organic compounds
7-Iodo-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, C8H4INO2, has a single planar molecule in the with the non-H atoms possessing a mean deviation from planarity of 0.058 Å. The molecules dimerize in the solid state through N—H⋯O hydrogen bonds. There are intermolecular I⋯O close contacts of 3.193 (4) Å that link the molecules into infinite chains along [20-1]. No π–π interactions were observed in the structure.
Keywords: crystal structure; hydrogen bonding; isatins; halogen–oxygen interactions.
CCDC reference: 1463777
Structure description
We report herein the ). The molecule is nearly planar, with the non-H atoms possessing a mean deviation from planarity of 0.058 Å, and exhibits bond lengths and angles similar to those observed in isatin (Goldschmidt & Llewellyn, 1950). In the crystal, molecules dimerize through N1—H1⋯O1i hydrogen bonds (see Table 1 for symmetry code), which are further linked through I1⋯O2 close contacts [symmetry code: (i) 1 + x, − y, − + z] of 3.193 (4) Å, leading to infinite chains along [20]. Similar I⋯O interactions are observed in the structures of 4-iodoisatin (Golen & Manke, 2016a) and 5-iodoisatin (Garden et al., 2006). The structure of 7-bromoisatin also demonstrates a similar halogen–oxygen interaction (Golen & Manke, 2016b). The packing of the title compound, indicating the hydrogen bonding, is shown in Fig. 2.
of 7-iodoisatin (Fig. 1Synthesis and crystallization
A commercial sample (AK Scientific) of 7-iodo-1H-indole-2,3-dione was used for crystallization. A sample suitable for single-crystal X-ray analysis was grown by slow evaporation from an acetone solution.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1463777
10.1107/S2414314616004120/ff4004sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616004120/ff4004Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616004120/ff4004Isup3.cml
A commercial sample (AK Scientific) of 7-iodo-1H-indole-2,3-dione was used for crystallization. A sample suitable for single-crystal X-ray analysis was grown by slow evaporation from an acetone solution.
We report herein the 1]. Similar I···O interactions are observed in the structures of 4-iodoisatin (Golen & Manke, 2016a) and 5-iodoisatin (Garden et al., 2006). The structure of 7-bromoisatin also demonstrates a similar halogen–oxygen interaction (Golen & Manke, 2016b). The packing of the title compound, indicating the hydrogen bonding, is shown in Fig. 2.
of 7-iodoisatin (Fig. 1). The molecule is nearly planar, with the non-H atoms possessing a mean deviation from planarity of 0.058 Å, and exhibits bond lengths and angles similar to those observed in isatin (Goldschmidt & Llewellyn, 1950). In the crystal, molecules dimerize through N1—H1···O1i hydrogen bonds (see Table 1 for symmetry code), which are further linked through I1···O2 close contacts [symmetry code needed here?] of 3.193 (4) Å, leading to infinite chains along [20Data 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).Fig. 1. The 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. | |
Fig. 2. The molecular packing of the title compound, with hydrogen bonding shown as dashed lines and iodine–oxygen interactions shown as thin solid lines. |
C8H4INO2 | F(000) = 512 |
Mr = 273.02 | Dx = 2.210 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54178 Å |
a = 4.0896 (3) Å | Cell parameters from 7596 reflections |
b = 13.2139 (10) Å | θ = 4.4–67.8° |
c = 15.1946 (11) Å | µ = 30.33 mm−1 |
β = 92.325 (4)° | T = 296 K |
V = 820.43 (10) Å3 | BLOCK, red |
Z = 4 | 0.2 × 0.1 × 0.08 mm |
Bruker D8 Venture CMOS diffractometer | 1479 independent reflections |
Radiation source: Cu | 1321 reflections with I > 2σ(I) |
HELIOS MX monochromator | Rint = 0.061 |
φ and ω scans | θmax = 68.1°, θmin = 4.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | h = −4→4 |
Tmin = 0.037, Tmax = 0.167 | k = −15→15 |
11737 measured reflections | l = −18→18 |
Refinement on F2 | 1 restraint |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.034 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.076 | w = 1/[σ2(Fo2) + (0.0197P)2 + 2.0314P] where P = (Fo2 + 2Fc2)/3 |
S = 1.12 | (Δ/σ)max = 0.001 |
1479 reflections | Δρmax = 0.48 e Å−3 |
113 parameters | Δρmin = −0.49 e Å−3 |
C8H4INO2 | V = 820.43 (10) Å3 |
Mr = 273.02 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 4.0896 (3) Å | µ = 30.33 mm−1 |
b = 13.2139 (10) Å | T = 296 K |
c = 15.1946 (11) Å | 0.2 × 0.1 × 0.08 mm |
β = 92.325 (4)° |
Bruker D8 Venture CMOS diffractometer | 1479 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | 1321 reflections with I > 2σ(I) |
Tmin = 0.037, Tmax = 0.167 | Rint = 0.061 |
11737 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 1 restraint |
wR(F2) = 0.076 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.12 | Δρmax = 0.48 e Å−3 |
1479 reflections | Δρmin = −0.49 e Å−3 |
113 parameters |
Experimental. Absorption correction: SADABS2014/4 (Bruker,2014/4) was used for absorption correction. wR2(int) was 0.1330 before and 0.0872 after correction. The Ratio of minimum to maximum transmission is 0.2240. The λ/2 correction factor is 0.00150. |
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 | ||
I1 | 0.19785 (10) | 0.18336 (3) | 0.57456 (2) | 0.05351 (16) | |
O1 | 0.7430 (14) | 0.5226 (3) | 0.4045 (3) | 0.0806 (16) | |
O2 | 0.9639 (13) | 0.3999 (3) | 0.2590 (3) | 0.0719 (14) | |
N1 | 0.5378 (14) | 0.3695 (3) | 0.4492 (3) | 0.0529 (12) | |
C1 | 0.6936 (17) | 0.4330 (4) | 0.3954 (4) | 0.0587 (16) | |
C2 | 0.8030 (16) | 0.3679 (4) | 0.3167 (3) | 0.0525 (14) | |
C3 | 0.6755 (14) | 0.2681 (4) | 0.3337 (3) | 0.0451 (12) | |
C4 | 0.6910 (18) | 0.1779 (4) | 0.2852 (4) | 0.0578 (16) | |
H4 | 0.7903 | 0.1760 | 0.2312 | 0.069* | |
C5 | 0.5550 (17) | 0.0925 (4) | 0.3200 (4) | 0.0617 (16) | |
H5 | 0.5622 | 0.0318 | 0.2891 | 0.074* | |
C6 | 0.4069 (16) | 0.0956 (4) | 0.4006 (4) | 0.0555 (14) | |
H6 | 0.3138 | 0.0370 | 0.4224 | 0.067* | |
C7 | 0.3947 (14) | 0.1848 (4) | 0.4495 (3) | 0.0439 (11) | |
C8 | 0.5242 (14) | 0.2709 (4) | 0.4142 (3) | 0.0430 (12) | |
H1 | 0.463 (13) | 0.387 (4) | 0.4997 (18) | 0.046 (15)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.0581 (3) | 0.0575 (2) | 0.0458 (2) | −0.00171 (17) | 0.01231 (16) | 0.00592 (15) |
O1 | 0.138 (5) | 0.041 (2) | 0.065 (3) | −0.007 (2) | 0.040 (3) | −0.0021 (18) |
O2 | 0.111 (4) | 0.051 (2) | 0.056 (2) | 0.002 (2) | 0.036 (3) | 0.0072 (18) |
N1 | 0.085 (4) | 0.040 (2) | 0.035 (2) | 0.004 (2) | 0.017 (2) | −0.0001 (18) |
C1 | 0.092 (5) | 0.040 (3) | 0.045 (3) | 0.000 (3) | 0.015 (3) | 0.000 (2) |
C2 | 0.076 (4) | 0.046 (3) | 0.036 (3) | 0.010 (3) | 0.010 (3) | 0.009 (2) |
C3 | 0.055 (4) | 0.045 (3) | 0.036 (2) | 0.008 (2) | 0.005 (2) | 0.003 (2) |
C4 | 0.084 (5) | 0.050 (3) | 0.040 (3) | 0.009 (3) | 0.008 (3) | −0.002 (2) |
C5 | 0.083 (5) | 0.046 (3) | 0.056 (3) | −0.001 (3) | 0.001 (3) | −0.013 (3) |
C6 | 0.068 (4) | 0.044 (3) | 0.054 (3) | −0.006 (3) | −0.001 (3) | −0.002 (2) |
C7 | 0.047 (3) | 0.045 (3) | 0.040 (2) | 0.003 (2) | 0.005 (2) | 0.005 (2) |
C8 | 0.053 (3) | 0.042 (3) | 0.034 (2) | 0.003 (2) | 0.005 (2) | 0.002 (2) |
I1—C7 | 2.094 (5) | C3—C8 | 1.395 (7) |
O1—C1 | 1.207 (7) | C4—H4 | 0.9300 |
O2—C2 | 1.196 (6) | C4—C5 | 1.373 (8) |
N1—C1 | 1.350 (7) | C5—H5 | 0.9300 |
N1—C8 | 1.408 (6) | C5—C6 | 1.389 (8) |
N1—H1 | 0.869 (5) | C6—H6 | 0.9300 |
C1—C2 | 1.553 (7) | C6—C7 | 1.395 (7) |
C2—C3 | 1.445 (8) | C7—C8 | 1.372 (7) |
C3—C4 | 1.404 (7) | ||
C1—N1—C8 | 111.0 (4) | C5—C4—H4 | 121.0 |
C1—N1—H1 | 124 (4) | C4—C5—H5 | 119.6 |
C8—N1—H1 | 125 (4) | C4—C5—C6 | 120.9 (5) |
O1—C1—N1 | 128.3 (5) | C6—C5—H5 | 119.6 |
O1—C1—C2 | 125.4 (5) | C5—C6—H6 | 119.3 |
N1—C1—C2 | 106.2 (4) | C5—C6—C7 | 121.4 (5) |
O2—C2—C1 | 123.5 (5) | C7—C6—H6 | 119.3 |
O2—C2—C3 | 131.9 (5) | C6—C7—I1 | 119.9 (4) |
C3—C2—C1 | 104.6 (4) | C8—C7—I1 | 122.0 (4) |
C4—C3—C2 | 131.1 (5) | C8—C7—C6 | 118.0 (5) |
C8—C3—C2 | 108.0 (4) | C3—C8—N1 | 110.1 (4) |
C8—C3—C4 | 121.0 (5) | C7—C8—N1 | 129.0 (4) |
C3—C4—H4 | 121.0 | C7—C8—C3 | 120.8 (5) |
C5—C4—C3 | 117.9 (5) | ||
I1—C7—C8—N1 | −3.2 (9) | C2—C3—C8—N1 | 2.1 (6) |
I1—C7—C8—C3 | 175.2 (4) | C2—C3—C8—C7 | −176.6 (5) |
O1—C1—C2—O2 | 4.0 (11) | C3—C4—C5—C6 | 0.0 (10) |
O1—C1—C2—C3 | −177.5 (7) | C4—C3—C8—N1 | −179.4 (6) |
O2—C2—C3—C4 | −2.8 (12) | C4—C3—C8—C7 | 1.9 (9) |
O2—C2—C3—C8 | 175.5 (7) | C4—C5—C6—C7 | −0.9 (10) |
N1—C1—C2—O2 | −175.9 (6) | C5—C6—C7—I1 | −175.7 (5) |
N1—C1—C2—C3 | 2.7 (7) | C5—C6—C7—C8 | 2.2 (9) |
C1—N1—C8—C3 | −0.2 (7) | C6—C7—C8—N1 | 178.9 (5) |
C1—N1—C8—C7 | 178.3 (6) | C6—C7—C8—C3 | −2.6 (9) |
C1—C2—C3—C4 | 178.9 (7) | C8—N1—C1—O1 | 178.6 (7) |
C1—C2—C3—C8 | −2.8 (6) | C8—N1—C1—C2 | −1.5 (7) |
C2—C3—C4—C5 | 177.6 (6) | C8—C3—C4—C5 | −0.5 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.87 (1) | 2.08 (2) | 2.915 (6) | 160 (5) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.869 (5) | 2.08 (2) | 2.915 (6) | 160 (5) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C8H4INO2 |
Mr | 273.02 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 4.0896 (3), 13.2139 (10), 15.1946 (11) |
β (°) | 92.325 (4) |
V (Å3) | 820.43 (10) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 30.33 |
Crystal size (mm) | 0.2 × 0.1 × 0.08 |
Data collection | |
Diffractometer | Bruker D8 Venture CMOS |
Absorption correction | Multi-scan (SADABS; Bruker, 2014) |
Tmin, Tmax | 0.037, 0.167 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11737, 1479, 1321 |
Rint | 0.061 |
(sin θ/λ)max (Å−1) | 0.602 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.076, 1.12 |
No. of reflections | 1479 |
No. of parameters | 113 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.48, −0.49 |
Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2014), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).
Acknowledgements
We greatly acknowledge support from the National Science Foundation (CHE-1429086).
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