Garden et al., 2006), though no such halogen-oxygen interactions are observed for the derivatives of 6-bromoisatin (Ji et al., 2009; Zhao et al., 2012).In the crystal, there is a half of a water molecule present in the π-π interactions [inter-centroid distances: 3.6989 (19) Å, 4.1227 (19) Å, inter-planar distances: 3.345 (2) Å, 3.341 (3) Å, slippage: 1.579 (4) Å, 2.415 (3) Å]. Halogen bonding of the type Br···O links layers along the c axis. The packing of the title compound indicating hydrogen bonding is shown in Fig. 2.
along with the organic molecule. The water molecule hydrogen bonds with isatin molecules through N1—H1···O3 and O3—H3···O2 hydrogen bonds, Table 1, to form a two-dimensional framework parallel to to the ab plane. The 9-membered rings of the isatins stack along a with parallel slippedA commercial sample (Matrix Scientific) of 6-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 acetone solution.
The carbon-bound H-atoms were placed in calculated positions (C—H = 0.95 Å) and were included in the
in the riding model approximation, with Uiso(H) set to 1.2Uequiv(C). The oxygen- and nitrogen-bound H-atoms were located in a difference Fourier map but were refined with a distance restraints of O—H = 0.86±0.02 Å and N—H = 0.87±0.02 Å, and with Uiso(H) set to 1.5Uequiv(O) and 1.2Uequiv(N).A commercial sample (Matrix Scientific) of 6-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 acetone solution.
Isatins are a class of compounds that have a wide use in organic synthesis and in pharmaceuticals. We have begun a study on the structure of halogenated isatin compounds, and herein report the
of 6-bromoisatin, Fig. 1. The structure exhibits a nearly planar molecule with the non-hydrogen atoms having a mean deviation from planarity of 0.028 Å. The bond lengths and angles observed are similar to those seen in isatin (Goldschmidt et al., 1950). The structure also demonstrates an intermolecular Br1···O1 close contact of 2.999 (2) Å. A related I···O interaction is observed in the structure of 6-iodoisatin (Garden et al., 2006), though no such halogen-oxygen interactions are observed for the derivatives of 6-bromoisatin (Ji et al., 2009; Zhao et al., 2012).In the crystal, there is a half of a water molecule present in the π–π interactions [inter-centroid distances: 3.6989 (19) and 4.1227 (19) Å, inter-planar distances: 3.345 (2) and 3.341 (3) Å, slippage: 1.579 (4) and 2.415 (3) Å]. Halogen bonding of the type Br···O links layers along the c axis. The packing of the title compound indicating hydrogen bonding is shown in Fig. 2.
along with the organic molecule. The water molecule hydrogen bonds with isatin molecules through N1—H1···O3 and O3—H3···O2 hydrogen bonds, Table 1, to form a two-dimensional framework parallel to to the ab plane. The nine-membered rings of the isatins stack along a with parallel slippedData 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).Fig. 1. Molecular structure of the title compound, showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. | |
Fig. 2. Molecular packing of the title compound with hydrogen bonding shown as dashed lines. |
C8H4BrNO2·0.5H2O | F(000) = 920 |
Mr = 235.04 | Dx = 1.995 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 6603 reflections |
a = 7.4556 (11) Å | θ = 3.2–25.4° |
b = 12.9055 (19) Å | µ = 5.21 mm−1 |
c = 16.334 (2) Å | T = 120 K |
β = 95.063 (5)° | Prism, orange |
V = 1565.5 (4) Å3 | 0.2 × 0.2 × 0.1 mm |
Z = 8 |
Bruker D8 Venture CMOS diffractometer | 1429 independent reflections |
Radiation source: Mo | 1253 reflections with I > 2σ(I) |
TRIUMPH monochromator | Rint = 0.050 |
φ and ω scans | θmax = 25.4°, θmin = 3.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2014/4) | h = −8→8 |
Tmin = 0.192, Tmax = 0.259 | k = −15→15 |
13613 measured reflections | l = −18→19 |
Refinement on F2 | 2 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.024 | w = 1/[σ2(Fo2) + (0.0315P)2 + 4.3923P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.065 | (Δ/σ)max < 0.001 |
S = 1.09 | Δρmax = 0.62 e Å−3 |
1429 reflections | Δρmin = −0.39 e Å−3 |
120 parameters |
C8H4BrNO2·0.5H2O | V = 1565.5 (4) Å3 |
Mr = 235.04 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 7.4556 (11) Å | µ = 5.21 mm−1 |
b = 12.9055 (19) Å | T = 120 K |
c = 16.334 (2) Å | 0.2 × 0.2 × 0.1 mm |
β = 95.063 (5)° |
Bruker D8 Venture CMOS diffractometer | 1429 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2014/4) | 1253 reflections with I > 2σ(I) |
Tmin = 0.192, Tmax = 0.259 | Rint = 0.050 |
13613 measured reflections |
R[F2 > 2σ(F2)] = 0.024 | 120 parameters |
wR(F2) = 0.065 | 2 restraints |
S = 1.09 | Δρmax = 0.62 e Å−3 |
1429 reflections | Δρmin = −0.39 e Å−3 |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.40315 (4) | 0.20161 (2) | 0.35694 (2) | 0.01836 (12) | |
O1 | 0.7463 (3) | 0.47056 (16) | 0.75002 (12) | 0.0226 (5) | |
O2 | 0.8623 (3) | 0.57877 (16) | 0.60676 (13) | 0.0207 (5) | |
O3 | 1.0000 | 0.6924 (2) | 0.7500 | 0.0188 (6) | |
H3 | 0.928 (4) | 0.655 (2) | 0.721 (2) | 0.028* | |
N1 | 0.6201 (3) | 0.3580 (2) | 0.65031 (15) | 0.0167 (5) | |
H1 | 0.586 (5) | 0.309 (2) | 0.6811 (19) | 0.020* | |
C1 | 0.7134 (4) | 0.4428 (2) | 0.67950 (18) | 0.0176 (6) | |
C2 | 0.7746 (4) | 0.4998 (2) | 0.60258 (18) | 0.0161 (6) | |
C3 | 0.7031 (4) | 0.4379 (2) | 0.53218 (18) | 0.0142 (6) | |
C4 | 0.7102 (4) | 0.4495 (2) | 0.44812 (18) | 0.0160 (6) | |
H4 | 0.7749 | 0.5054 | 0.4269 | 0.019* | |
C5 | 0.6213 (4) | 0.3780 (2) | 0.39562 (18) | 0.0172 (6) | |
H5 | 0.6249 | 0.3838 | 0.3378 | 0.021* | |
C6 | 0.5265 (4) | 0.2975 (2) | 0.42903 (18) | 0.0145 (6) | |
C7 | 0.5173 (4) | 0.2830 (2) | 0.51294 (18) | 0.0149 (6) | |
H7 | 0.4518 | 0.2273 | 0.5340 | 0.018* | |
C8 | 0.6093 (4) | 0.3546 (2) | 0.56402 (17) | 0.0141 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.01939 (18) | 0.01899 (18) | 0.01625 (18) | −0.00163 (12) | −0.00102 (11) | −0.00288 (11) |
O1 | 0.0291 (12) | 0.0215 (11) | 0.0166 (12) | 0.0020 (10) | −0.0014 (9) | −0.0030 (9) |
O2 | 0.0203 (11) | 0.0153 (11) | 0.0259 (12) | −0.0032 (9) | −0.0017 (9) | −0.0008 (8) |
O3 | 0.0219 (17) | 0.0156 (15) | 0.0180 (16) | 0.000 | −0.0038 (12) | 0.000 |
N1 | 0.0208 (13) | 0.0161 (13) | 0.0136 (12) | −0.0028 (10) | 0.0036 (10) | 0.0013 (9) |
C1 | 0.0167 (15) | 0.0168 (15) | 0.0188 (16) | 0.0031 (12) | −0.0006 (12) | −0.0003 (12) |
C2 | 0.0118 (14) | 0.0142 (14) | 0.0216 (16) | 0.0038 (12) | −0.0015 (11) | −0.0002 (12) |
C3 | 0.0102 (14) | 0.0123 (14) | 0.0197 (15) | 0.0006 (11) | −0.0007 (11) | 0.0003 (11) |
C4 | 0.0132 (14) | 0.0155 (14) | 0.0195 (16) | −0.0019 (11) | 0.0019 (11) | 0.0034 (11) |
C5 | 0.0180 (15) | 0.0184 (15) | 0.0153 (15) | 0.0015 (12) | 0.0027 (12) | 0.0031 (12) |
C6 | 0.0114 (14) | 0.0139 (14) | 0.0175 (15) | 0.0010 (11) | −0.0017 (11) | −0.0015 (11) |
C7 | 0.0142 (14) | 0.0119 (14) | 0.0187 (15) | −0.0008 (11) | 0.0034 (11) | 0.0008 (11) |
C8 | 0.0126 (14) | 0.0143 (14) | 0.0158 (14) | 0.0035 (11) | 0.0029 (11) | 0.0008 (11) |
Br1—C6 | 1.890 (3) | C3—C4 | 1.387 (4) |
O1—C1 | 1.210 (4) | C3—C8 | 1.406 (4) |
O2—C2 | 1.209 (4) | C4—H4 | 0.9500 |
O3—H3 | 0.833 (18) | C4—C5 | 1.388 (4) |
N1—H1 | 0.857 (18) | C5—H5 | 0.9500 |
N1—C1 | 1.361 (4) | C5—C6 | 1.394 (4) |
N1—C8 | 1.405 (4) | C6—C7 | 1.391 (4) |
C1—C2 | 1.559 (4) | C7—H7 | 0.9500 |
C2—C3 | 1.462 (4) | C7—C8 | 1.386 (4) |
C1—N1—H1 | 124 (2) | C5—C4—H4 | 120.6 |
C1—N1—C8 | 111.0 (2) | C4—C5—H5 | 120.5 |
C8—N1—H1 | 125 (2) | C4—C5—C6 | 119.0 (3) |
O1—C1—N1 | 128.7 (3) | C6—C5—H5 | 120.5 |
O1—C1—C2 | 125.3 (3) | C5—C6—Br1 | 118.7 (2) |
N1—C1—C2 | 105.9 (2) | C7—C6—Br1 | 117.5 (2) |
O2—C2—C1 | 123.2 (3) | C7—C6—C5 | 123.8 (3) |
O2—C2—C3 | 131.5 (3) | C6—C7—H7 | 122.0 |
C3—C2—C1 | 105.3 (2) | C8—C7—C6 | 116.0 (3) |
C4—C3—C2 | 132.5 (3) | C8—C7—H7 | 122.0 |
C4—C3—C8 | 120.8 (3) | N1—C8—C3 | 111.2 (2) |
C8—C3—C2 | 106.6 (3) | C7—C8—N1 | 127.3 (3) |
C3—C4—H4 | 120.6 | C7—C8—C3 | 121.5 (3) |
C3—C4—C5 | 118.8 (3) | ||
Br1—C6—C7—C8 | 180.0 (2) | C2—C3—C8—C7 | 177.0 (3) |
O1—C1—C2—O2 | −0.2 (5) | C3—C4—C5—C6 | 0.5 (4) |
O1—C1—C2—C3 | −179.9 (3) | C4—C3—C8—N1 | 179.9 (3) |
O2—C2—C3—C4 | −0.7 (6) | C4—C3—C8—C7 | −1.7 (4) |
O2—C2—C3—C8 | −179.2 (3) | C4—C5—C6—Br1 | 179.2 (2) |
N1—C1—C2—O2 | −179.6 (3) | C4—C5—C6—C7 | −1.0 (4) |
N1—C1—C2—C3 | 0.7 (3) | C5—C6—C7—C8 | 0.1 (4) |
C1—N1—C8—C3 | 2.0 (3) | C6—C7—C8—N1 | 179.4 (3) |
C1—N1—C8—C7 | −176.4 (3) | C6—C7—C8—C3 | 1.2 (4) |
C1—C2—C3—C4 | 178.9 (3) | C8—N1—C1—O1 | 179.0 (3) |
C1—C2—C3—C8 | 0.4 (3) | C8—N1—C1—C2 | −1.6 (3) |
C2—C3—C4—C5 | −177.6 (3) | C8—C3—C4—C5 | 0.7 (4) |
C2—C3—C8—N1 | −1.4 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2 | 0.83 (2) | 2.13 (3) | 2.873 (3) | 148 (4) |
N1—H1···O3i | 0.86 (2) | 2.02 (2) | 2.876 (3) | 178 (4) |
Symmetry code: (i) x−1/2, y−1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2 | 0.833 (18) | 2.13 (3) | 2.873 (3) | 148 (4) |
N1—H1···O3i | 0.857 (18) | 2.020 (19) | 2.876 (3) | 178 (4) |
Symmetry code: (i) x−1/2, y−1/2, z. |
Experimental details
Crystal data | |
Chemical formula | C8H4BrNO2·0.5H2O |
Mr | 235.04 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 120 |
a, b, c (Å) | 7.4556 (11), 12.9055 (19), 16.334 (2) |
β (°) | 95.063 (5) |
V (Å3) | 1565.5 (4) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 5.21 |
Crystal size (mm) | 0.2 × 0.2 × 0.1 |
Data collection | |
Diffractometer | Bruker D8 Venture CMOS |
Absorption correction | Multi-scan (SADABS; Bruker, 2014/4) |
Tmin, Tmax | 0.192, 0.259 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13613, 1429, 1253 |
Rint | 0.050 |
(sin θ/λ)max (Å−1) | 0.604 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.065, 1.09 |
No. of reflections | 1429 |
No. of parameters | 120 |
No. of restraints | 2 |
Δρmax, Δρmin (e Å−3) | 0.62, −0.39 |
Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2014), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), OLEX2 (Dolomanov et al., 2009), OLEX2 and publCIF (Westrip, 2010).
Acknowledgements
We greatly acknowledge support from the National Science Foundation (CHE-1429086).
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