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

Golen, J.A.; Manke, D.R.

doi:10.1107/S2414314616004120

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 3| March 2016| x160412

doi:10.1107/S2414314616004120

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access

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

James A. Golen ^a and David R. Manke ^a ^*

^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 K. Fejfarova, Institute of Biotechnology CAS, Czech Republic (Received 4 March 2016; accepted 10 March 2016; online 15 March 2016)

The title compound, C₈H₄INO₂, has a single planar molecule in the asymmetric unit, 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

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Chemical scheme

Structure description

We report herein the crystal structure 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: (i) 1 + x, $[1\over2]$ − y, − $[1\over2]$ + z] of 3.193 (4) Å, leading to infinite chains along [20 $[\overline{1}]$ ]. 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.

Table 1
Hydrogen-bond geometry (Å, °)

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.

Figure 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.

Figure 2
The molecular packing of the title compound, with hydrogen bonding shown as dashed lines and iodine–oxygen interactions shown as thin solid lines.

Synthesis 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 refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₈H₄INO₂
M_r	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 )
T_min, T_max	0.037, 0.167
No. of measured, independent and observed [I > 2σ(I)] reflections	11737, 1479, 1321
R_int	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
Δρ_max, Δρ_min (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 ), publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1463777

Crystal structure: contains datablock I. DOI: 10.1107/S2414314616004120/ff4004sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616004120/ff4004Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616004120/ff4004Isup3.cml

checkCIF report

Experimental top

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1.

Results and discussion top

Experimental top

Structure description top

We report herein the crystal structure 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 [201]. 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.

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).

Figures top

	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.

7-Iodo-1H-indole-2,3-dione top

Crystal data top

C₈H₄INO₂	F(000) = 512
M_r = 273.02	D_x = 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

Data collection top

Bruker D8 Venture CMOS diffractometer	1479 independent reflections
Radiation source: Cu	1321 reflections with I > 2σ(I)
HELIOS MX monochromator	R_int = 0.061
φ and ω scans	θ_max = 68.1°, θ_min = 4.4°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −4→4
T_min = 0.037, T_max = 0.167	k = −15→15
11737 measured reflections	l = −18→18

Refinement top

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(F_o²) + (0.0197P)² + 2.0314P] where P = (F_o² + 2F_c²)/3
S = 1.12	(Δ/σ)_max = 0.001
1479 reflections	Δρ_max = 0.48 e Å⁻³
113 parameters	Δρ_min = −0.49 e Å⁻³

Crystal data top

C₈H₄INO₂	V = 820.43 (10) Å³
M_r = 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)°

Data collection top

Bruker D8 Venture CMOS diffractometer	1479 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2014)	1321 reflections with I > 2σ(I)
T_min = 0.037, T_max = 0.167	R_int = 0.061
11737 measured reflections

Refinement top

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	Δρ_max = 0.48 e Å⁻³
1479 reflections	Δρ_min = −0.49 e Å⁻³
113 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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.

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.037, 0.167
No. of measured, independent and observed [I > 2σ(I)] reflections	11737, 1479, 1321
R_int	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
Δρ_max, Δρ_min (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).

References

Bruker (2014). APEX2, SAINT, and SADABS. Bruker AXS Inc. Madison, Wisconsin, USA. Google Scholar
Dolomanov, 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
Garden, S. J., Pinto, A. C., Wardell, J. L., Low, J. N. & Glidewell, C. (2006). Acta Cryst. C62, o321–o323. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Goldschmidt, G. H. & Llewellyn, F. J. (1950). Acta Cryst. 3, 294–305. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Golen, J. A. & Manke, D. R. (2016a). IUCrData 1, x160215. Google Scholar
Golen, J. A. & Manke, D. R. (2016b). IUCrData 1, x160268. Google Scholar
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Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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IUCrDATA

ISSN: 2414-3146

Volume 1| Part 3| March 2016| x160412

doi:10.1107/S2414314616004120

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

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

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds