Crystal structure of 1-ethyl-5-iodo­indolin-2-one

Zhang, M.; Shen, Y.-X.; Fang, Q.; Wang, L.; Li, D.-Z.

doi:10.1107/S2056989015009937

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ISSN: 2056-9890

Volume 71| Part 6| June 2015| Pages 712-715

doi:10.1107/S2056989015009937

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Crystal structure of 1-ethyl-5-iodoindolin-2-one

Man Zhang,^a Yu-Xiang Shen,^b Qi Fang,^b ^* Lei Wang ^a and Da-Zhi Li ^c

^aSchool of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, People's Republic of China, ^bState Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, People's Republic of China, and ^cBinzhou Key Laboratory of Material Chemistry, Department of Chemical Engineering, Binzhou University, Binzhou 256603, People's Republic of China
^*Correspondence e-mail: fangqi@sdu.edu.cn

Edited by M. Gdaniec, Adam Mickiewicz University, Poland (Received 7 April 2015; accepted 22 May 2015; online 28 May 2015)

In the title indolinone derivative, C₁₀H₁₀INO, all the non-H atoms, except the terminal methyl C atom, are almost coplanar. The molecules are arranged into columns extending along the a-axis direction and interact with the molecules in adjacent columns via C—H⋯O hydrogen bonds [H⋯O distance = 2.57 (3) Å] and I⋯I short contacts of 3.8986 (3) Å. A one-dimensional zigzag iodine chain along the a axis is apparent between two neighbouring columns.

Keywords: crystal structure; indolinone derivatives; hydrogen bonding; intermolecular interactions; dipole moment.

CCDC reference: 1028641

1. Chemical context

Indolinone derivatives play an important role in the pharmaceutical industry and some of them show antineoplastic (Cane et al., 2000 ), antibacterial (Kumar et al., 2013 ) and anti-inflammatory (Mammone et al., 2006 ) activities. The indolinone skeleton can be also found in many known bioactive drugs, such as horsfiline (Murphy et al., 2005 ), rhynchophylline (Deiters et al., 2006 ) and the gelsemium alkaloids (Kitajima et al., 2006 ). In addition, indolinone derivatives are widely used in the spice industry and agriculture, as functional materials (Ji et al., 2010 ) and dye intermediates.

In recent years, the synthesis and crystal structures of many indolinone derivatives have been reported including 6-chloro-5-(2-chloroethyl)oxindole (Nadkarni & Hallissey, 2008 ). We have recently synthesized and reported the crystal structures of several indolin-2-one derivatives including 1-phenyl-indolin-2-one (Wang et al., 2015 ). As a continuation of our work in this field, we report here the synthesis and crystal structure of the title compound, 1-ethyl-5-iodoindolin-2-one.

2. Structural commentary

The title molecule is shown in Fig. 1. The non-H atoms of the indoline core are virtually coplanar [mean deviation is 0.011 (3) Å with a maximum deviation of 0.023 (3) Å for C1]. The atoms C9, O1 and I1 are essentially co-planar with the indoline core, with deviations of 0.019 (4) Å for C9, 0.070 (3) Å for O1, and 0.127 (1) Å for I1. The sum of valence angles around N1 is 360.0°, indicating an sp² hybridization of this atom. The two C—N bonds in the five-membered ring have a partial double-bond character [N1 C1 1.370 (4) Å; N1 C8 1.400 (3) Å], indicating conjugation of the π-electrons of the NC=O group with the π-electrons of the benzene ring.

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

3. Supramolecular features

The crystal packing in the title compound is shown in Figs. 2 and 3. The molecules are face-to-face parallel-packed forming a column along the a axis with π–π interactions centroid–centroid distances = 4.130 (2) and 4.462 (2) Å]. Molecules from neighbouring columns are connected by a C—H⋯O hydrogen bond (Table 1) with the formation of a layer-type aggregate parallel to (001). There is an I⋯I contact shorter than the sum (3.96 Å) of the van der Waals radii [I⋯Iⁱ 3.8986 (3) Å, C—I⋯Iⁱ 173.3 (3)°; symmetry code: (i) x − $[{\script{1\over 2}}]$ , −y − $[{\script{1\over 2}}]$ , −z + 2] joining the columns of molecules in adjacent layers and forming a kind of 1-D zigzag chain along the a-axis direction (see Fig. 3). An important feature of the columns is that they are polar, i.e. all molecular dipole moments in the same column point in the same direction.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O1ⁱ	0.99 (3)	2.57 (4)	3.554 (4)	169 (3)
Symmetry code: (i) $[-x+3, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
The view of the structure along the a axis, showing the C—H⋯O hydrogen bond between columns and the I⋯I interactions between columns. [Symmetry codes: (i) −x + 3, y + $[{1\over 2}]$ , −z + $[{3\over 2}]$ ; (ii) −x + 3, y − $[{1\over 2}]$ , −z + $[{3\over 2}]$ ; (iii) x − $[{1\over 2}]$ , −y − $[{1\over 2}]$ , −z + 2.]

Figure 3
The view of the structure along the b axis, showing the one-dimensional columnar structure and the zigzag iodine chains along the a axis.

DFT/b3lyp/genecp calculations were carried out, which took the pseudopotential basis set LanL2DZ for the iodine atom and the 6–311g(d) basis set for the other atoms, to optimize the molecular geometry and calculate the dipole moment using the GAUSSIAN03 program (Frisch et al., 2003 ). The dipole moment of the title molecule (1.707 D) is much smaller than that of its precursor molecule, 1-ethyl-5-iodoindolin-2,3-dione (5.432 D). This difference may partly explain the non-centrosymmetry of the title crystal (space group P2₁2₁2₁) and the centrosymmetry of the crystal of the precursor (Wang et al.,2014 ). On the other hand, the non-centrosymmetry of the title crystal may be better explained by the I⋯I intermolecular interactions, for there are no I⋯I short contacts in the above centrosymmetric precursor crystal.

4. Database survey

A search of the Cambridge Structural Database (WebCSD, Version 5.36; last update April 2015; Groom & Allen, 2014 ) for 5-iodoindolin-2-one derivatives gave 15 hits. Of these 16 structures (with the title structure included), the number of non-centrosymmetric structures (9) is slightly greater than the number of centrosymmetric structures (7). In these 16 structures, there are four structures which exhibit I⋯I short intermolecular contacts and all the four structures are non-centrosymmetric (three of them belong to the P2₁2₁2₁ space group and the other one belongs to the P6₃ space group; Takahashi et al., 2014 ). Therefore, the I⋯I contacts seem to promote non-centrosymmetric packing in this kind of compound.

5. Synthesis and crystallization

The title compound was synthesized by reduction of the precursor with an 80% hydrazine hydrate (see reaction scheme) . 1-Ethyl-5-iodoindolin-2,3-dione precursor (1.714 g, 5.69 mmol) and 80% NH₂NH₂·H₂O (19.0 mL) were added into a 50 mL flask and the mixture was stirred under reflux. The reaction progress was tracked by TLC. After 4.5 h, the reaction mixture was cooled down and poured into 100 mL water with precipitation of yellow solid. Then the mixture was extracted with CH₂Cl₂, the organic phase was washed with water and dried with MgSO₄. The solvent was removed under reduced pressure and the crude product was purified by silica gel column chromatography with CHCl₃ as eluent. The title compound was obtained as a colorless solid (1.509 g, yield 92.3%). m.p. 403–404 K. Crystals suitable for X-ray diffraction were obtained by slow evaporation of a CHCl₃ solution.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms bound to aromatic C atoms and methylene C atoms were located in difference maps and freely refined, leading to C—H distances of 0.91 to 1.02 Å. The three H atoms bound to methyl C atoms could also be located in difference maps but they were placed at calculated positions and treated using a riding-model approximation with C—H = 0.96 Å and U_iso(H) = 1.5 U_eq(C).

Table 2
Experimental details

Crystal data
Chemical formula	C₁₀H₁₀INO
M_r	287.09
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	295
a, b, c (Å)	4.4622 (1), 8.2664 (2), 27.4400 (5)
V (Å³)	1012.16 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	3.12
Crystal size (mm)	0.42 × 0.32 × 0.16

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005 )
T_min, T_max	0.354, 0.635
No. of measured, independent and observed [I > 2σ(I)] reflections	12175, 2938, 2878
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.704

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.050, 1.21
No. of reflections	2938
No. of parameters	148
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.69
Absolute structure	Flack (1983 ), 1183 Friedel pairs
Absolute structure parameter	0.02 (2)
Computer programs: APEX2 and SAINT (Bruker, 2005), SHELXS97, SHELXL97 and SHELXTL (Sheldrick, 2008 ).

Supporting information

CCDC reference: 1028641

Crystal structure: contains datablock I. DOI: 10.1107/S2056989015009937/gk2630sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015009937/gk2630Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015009937/gk2630Isup3.cml

checkCIF report

Chemical context top

Indolinone derivatives play an important role in pharmaceutical industry and some of them show antineoplastic (Cane et al., 2000), antibacterial (Kumar et al., 2013) and anti-inflammatory (Mammone et al., 2006) activities. The indolinone skeleton can be also found in many known bioactive drugs, such as horsfiline (Murphy et al., 2005), rhynchophylline (Deiters et al., 2006) and the gelsemium alkaloids (Kitajima et al., 2006). In addition, indolinone derivatives are widely used in the spice industry and agriculture, as functional materials (Ji et al., 2010) and dye intermediates.

In recent years, the synthesis and crystal structures of many indolinone derivatives have been reported including 6-chloro-5-(2-chloroethyl)oxindole (Nadkarni & Hallissey, 2008). We have recently synthesized and reported the crystal structures of several indolin-2-one derivatives including 1-phenyl-indolin-2-one (Wang et al., 2015). As a continuation of our work in this field, we report here the synthesis and crystal structure of the title compound, 1-ethyl-5-iodoindolin-2-one.

Structural commentary top

The title molecule is shown in Fig. 1. The non-H atoms of the indoline core are virtually coplanar [mean deviation is 0.011 (3) Å with a maximum deviation of 0.023 (3) Å for C1]. The substituents C9, O1 and I1 are essentially co-planar with the indoline core, with deviations of 0.019 (4) Å for C9, 0.070 (3) Å for O1, and 0.127 (1) Å for I1. The sum of valence angles around N1 is 360.0°, indicating an sp² hybridization of this atom. The two C—N bonds in the five-membered ring have a partial double-bond character [N1≐ C1 1.370 (4) Å; N1≐C8 1.400 (3) Å) indicating conjugation of the π-electrons of the NC=O group with the π-electrons of the benzene ring.

Supramolecular features top

The crystal packing in the title compound is shown in Figs. 2 and 3. The molecules are face-to-face parallel-packed forming a one-dimensional column along the a axis with π–π interactions centroid–centroid distances = 4.130 (2) and 4.462 (2) Å]. Molecules from neighbouring columns are connected by a C—H···O hydrogen bond (Table 1) with the formation of a layer-type aggregate parallel to (001). There is an I···I contact shorter than the sum of van der Waals radii [I···I 3.8986 (3) Å, C—I···I 173.3 (3) °] joining the columns of molecules in adjacent layers and forming a kind of 1-D zigzag chain along the a-axis direction (see Fig. 3). An important feature of the columns is that they are polar, i.e. all molecular dipole moments in the same column point in the same direction.

DFT/b3lyp/genecp calculations were carried out, which took the pseudopotential basis set LanL2DZ for the iodine atom and the 6–311g(d) basis set for the other atoms, to optimize the molecular geometry and calculate the dipole moment using the GAUSSIAN03 program (Frisch et al., 2003). The dipole moment of the title molecule (1.707 D) is much smaller than that of its precursor molecule, 1-ethyl-5-iodoindolin-2,3-dione (5.432 D). This difference may partly explain the non-centrosymmetry of the title crystal (space group P2₁2₁2₁) and the centrosymmetry of the crystal of the precursor (Wang et al.,2014). On the other hand, the non-centrosymmetry of the title crystal may be better explained by the I···I intermolecular interactions, for there are no I···I short contacts in the above centrosymmetric precursor crystal.

Database survey top

A search of the Cambridge Structural Database (WebCSD, Version 5.36; last update April 2015; Groom & Allen, 2014) for 5-iodoindolin-2-one derivatives gave 15 hits. Of these 16 structures (with the title structure included), the number of non-centrosymmetric structures (9) is slightly greater than the number of centrosymmetric structures (7). In these 16 structures, there are four structures which exhibit I···I short intermolecular contacts and all the four structures are non-centrosymmetric (three of them belong to the P2₁2₁2₁ space group and the other one belongs to the P6₃ space group (Takahashi et al., 2014). Therefore, the I···I contacts seem to promote non-centrosymmetric packing in this kind of compound.

Synthesis and crystallization top

The title compound was synthesized by reduction of the precursor with an 80% hydrazine hydrate (see reaction scheme ). 1-Ethyl-5-iodoindolin-2,3-dione precursor (1.714 g, 5.69 mmol) and 80% NH₂NH₂·H₂O (19.0 mL) were added into a 50 mL flask and the mixture was stirred under reflux. The reaction progress was tracked by TLC. After 4.5 h, the reaction mixture was cooled down and poured into 100 mL water with precipitation of yellow solid. Then the mixture was extracted with CH₂Cl₂, the organic phase was washed with water and dried with MgSO₄. The solvent was removed under reduced pressure and the crude product was purified by silica gel column chromatography with CHCl₃ as eluent. The title compound was obtained as a colorless solid (1.509 g, yield 92.3%). m.p. 403–404 K. Crystals suitable for X-ray diffraction were obtained by slowly evaporation of CHCl₃ solution.

Refinement top

Related literature top

For related literature, see: Cane et al. (2000); Deiters et al. (2006); Durgesh & James (2008); Frisch et al. (2003); Groom & Allen (2014); Ji et al. (2010); Murphy et al. (2005); Kitajima et al. (2006); Kumar et al. (2013); Mammone et al. (2006); Takahashi et al. (2014); Wang et al. (2014, 2015).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The view of the structure along the a axis, showing the C—H···O hydrogen bond between columns and the I···I interactions between columns. [Symmetry codes: (i) -x + 3, y + 1/2, -z + 3/2; (ii) -x + 3, y - 1/2, -z + 3/2; (iii) x - 1/2, -y - 1/2, -z + 2.]
	Fig. 3. The view of the structure along the b axis, showing the one-dimensional columnar structure and the zigzag iodine chains along the a axis.

1-Ethyl-5-iodoindolin-2-one top

Crystal data top

C₁₀H₁₀INO	D_x = 1.884 Mg m⁻³
M_r = 287.09	Melting point = 403–404 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9948 reflections
a = 4.4622 (1) Å	θ = 2.5–30.0°
b = 8.2664 (2) Å	µ = 3.12 mm⁻¹
c = 27.4400 (5) Å	T = 295 K
V = 1012.16 (4) Å³	Parallelepiped, orange
Z = 4	0.42 × 0.32 × 0.16 mm
F(000) = 552

Data collection top

Bruker APEXII CCD diffractometer	2938 independent reflections
Radiation source: fine-focus sealed tube	2878 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
Detector resolution: 8.3 pixels mm^-1	θ_max = 30.0°, θ_min = 2.6°
ω scans	h = −6→6
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −11→9
T_min = 0.354, T_max = 0.635	l = −37→33
12175 measured reflections

Refinement top

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)] = 0.021	w = 1/[σ²(F_o²) + (0.0144P)² + 0.4592P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.050	(Δ/σ)_max = 0.002
S = 1.21	Δρ_max = 0.47 e Å⁻³
2938 reflections	Δρ_min = −0.69 e Å⁻³
148 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0014 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1183 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.02 (2)

Crystal data top

C₁₀H₁₀INO	V = 1012.16 (4) Å³
M_r = 287.09	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 4.4622 (1) Å	µ = 3.12 mm⁻¹
b = 8.2664 (2) Å	T = 295 K
c = 27.4400 (5) Å	0.42 × 0.32 × 0.16 mm

Data collection top

Bruker APEXII CCD diffractometer	2938 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2878 reflections with I > 2σ(I)
T_min = 0.354, T_max = 0.635	R_int = 0.020
12175 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.021	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.050	Δρ_max = 0.47 e Å⁻³
S = 1.21	Δρ_min = −0.69 e Å⁻³
2938 reflections	Absolute structure: Flack (1983), 1183 Friedel pairs
148 parameters	Absolute structure parameter: 0.02 (2)
0 restraints

Special details top

Experimental. Scan width 0.4° ω, Crystal to detector distance 6.20 cm, exposure time 20 s, 17 h for data collection

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
I1	0.57349 (4)	−0.10015 (2)	0.963176 (7)	0.05126 (7)
C5	0.7961 (6)	0.0703 (3)	0.91955 (9)	0.0404 (5)
O1	1.3877 (6)	0.3521 (3)	0.74792 (8)	0.0644 (7)
C4	0.8354 (6)	0.0383 (3)	0.87003 (10)	0.0410 (5)
C3	0.9948 (5)	0.1476 (3)	0.84294 (9)	0.0386 (6)
C8	1.1096 (6)	0.2881 (3)	0.86420 (9)	0.0394 (5)
N1	1.2652 (5)	0.3781 (3)	0.82916 (8)	0.0429 (5)
C9	1.4198 (8)	0.5309 (4)	0.83826 (12)	0.0505 (6)
C10	1.2102 (8)	0.6717 (4)	0.84543 (12)	0.0539 (7)
H10A	1.0772	0.6795	0.8180	0.081*
H10B	1.3242	0.7698	0.8482	0.081*
H10C	1.0955	0.6557	0.8746	0.081*
C1	1.2634 (7)	0.3027 (3)	0.78470 (10)	0.0472 (6)
C2	1.0825 (9)	0.1476 (3)	0.78985 (10)	0.0488 (6)
C7	1.0700 (8)	0.3218 (3)	0.91288 (10)	0.0456 (5)
C6	0.9096 (8)	0.2096 (4)	0.94064 (9)	0.0472 (6)
H2A	1.216 (8)	0.054 (4)	0.7827 (11)	0.053 (9)*
H2B	0.899 (12)	0.165 (5)	0.7685 (17)	0.103 (16)*
H4	0.754 (8)	−0.062 (4)	0.8534 (12)	0.058 (9)*
H6	0.884 (8)	0.234 (4)	0.9737 (11)	0.051 (9)*
H7	1.143 (7)	0.419 (4)	0.9266 (11)	0.053 (9)*
H9A	1.548 (9)	0.555 (4)	0.8089 (13)	0.067 (11)*
H9B	1.528 (10)	0.520 (5)	0.8662 (14)	0.075 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.05236 (10)	0.05416 (11)	0.04726 (10)	−0.00328 (9)	0.00305 (9)	0.01516 (8)
C5	0.0395 (12)	0.0407 (14)	0.0410 (12)	0.0021 (10)	0.0017 (10)	0.0086 (10)
O1	0.0785 (16)	0.0576 (13)	0.0570 (13)	−0.0032 (13)	0.0277 (13)	0.0062 (10)
C4	0.0445 (13)	0.0333 (12)	0.0451 (13)	0.0004 (9)	0.0016 (10)	0.0007 (10)
C3	0.0434 (14)	0.0350 (12)	0.0374 (12)	0.0044 (8)	0.0043 (9)	−0.0006 (9)
C8	0.0386 (12)	0.0356 (11)	0.0440 (12)	0.0026 (10)	0.0029 (10)	0.0009 (10)
N1	0.0479 (11)	0.0335 (11)	0.0473 (11)	−0.0035 (10)	0.0100 (10)	−0.0003 (9)
C9	0.0432 (13)	0.0488 (15)	0.0596 (17)	−0.0113 (14)	0.0002 (15)	0.0038 (12)
C10	0.0615 (18)	0.0403 (15)	0.0598 (17)	−0.0119 (14)	−0.0008 (15)	−0.0031 (13)
C1	0.0537 (16)	0.0393 (13)	0.0486 (15)	0.0047 (13)	0.0125 (13)	0.0039 (12)
C2	0.0664 (17)	0.0389 (13)	0.0412 (13)	−0.0003 (15)	0.0159 (15)	−0.0040 (10)
C7	0.0526 (14)	0.0414 (13)	0.0428 (13)	−0.0052 (14)	−0.0023 (13)	−0.0048 (10)
C6	0.0530 (14)	0.0538 (15)	0.0349 (12)	−0.0018 (15)	0.0015 (13)	0.0009 (11)

Geometric parameters (Å, º) top

I1—C5	2.099 (3)	C9—C10	1.506 (5)
C5—C6	1.384 (4)	C9—H9A	1.01 (4)
C5—C4	1.395 (4)	C9—H9B	0.91 (4)
O1—C1	1.222 (3)	C10—H10A	0.9600
C4—C3	1.369 (4)	C10—H10B	0.9600
C4—H4	1.02 (3)	C10—H10C	0.9600
C3—C8	1.397 (4)	C1—C2	1.521 (4)
C3—C2	1.508 (4)	C2—H2A	0.99 (3)
C8—C7	1.376 (4)	C2—H2B	1.02 (5)
C8—N1	1.400 (3)	C7—C6	1.398 (4)
N1—C1	1.370 (4)	C7—H7	0.95 (3)
N1—C9	1.461 (4)	C6—H6	0.94 (3)

C6—C5—C4	121.3 (2)	C9—C10—H10A	109.5
C6—C5—I1	119.53 (19)	C9—C10—H10B	109.5
C4—C5—I1	119.2 (2)	H10A—C10—H10B	109.5
C3—C4—C5	118.0 (3)	C9—C10—H10C	109.5
C3—C4—H4	118.8 (19)	H10A—C10—H10C	109.5
C5—C4—H4	123.3 (19)	H10B—C10—H10C	109.5
C4—C3—C8	120.8 (2)	O1—C1—N1	125.5 (3)
C4—C3—C2	131.2 (3)	O1—C1—C2	126.8 (3)
C8—C3—C2	108.0 (2)	N1—C1—C2	107.7 (2)
C7—C8—C3	121.8 (3)	C3—C2—C1	103.1 (2)
C7—C8—N1	128.5 (3)	C3—C2—H2A	110.2 (18)
C3—C8—N1	109.7 (2)	C1—C2—H2A	108 (2)
C1—N1—C8	111.5 (2)	C3—C2—H2B	110 (3)
C1—N1—C9	123.3 (2)	C1—C2—H2B	105 (3)
C8—N1—C9	125.2 (2)	H2A—C2—H2B	118 (3)
N1—C9—C10	113.4 (3)	C8—C7—C6	117.4 (3)
N1—C9—H9A	107 (2)	C8—C7—H7	121 (2)
C10—C9—H9A	108 (2)	C6—C7—H7	121.6 (19)
N1—C9—H9B	108 (3)	C5—C6—C7	120.8 (2)
C10—C9—H9B	107 (3)	C5—C6—H6	122 (2)
H9A—C9—H9B	113 (3)	C7—C6—H6	117 (2)

C6—C5—C4—C3	1.2 (4)	C8—N1—C1—O1	−178.2 (3)
I1—C5—C4—C3	−176.70 (19)	C9—N1—C1—O1	0.1 (5)
C5—C4—C3—C8	−1.1 (4)	C8—N1—C1—C2	1.3 (3)
C5—C4—C3—C2	178.5 (3)	C9—N1—C1—C2	179.6 (3)
C4—C3—C8—C7	0.5 (4)	C4—C3—C2—C1	−178.6 (3)
C2—C3—C8—C7	−179.1 (3)	C8—C3—C2—C1	1.0 (3)
C4—C3—C8—N1	179.4 (2)	O1—C1—C2—C3	178.1 (3)
C2—C3—C8—N1	−0.3 (3)	N1—C1—C2—C3	−1.4 (3)
C7—C8—N1—C1	178.0 (3)	C3—C8—C7—C6	0.0 (4)
C3—C8—N1—C1	−0.7 (3)	N1—C8—C7—C6	−178.6 (3)
C7—C8—N1—C9	−0.2 (5)	C4—C5—C6—C7	−0.7 (5)
C3—C8—N1—C9	−178.9 (3)	I1—C5—C6—C7	177.2 (2)
C1—N1—C9—C10	108.7 (3)	C8—C7—C6—C5	0.0 (5)
C8—N1—C9—C10	−73.2 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O1ⁱ	0.99 (3)	2.57 (4)	3.554 (4)	169 (3)

Symmetry code: (i) −x+3, y−1/2, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O1ⁱ	0.99 (3)	2.57 (4)	3.554 (4)	169 (3)

Symmetry code: (i) −x+3, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₀INO
M_r	287.09
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	295
a, b, c (Å)	4.4622 (1), 8.2664 (2), 27.4400 (5)
V (Å³)	1012.16 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.12
Crystal size (mm)	0.42 × 0.32 × 0.16

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.354, 0.635
No. of measured, independent and observed [I > 2σ(I)] reflections	12175, 2938, 2878
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.704

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.050, 1.21
No. of reflections	2938
No. of parameters	148
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.69
Absolute structure	Flack (1983), 1183 Friedel pairs
Absolute structure parameter	0.02 (2)

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by the National Science Foundation of China (grant Nos. 21472116 and 20972089).

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Volume 71| Part 6| June 2015| Pages 712-715

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