organic compounds
4,6-Dichloro-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, C8H3Cl2NO2, has a single, almost planar, molecule in the with the non-H atoms having a mean deviation from planarity of 0.027 Å. In the crystal, N—H⋯O hydrogen bonds form infinite C(4) chains along [100]. No π–π interactions were observed in the structure.
Keywords: crystal structure; hydrogen bonding; isatins.
CCDC reference: 1476205
Structure description
Herein we report the ), which has a near planar molecule in the with non-H atoms possessing a mean deviation from planarity of 0.027 Å. The distances and angles are consistent with those reported for 1H-indole-2,3-dione (Goldschmidt & Llewellyn, 1950).
of 4,6-dichloroisatin (Fig. 1In the crystal, the molecules are linked through N1—H1⋯O1 hydrogen bonds (Table 1) to form infinite chains along [100] (Fig. 2). No other intermolecular hydrogen bonding or π–π interactions are observed. In addition to N—H⋯O hydrogen bonding, the monosubstituted 4-chloroisatin possesses C—H⋯Cl close contacts (Juma et al., 2016) and 6-chloroisatin possesses C—H⋯O interactions (Golen & Manke, 2016), neither of which are observed in the title compound.
Synthesis and crystallization
A commercial sample (Matrix Scientific) of 4,6-dichloro-1H-indole-2,3-dione was used for the crystallization. Orange blocks were grown from the slow evaporation of an acetone solution.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1476205
10.1107/S2414314616006957/hb4042sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616006957/hb4042Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616006957/hb4042Isup3.cml
A commercial sample (Matrix Scientific) of 4,6-dichloro-1H-indole-2,3-dione was used for the crystallization. Orange blocks were grown from the slow evaporation of an acetone solution.
Herein we report the π–π interactions are observed. In addition to N—H···O hydrogen bonding, the monosubstituted 4-chloroisatin possesses C—H···Cl close contacts (Juma et al., 2016) and 6-chloroisatin possesses C—H···O interactions (Golen & Manke, 2016), neither of which are observed in the title compound.
of 4,6-dichloroisatin (Fig. 1), which has a near planar molecule in the with non-H atoms possessing a mean deviation from planarity of 0.027 Å. The distances and angles are consistent with those reported for 1H-indole-2,3-dione (Goldschmidt & Llewellyn, 1950). In the crystal, the molecules are linked through N1—H1···O1 hydrogen bonds to form infinite chains along [100] (Fig. 2). No other intermolecular hydrogen bonding orData 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. The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level. H atoms are drawn as spheres of arbitrary radius | |
Fig. 2. Molecular packing of the title compound along the b axis, with hydrogen bonding shown as dashed lines. |
C8H3Cl2NO2 | F(000) = 864 |
Mr = 216.01 | Dx = 1.776 Mg m−3 |
Orthorhombic, Pbca | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 8528 reflections |
a = 8.6253 (19) Å | θ = 3.4–72.4° |
b = 7.1250 (16) Å | µ = 6.92 mm−1 |
c = 26.289 (6) Å | T = 120 K |
V = 1615.6 (6) Å3 | Block, orange |
Z = 8 | 0.25 × 0.2 × 0.1 mm |
Bruker Venture D8 CMOS diffractometer | 1604 independent reflections |
Radiation source: Cu | 1531 reflections with I > 2σ(I) |
HELIOS MX monochromator | Rint = 0.057 |
φ and ω scans | θmax = 72.7°, θmin = 3.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | h = −10→10 |
Tmin = 0.190, Tmax = 0.386 | k = −8→8 |
13414 measured reflections | l = −32→32 |
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.038 | w = 1/[σ2(Fo2) + (0.0427P)2 + 2.2094P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.098 | (Δ/σ)max < 0.001 |
S = 1.10 | Δρmax = 0.34 e Å−3 |
1604 reflections | Δρmin = −0.26 e Å−3 |
122 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.0017 (3) |
C8H3Cl2NO2 | V = 1615.6 (6) Å3 |
Mr = 216.01 | Z = 8 |
Orthorhombic, Pbca | Cu Kα radiation |
a = 8.6253 (19) Å | µ = 6.92 mm−1 |
b = 7.1250 (16) Å | T = 120 K |
c = 26.289 (6) Å | 0.25 × 0.2 × 0.1 mm |
Bruker Venture D8 CMOS diffractometer | 1604 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | 1531 reflections with I > 2σ(I) |
Tmin = 0.190, Tmax = 0.386 | Rint = 0.057 |
13414 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 1 restraint |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | Δρmax = 0.34 e Å−3 |
1604 reflections | Δρmin = −0.26 e Å−3 |
122 parameters |
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 | ||
Cl1 | 0.29514 (7) | 0.91432 (9) | 0.57109 (2) | 0.0280 (2) | |
Cl2 | 0.90946 (7) | 0.85524 (8) | 0.54527 (2) | 0.0266 (2) | |
O1 | 0.4268 (2) | 0.5417 (3) | 0.76169 (6) | 0.0307 (4) | |
O2 | 0.2373 (2) | 0.7287 (3) | 0.68422 (6) | 0.0340 (5) | |
N1 | 0.6227 (2) | 0.6103 (3) | 0.70490 (7) | 0.0233 (4) | |
H1 | 0.706 (2) | 0.586 (4) | 0.7219 (10) | 0.028* | |
C8 | 0.6327 (3) | 0.6988 (3) | 0.65726 (8) | 0.0199 (5) | |
C4 | 0.4730 (3) | 0.8391 (3) | 0.59277 (9) | 0.0211 (5) | |
C3 | 0.4861 (3) | 0.7546 (3) | 0.64011 (8) | 0.0216 (5) | |
C7 | 0.7662 (3) | 0.7288 (3) | 0.62975 (8) | 0.0219 (5) | |
H7 | 0.8654 | 0.6946 | 0.6424 | 0.026* | |
C6 | 0.7471 (3) | 0.8124 (3) | 0.58219 (8) | 0.0208 (5) | |
C5 | 0.6037 (3) | 0.8662 (3) | 0.56284 (9) | 0.0225 (5) | |
H5 | 0.5954 | 0.9202 | 0.5299 | 0.027* | |
C2 | 0.3748 (3) | 0.7047 (4) | 0.68032 (9) | 0.0240 (5) | |
C1 | 0.4750 (3) | 0.6071 (4) | 0.72214 (9) | 0.0255 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0227 (3) | 0.0336 (4) | 0.0277 (3) | 0.0046 (2) | −0.0042 (2) | 0.0030 (2) |
Cl2 | 0.0233 (3) | 0.0291 (3) | 0.0273 (3) | −0.0025 (2) | 0.0057 (2) | 0.0015 (2) |
O1 | 0.0293 (9) | 0.0422 (11) | 0.0205 (8) | 0.0017 (8) | 0.0032 (7) | 0.0037 (8) |
O2 | 0.0229 (9) | 0.0498 (12) | 0.0291 (9) | 0.0048 (8) | 0.0039 (7) | 0.0043 (8) |
N1 | 0.0212 (10) | 0.0314 (11) | 0.0172 (9) | 0.0039 (8) | −0.0006 (7) | 0.0013 (8) |
C8 | 0.0226 (11) | 0.0206 (11) | 0.0165 (10) | −0.0002 (9) | −0.0002 (8) | −0.0037 (8) |
C4 | 0.0211 (11) | 0.0206 (11) | 0.0215 (11) | 0.0019 (9) | −0.0024 (9) | −0.0029 (9) |
C3 | 0.0223 (11) | 0.0226 (11) | 0.0198 (10) | −0.0017 (9) | 0.0013 (9) | −0.0030 (9) |
C7 | 0.0210 (11) | 0.0227 (11) | 0.0220 (10) | −0.0005 (9) | −0.0005 (9) | −0.0041 (9) |
C6 | 0.0217 (11) | 0.0198 (11) | 0.0210 (10) | −0.0020 (9) | 0.0036 (9) | −0.0034 (8) |
C5 | 0.0307 (13) | 0.0187 (11) | 0.0181 (10) | −0.0037 (10) | −0.0028 (9) | −0.0006 (8) |
C2 | 0.0225 (12) | 0.0286 (12) | 0.0208 (11) | 0.0019 (10) | 0.0014 (9) | −0.0022 (9) |
C1 | 0.0273 (12) | 0.0296 (13) | 0.0195 (11) | 0.0030 (10) | 0.0010 (9) | −0.0023 (9) |
Cl1—C4 | 1.722 (2) | C4—C3 | 1.387 (3) |
Cl2—C6 | 1.731 (2) | C4—C5 | 1.388 (3) |
O1—C1 | 1.213 (3) | C3—C2 | 1.471 (3) |
O2—C2 | 1.202 (3) | C7—H7 | 0.9500 |
N1—H1 | 0.865 (17) | C7—C6 | 1.395 (3) |
N1—C8 | 1.405 (3) | C6—C5 | 1.391 (3) |
N1—C1 | 1.352 (3) | C5—H5 | 0.9500 |
C8—C3 | 1.400 (3) | C2—C1 | 1.562 (3) |
C8—C7 | 1.377 (3) | ||
C8—N1—H1 | 120 (2) | C6—C7—H7 | 122.0 |
C1—N1—H1 | 127.4 (19) | C7—C6—Cl2 | 118.82 (19) |
C1—N1—C8 | 111.3 (2) | C5—C6—Cl2 | 117.76 (17) |
C3—C8—N1 | 111.1 (2) | C5—C6—C7 | 123.4 (2) |
C7—C8—N1 | 126.1 (2) | C4—C5—C6 | 118.4 (2) |
C7—C8—C3 | 122.8 (2) | C4—C5—H5 | 120.8 |
C3—C4—Cl1 | 120.31 (18) | C6—C5—H5 | 120.8 |
C3—C4—C5 | 120.2 (2) | O2—C2—C3 | 132.1 (2) |
C5—C4—Cl1 | 119.49 (18) | O2—C2—C1 | 123.3 (2) |
C8—C3—C2 | 106.8 (2) | C3—C2—C1 | 104.6 (2) |
C4—C3—C8 | 119.1 (2) | O1—C1—N1 | 128.1 (2) |
C4—C3—C2 | 134.1 (2) | O1—C1—C2 | 125.8 (2) |
C8—C7—H7 | 122.0 | N1—C1—C2 | 106.14 (19) |
C8—C7—C6 | 116.0 (2) | ||
Cl1—C4—C3—C8 | −178.52 (17) | C8—C7—C6—C5 | 0.8 (3) |
Cl1—C4—C3—C2 | 1.4 (4) | C4—C3—C2—O2 | −2.5 (5) |
Cl1—C4—C5—C6 | 176.95 (17) | C4—C3—C2—C1 | 178.3 (3) |
Cl2—C6—C5—C4 | −177.68 (17) | C3—C8—C7—C6 | −2.5 (3) |
O2—C2—C1—O1 | 1.9 (4) | C3—C4—C5—C6 | −2.1 (3) |
O2—C2—C1—N1 | −178.5 (3) | C3—C2—C1—O1 | −178.7 (2) |
N1—C8—C3—C4 | −177.9 (2) | C3—C2—C1—N1 | 0.8 (3) |
N1—C8—C3—C2 | 2.2 (3) | C7—C8—C3—C4 | 1.9 (4) |
N1—C8—C7—C6 | 177.3 (2) | C7—C8—C3—C2 | −178.0 (2) |
C8—N1—C1—O1 | −180.0 (2) | C7—C6—C5—C4 | 1.5 (4) |
C8—N1—C1—C2 | 0.5 (3) | C5—C4—C3—C8 | 0.5 (3) |
C8—C3—C2—O2 | 177.5 (3) | C5—C4—C3—C2 | −179.6 (2) |
C8—C3—C2—C1 | −1.8 (3) | C1—N1—C8—C3 | −1.7 (3) |
C8—C7—C6—Cl2 | 179.91 (17) | C1—N1—C8—C7 | 178.5 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.87 (2) | 1.98 (2) | 2.809 (3) | 161 (3) |
Symmetry code: (i) x+1/2, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.865 (17) | 1.977 (19) | 2.809 (3) | 161 (3) |
Symmetry code: (i) x+1/2, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C8H3Cl2NO2 |
Mr | 216.01 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 120 |
a, b, c (Å) | 8.6253 (19), 7.1250 (16), 26.289 (6) |
V (Å3) | 1615.6 (6) |
Z | 8 |
Radiation type | Cu Kα |
µ (mm−1) | 6.92 |
Crystal size (mm) | 0.25 × 0.2 × 0.1 |
Data collection | |
Diffractometer | Bruker Venture D8 CMOS |
Absorption correction | Multi-scan (SADABS; Bruker, 2014) |
Tmin, Tmax | 0.190, 0.386 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13414, 1604, 1531 |
Rint | 0.057 |
(sin θ/λ)max (Å−1) | 0.619 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.098, 1.10 |
No. of reflections | 1604 |
No. of parameters | 122 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.34, −0.26 |
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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