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

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

doi:10.1107/S2414314616002157

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 2| February 2016| x160215

https://doi.org/10.1107/S2414314616002157

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access

4-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 H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 3 February 2016; accepted 3 February 2016; online 10 February 2016)

The title compound, C₈H₄INO₂, is an almost planar molecule having an r.m.s. deviation of 0.03 Å for all non-H atoms. In the crystal, molecules dimerize through pairs of N—H⋯O hydrogen bonds. These inversion dimers are linked through pairs of weak I⋯O interactions [3.184 (4) Å] to form zigzag chains along [010]. The chains are linked in the c-axis direction by parallel-slipped π–π interactions [intercentroid distance = 3.623 (3) Å, interplanar distance = 3.423 (2) Å and slippage = 1.667 (5) Å], forming corrugated sheets parallel to (011).

Keywords: crystal structure; isatins; N—H⋯O hydrogen bonding; halogen–oxygen interactions; π–π interactions..

CCDC reference: 1451748

Structure description

Isatin molecules have found widespread use in organic synthesis and in pharmaceutical applications. We have an ongoing study of the solid state structure of halogenated isatins, and report herein on the crystal structure of 4-iodoisatin. The title compound, Fig. 1, exhibits a near planar molecule with the non-H atoms possessing a mean deviation from planarity of 0.03 Å. The observed bond lengths and angles are consistent with the parent isatin (Goldschmidt et al., 1950 ).

Figure 1
The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

In the crystal, pairs of N—H⋯O hydrogen bonds link the molecules to form inversion dimers (Table 1 and Fig. 2). The dimers are further linked into zigzag chains along [010] by pairs of weak I⋯O interactions [I1⋯O2ⁱ = 3.184 (4) Å; symmetry code (i): −x + 2, −y + 1, −z + 1]. Similar I⋯O interactions have been observed in 5-iodoisatin and its derivatives (Abid et al., 2008 ; Garden et al., 2006 ; Wang et al., 2014 ). The closely related 4-bromoisatin also exhibits a weak halogen–oxygen interaction in the solid state (Huang et al., 2016 ). The chains stack along [001] and are linked via parallel slipped π–π interactions [Cg2⋯Cg2ⁱⁱ = 3.699 (3) Å, where Cg2 is the centroid of ring C3–C8, inter-planar distance = 3.428 (2) Å, slippage = 1.383 Å, symmetry code (ii): x, −y + $[{3\over 2}]$ , z + $[{1\over 2}]$ ], leading to the formation of undulating sheets lying parallel to (011).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.87 (2)	2.05 (2)	2.910 (6)	173 (7)
Symmetry code: (i) -x+2, -y+2, -z+1.

Figure 2
The crystal packing of the title compound, viewed along the c-axis direction. The N—H⋯O hydrogen bonds (see Table 1

) and I⋯O interactions are shown as dashed lines.

Synthesis and crystallization

A commercial sample (Matrix Scientific) of 4-iodo-1H-indole-2,3-dione was used for crystallization. Orange rod-like crystals, suitable for X-ray diffraction analysis, were grown by slow evaporation of a solution in acetone.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The NH H atom was refined with U_iso(H) = 1.2U_eq(N).

Table 2
Experimental details

Crystal data
Chemical formula	C₈H₄INO₂
M_r	273.02
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	7.6138 (9), 13.9658 (17), 7.3866 (10)
β (°)	91.249 (5)
V (Å³)	785.25 (17)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	4.03
Crystal size (mm)	0.25 × 0.1 × 0.08

Data collection
Diffractometer	Bruker D8 Venture CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.182, 0.259
No. of measured, independent and observed [I > 2σ(I)] reflections	16058, 1491, 1268
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.611

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.082, 1.19
No. of reflections	1491
No. of parameters	112
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.95, −0.83
Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2014), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), OLEX2 (Dolomanov et al., 2009 ), Mercury (Macrae et al., 2008 ), publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1451748

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314616002157/su4013sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616002157/su4013Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616002157/su4013Isup3.cml

checkCIF report

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) and Mercury (Macrae et al., 2008); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

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

Crystal data top

C₈H₄INO₂	F(000) = 512
M_r = 273.02	D_x = 2.309 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.6138 (9) Å	Cell parameters from 7683 reflections
b = 13.9658 (17) Å	θ = 2.9–25.7°
c = 7.3866 (10) Å	µ = 4.03 mm⁻¹
β = 91.249 (5)°	T = 298 K
V = 785.25 (17) Å³	Rod, orange
Z = 4	0.25 × 0.1 × 0.08 mm

Data collection top

Bruker D8 Venture CMOS diffractometer	1268 reflections with I > 2σ(I)
Radiation source: Mo	R_int = 0.050
φ and ω scans	θ_max = 25.7°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −9→9
T_min = 0.182, T_max = 0.259	k = −17→17
16058 measured reflections	l = −9→9
1491 independent reflections

Refinement top

Refinement on F²	1 restraint
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.033	H-atom parameters constrained
wR(F²) = 0.082	w = 1/[σ²(F_o²) + (0.026P)² + 3.7223P] where P = (F_o² + 2F_c²)/3
S = 1.19	(Δ/σ)_max = 0.001
1491 reflections	Δρ_max = 0.95 e Å⁻³
112 parameters	Δρ_min = −0.83 e Å⁻³

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

	x	y	z	U_iso*/U_eq
I1	0.76809 (5)	0.52256 (3)	0.58699 (6)	0.03698 (15)
O1	1.1415 (6)	0.8920 (3)	0.4389 (7)	0.0440 (11)
O2	1.0723 (6)	0.6869 (3)	0.4540 (7)	0.0438 (11)
N1	0.8656 (7)	0.8997 (3)	0.5598 (7)	0.0349 (11)
H1	0.854 (9)	0.9613 (16)	0.561 (9)	0.042*
C1	1.0079 (8)	0.8563 (4)	0.4961 (8)	0.0334 (13)
C2	0.9695 (7)	0.7460 (4)	0.5078 (7)	0.0284 (12)
C3	0.7944 (7)	0.7395 (4)	0.5841 (7)	0.0242 (11)
C4	0.6850 (7)	0.6629 (4)	0.6254 (7)	0.0265 (11)
C5	0.5197 (7)	0.6816 (4)	0.6915 (8)	0.0320 (13)
H5	0.4451	0.6315	0.7211	0.038*
C6	0.4664 (8)	0.7758 (5)	0.7130 (8)	0.0369 (14)
H6	0.3549	0.7873	0.7571	0.044*
C7	0.5710 (8)	0.8532 (4)	0.6722 (8)	0.0350 (13)
H7	0.5316	0.9157	0.6859	0.042*
C8	0.7365 (7)	0.8335 (4)	0.6102 (7)	0.0268 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.0378 (2)	0.0255 (2)	0.0478 (3)	−0.00292 (17)	0.00400 (16)	0.00133 (19)
O1	0.039 (2)	0.029 (2)	0.064 (3)	−0.0036 (19)	0.013 (2)	0.003 (2)
O2	0.037 (2)	0.028 (2)	0.067 (3)	0.0010 (18)	0.015 (2)	0.000 (2)
N1	0.041 (3)	0.021 (2)	0.043 (3)	0.002 (2)	0.006 (2)	−0.001 (2)
C1	0.037 (3)	0.029 (3)	0.035 (3)	−0.001 (2)	0.003 (2)	0.001 (2)
C2	0.026 (3)	0.028 (3)	0.031 (3)	0.000 (2)	0.003 (2)	−0.001 (2)
C3	0.025 (3)	0.026 (3)	0.022 (3)	0.001 (2)	0.001 (2)	0.000 (2)
C4	0.034 (3)	0.026 (3)	0.019 (3)	−0.001 (2)	−0.003 (2)	0.000 (2)
C5	0.027 (3)	0.041 (3)	0.028 (3)	−0.003 (2)	0.003 (2)	−0.003 (3)
C6	0.032 (3)	0.053 (4)	0.026 (3)	0.008 (3)	0.004 (2)	−0.006 (3)
C7	0.035 (3)	0.035 (3)	0.034 (3)	0.010 (3)	0.001 (3)	−0.006 (3)
C8	0.032 (3)	0.028 (3)	0.021 (3)	−0.002 (2)	−0.002 (2)	−0.002 (2)

Geometric parameters (Å, º) top

I1—C4	2.081 (5)	C3—C8	1.399 (8)
O1—C1	1.216 (7)	C4—C5	1.385 (8)
O2—C2	1.211 (7)	C5—H5	0.9300
N1—H1	0.87 (2)	C5—C6	1.386 (9)
N1—C1	1.336 (8)	C6—H6	0.9300
N1—C8	1.406 (7)	C6—C7	1.380 (9)
C1—C2	1.571 (8)	C7—H7	0.9300
C2—C3	1.462 (7)	C7—C8	1.378 (8)
C3—C4	1.393 (8)

C1—N1—H1	123 (5)	C5—C4—C3	119.0 (5)
C1—N1—C8	111.8 (5)	C4—C5—H5	120.3
C8—N1—H1	125 (5)	C4—C5—C6	119.3 (5)
O1—C1—N1	128.8 (6)	C6—C5—H5	120.3
O1—C1—C2	125.4 (5)	C5—C6—H6	118.4
N1—C1—C2	105.8 (5)	C7—C6—C5	123.1 (6)
O2—C2—C1	121.9 (5)	C7—C6—H6	118.4
O2—C2—C3	133.3 (5)	C6—C7—H7	121.6
C3—C2—C1	104.8 (4)	C8—C7—C6	116.9 (5)
C4—C3—C2	133.4 (5)	C8—C7—H7	121.6
C4—C3—C8	119.9 (5)	C3—C8—N1	110.9 (5)
C8—C3—C2	106.7 (5)	C7—C8—N1	127.3 (5)
C3—C4—I1	120.5 (4)	C7—C8—C3	121.8 (5)
C5—C4—I1	120.5 (4)

I1—C4—C5—C6	−179.0 (4)	C2—C3—C8—N1	−1.5 (6)
O1—C1—C2—O2	−2.2 (10)	C2—C3—C8—C7	176.6 (5)
O1—C1—C2—C3	−179.8 (6)	C3—C4—C5—C6	0.7 (8)
O2—C2—C3—C4	1.6 (11)	C4—C3—C8—N1	−179.7 (5)
O2—C2—C3—C8	−176.3 (7)	C4—C3—C8—C7	−1.6 (8)
N1—C1—C2—O2	177.5 (6)	C4—C5—C6—C7	−0.2 (9)
N1—C1—C2—C3	−0.1 (6)	C5—C6—C7—C8	−1.1 (9)
C1—N1—C8—C3	1.5 (7)	C6—C7—C8—N1	179.8 (6)
C1—N1—C8—C7	−176.5 (6)	C6—C7—C8—C3	2.0 (8)
C1—C2—C3—C4	178.8 (6)	C8—N1—C1—O1	178.9 (6)
C1—C2—C3—C8	1.0 (6)	C8—N1—C1—C2	−0.8 (7)
C2—C3—C4—I1	2.2 (8)	C8—C3—C4—I1	179.8 (4)
C2—C3—C4—C5	−177.4 (6)	C8—C3—C4—C5	0.2 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.87 (2)	2.05 (2)	2.910 (6)	173 (7)

Symmetry code: (i) −x+2, −y+2, −z+1.

Acknowledgements

We gratefully acknowledge support from the National Science Foundation (CHE-1429086).

References

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IUCrDATA

ISSN: 2414-3146

Volume 1| Part 2| February 2016| x160215

https://doi.org/10.1107/S2414314616002157

Open

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

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

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds