Three 1-phenyl­indolin-2-one derivatives displaying different mol­ecular dipole moments and different crystallographic symmetries

Three 1-phenyl­indolin-2-one derivatives, namely 1-phenyl­indolin-2-one, C₁₄H₁₁NO, (I), 5-bromo-1-phenyl­indolin-2-one, C₁₄H₁₀BrNO, (II), and 5-iodo-1-phenyl­indolin-2-one, C₁₄H₁₀INO, (III), have been synthesized and their structures determined. Compounds (I) and (II) crystallized in the centrosymmetric space groups Pbca and P2₁/c, respectively, while compound (III) crystallized in the polar space group Aea2. Density functional theory (DFT) calculations show that the mol­ecular dipole moment gradually decreases in the order (I) > (II) > (III). The relatively smaller dipole moment of (III) and the larger non-electrostatic inter­molecular inter­actions may be the main reasons for the noncentrosymmetric and polar structure of (III).

S1. Introduction

Heterocyclic indolin-2-one and its derivatives have been well known for their wide-ranging applications in the pharmaceutical industry (Silva et al., 2001; Hibino & Choshi, 2002; Somei & Yamada, 2003; Gallagher et al., 1985; Ma et al., 2009) and in the field of functional materials (Ji et al., 2010). The indolin-2-one skeleton is a critical structural moiety in many known bioactive drugs, such as Horsfiline, Paraherqu­amide, Rhyncophylline and the Gelsemium alkaloids. Also, indolin-2-one derivatives are the key precursors in the synthesis of various functional materials, such as isoindigo (Lei et al., 2012), tri­indole (Zhu et al., 2012) and tetra­indole compounds (Wang, Li et al., 2014; OR Wang, Shen et al., 2014).

Although many indolin-2-one derivatives have been reported (Parrish et al., 2004; Usman et al., 2002; Wang, Li et al., 2014; OR Wang, Shen et al., 2014), there are only 20 structures of 1-aryl­indolin-2-one derivatives recorded in the Cambridge Structural Database (Version 5.35, update October 2014; Groom & Allen, 2014). Of these, the number (11) of centrosymmetric structures is slightly greater than the number (9) of noncentrosymmetric structures, and of the noncentrosymmetric structures, four have polar space groups. In this paper, we report the syntheses and structures of three 1-phenyl­indolin-2-one derivatives, namely, 1-phenyl­indolin-2-one, (I), 5-bromo-1-phenyl­indolin-2-one, (II), and 5-iodo-1-phenyl­indolin-2-one, (III).

S2. Experimental

S2.1. Synthesis and crystallization

The synthetic route for the title compounds is shown in Scheme 1. The precursor 2-chloro-N,N-di­phenyl­acetamide and (I) were synthesized according to the method reported by Shindikar et al. (2006).

S2.1.1. Synthesis of 2-chloro-N,N-di­phenyl­acetamide

A mixture of di­phenyl­amine (2.015 g, 12.0 mmol), chloro­acetyl chloride (2.0 ml, 26.6 mmol) and di­methyl­formamide (2.0 ml) was heated and stirred at 353 K for 2 h. After cooling to room temperature, water was added to precipitate the solid product, which was rinsed with a small amount of ethanol (yield 94.3%).

S2.1.2. Synthesis of 1-phenyl­indolin-2-one, (I)

2-Chloro-N,N-di­phenyl­acetamide (2.503 g, 10.18 mmol) and anhydrous AlCl₃ (3.111 g, 23.33 mmol) were added to a two-necked flask. The mixture was heated with mechanical stirring for 10 min at 358 K. After cooling to room temperature, crushed ice, hydro­chloric acid and CH₂Cl₂ were added to the flask in turn. The organic phase was separated and washed with 5% Na₂CO₃ solution and water separately. After drying over anhydrous Na₂SO₄ and removing the solvent, the residue was purified on a silica-gel column using petroleum ether–ethyl acetate (15:1 v/v) [OK?] as the eluent to obtain a colourless solid (yield 89.1%). ¹H NMR (400 MHz, CDCl₃): δ 7.53 (t, 2H, J = 7.7 Hz), 7.43–7.39 (m, 3H), 7.31 (d, 1H, J = 7.3 Hz), 7.20 (t, 1H, J = 7.8 Hz), 7.07 (t, 1H, J = 7.9 Hz), 6.79 (d, 1H, J = 7.9 Hz), 3.72 (s, 2H).

S2.1.3. Synthesis of 5-bromo-1-phenyl­indolin-2-one, (II)

Compound (I) (2.095 g, 10.01 mmol) was dissolved in aceto­nitrile (17 ml) and a solution of N-bromo­succinimide (NBS; 1.789 g, 10.05 mmol) in aceto­nitrile (15 ml) was added slowly dropwise at 273 K. The mixture was stirred for 90 min at 273 K and for 30 min at room temperature. After the solvent had been removed, the crude product was washed with water (30 × 2 ml) and ethanol (10 × 2 ml) separately, yielding a colourless powder (yield 2.692 g, 93.3%). ¹H NMR (400 MHz, CDCl₃): δ 7.53 (t, 2H, J = 7.6 Hz), 7.44–7.37 (m, 4H), 7.33 (d, 2H, J = 8.4 Hz), 6.66 (d, 1H, J = 8.4 Hz), 3.71 (s, 2H).

S2.1.4. Synthesis of 5-iodo-1-phenyl­indolin-2-one, (III)

Compound (I) (0.149 g, 0.71 mmol) and red HgO (0.156 g, 0.72 mmol) were dissolved in acetic acid (8 ml), and a solution of I₂ (0.092 g, 0.36 mmol) in acetic acid (15 ml) was added slowly. The mixture was stirred for 3 h at room temperature to form a flaxen suspension, which was treated with a saturated NaHSO₃ solution (~30 ml). The mixture was extracted with CH₂Cl₂ and the separated CH₂Cl₂ solution was dried over anhydrous Na₂SO₄. The solvent was removed and the crude product was purified by column chromatography using petroleum ether–ethyl acetate (15:1 v/v) [OK?] to obtain colourless plate-shaped crystals of (III) (yield 89.0%). ¹H NMR (400 MHz, CDCl₃): δ 7.62 (s, 1H), 7.53 (m, 3H), 7.42 (t, 1H, J = 7.4 Hz), 7.37 (d, 2H, J = 7.4 Hz), 6.57 (d, 1H, J = 8.3 Hz), 3.72 (s, 2H).

Crystals of (I), (II) and (III) suitable for X-ray diffraction were grown by slow evaporation of CH₂Cl₂ solutions at room temperature in the dark.

S2.2. Refinement

Crystal data, diffraction data and refinement details are summarized in Table 1. All H atoms in (I) and (II) were located from difference electron-density maps and were refined freely. For (III), most H atoms were found in difference electron-density maps and refined freely. Two aromatic H atoms were treated as riding on their parent C atoms.

S3. Results and discussion

S3.1. Molecular structures

The indoline cores (defined by the nine non-H atoms C1–C8/N1) of all three structures are perfect planar (Figs. 1–3). The sum of the angles around N atom is 359.98 (7)° for (I), 359.96 (13)° for (II) and 360.0 (3)° for (III), indicating the sp²-hybridized state of the N atom. As a consequence, atom C9 is coplanar with the indoline plane and the N1—C9 bond length is shorter than the length of a single C—N bond. The other two C—N bonds (N1—C1 and N1—C8) also display aromatic character, however, the C—C bonds (C1—C2 and C2—C3) in the five-membered heterocycle reatin the single-bond character. The N1—C1 bond length is shorter than the N1—C8 bond length in all three structures, which reflects the influence of the carbonyl group (Table 2).

As shown in Fig. 1, if there were no steric hindrance between atoms H7 and H10, we believe that the indoline plane and the phenyl plane would tend to be coplanar to form a larger π-system. However, as a balance between π-inter­action and steric repulsion, there exists a dihedral angle between the indoline plane and the phenyl plane of 56.10 (4)° in (I), 50.79 (7)° in (II) and 52.88 (16)° in (III). These angles are far from perpendicular and hence indicate certain π–π inter­actions between these two planes. A larger angle of 72.2 (1)° has been found in 1-(2,6-di­chloro­phenyl)­indolin-2-one (Hanif et al., 2009).

S3.2. Packing features

As shown in Fig. 4, the indoline plane of (I) is parallel to that of another centrosymmetrically related molecule at (-x+1, -y+1, -z+1), with the inter­planar spacing being 3.450 (1) Å. There are three C—H···O hydrogen bonds between one molecule and two adjacent molecules (Table 3).

As shown in Fig. 5, the molecules of (II) are packed into columns by π–π inter­actions along the a axis. Two neighbouring columns are related to one another by a symmetric inversion operation. For the two neighbouring parallel molecules in a column, the spacing between two indoline planes is 3.564 (2) Å and that between two phenyl-ring planes is 3.557 (2) Å. There are four C—H···O hydrogen bonds between one molecule and four neighbouring molecules. By these hydrogen bonds and π–π inter­actions, two-dimensional networks, parallel to the (010) plane, are constructed.

Compound (III) belongs to the polar Aea2 space group (formerly denoted Aba2), which is characterized by the double-glide. As shown in Fig. 6, the hydrogen bond C6—H6···O1(x+1, y, z) helps to build a one-dimensional chain along the a axis. Two such chains are further connected to form a ribbon by C10—H10···O1(x+1/2, -y+3/2, z) bonding and other short inter­molecular contacts, such as a 3.367 (4) Å contact of C7···C1(x+1/2, -y+3/2, z).

All the molecules in the same ribbon are oriented in the same direction, with all the C5—I1 bonds pointing in the [2.2,0,1] direction. In neighbouring ribbons, however, all molecules are oriented in another direction with the C5—I1 bonds pointing in the [-2.2,0,1] direction.

The [2.2,0,1] and [-2.2,0,1] ribbons (Fig. 7) are nested to construct the three-dimensional structure, in which all ribbons are extended along the a-axis direction. The same kind of ribbons, e.g. [2.2,0,1] ribbons, are connected by C13—H13···I1(x-1/2, -y+1, z-1/2) inter­actions (Table 3).

The electronic transfer integral (t) is a measure of the inter­molecular inter­action. It has been obtained by calculating the energy difference between HOMO (highest occupied molecular ortital) and HOMO-1 orbitals of a dimer (Deng & Goddard, 2004) and by the DFT/b3lyp/6-311g(d) method. As shown in Fig. 6, the two molecules of the dimer-in-ribbon are related to each other by the a-glide and short contacts with the t value being 0.092 eV; the two molecules of the dimer-between-ribbon are related by the twofold rotation and π–π inter­actions [3.454 (5) Å between indoline planes], with a t value of 0.0047 eV. Actually, the much stronger dimer-in-ribbon inter­actions and the C6—H6···O1(x+1, y, z) hydrogen bond link such dimers are the factual reasons of drawing the `ribbon' from the structure.

The three title compounds have similar molecular units. However, why has the space-group symmetry changed from the centrosymmetric Pbca in (I) and P2₁/c in (II) to the Aea2 polar space group in (III)? We invoked a molecular calculation to answer this question.

S3.3. The molecular dipole moment and the crystallographic symmetry

Density functional theory (DFT) calculations were carried out to acquire the molecular dipole moments using the GAUSSIAN03 program (Frisch et al., 2003). The five molecules listed in Table 4 have different substituent groups at the 5-position of the 1-phenyl­indolin-2-one core. Methyl-substituted (the electron-donating group) (IV) and chlorine-substituted (the electron-withdrawing atom) (V) are the reference molecules, and neither of these have records in the Cambridge Structural Database (Groom & Allen, 2014) and so have been designed and geometrically optimized.

For (I) and (IV), the b3lyp/6–311g(d) method was adopted. For (III), because of the unavailability of the common basis sets for the heavy I atom, the b3lyp/genecp method was adopted, which took the pseudopotential basis set LanL2DZ for the I atom and the 6–311g(d) basis set for the other atoms. For (II) and (V), both b3lyp/6–311g(d) and b3lyp/genecp (LanL2DZ for Br and Cl atoms) methods were used. In order to check the consistency and reliability of the results, 6–311g(d) and 6–31g(d) basis sets were used separately for the non-halogen atoms of (II), (III) and (V) in the b3lyp/genecp method. The results in Table 4 indicate that the dipole moments consistently decrease from the upper value for methyl-substited (IV) to the lower value for iodine-substited (III).

Generally, the inter­molecular inter­actions in a neutral organic crystal can be classified as electrostatic dipole–dipole inter­actions and non-electrostatic chemical inter­actions, such as π–π inter­actions, hydrogen bonding and other short inter­molecular contacts. The dipole–dipole inter­actions always tend to form an anti­parallel centrosymmetric molecular aggregation (with the neighbouring dipole moment pointing in the opposite direction) to minimize the electrostatic potential. On the other hand, the non-electrostatic chemical inter­actions in the title 1-phenyl­indolin-2-one derivatives may tend to break the electrostatic anti­parallel lock and to noncentrosymmetrically pack the molecules. In short, the resultant packing symmetry (centrosymmetry or noncentrosymmetry) would be the balance between the above electrostatic inter­actions and the non-electrostatic inter­actions.

In fact, the non-electrostatic inter­actions in (III) are so strong that they line up all the molecular dipole moments in a ribbon in the same direction (Fig. 6). Two molecules of a dimer-between-ribbon are also noncentrosymmetrically oriented (Fig. 6). Note that the dipole–dipole inter­action energy is proportional to the fourth power of the dipole moment. The slightly lower dipole moment of (III), relative to that of (II), can remarkably weaken the electrostatic inter­actions in (III). On the other hand, due to the more numerous and intense short non-H-atom inter­molecular contacts in (III), the non-electrostatic inter­actions in (III) are stronger than those in (II) and (I). This may be the main reason why (III) is noncentrosymmetric while (II) and (I) are centrosymmetric.

The calculated dipole moment of (III) is approximately along the direction of the C3 → C7 vector, which is about 51 (2)° from the c axix (the direction of the macro polarization).

As we know, noncentrosymmetry is the necessary structural condition for the frequency doubling effect of molecules and crystals. Indeed, we have observed green 532 nm light from the powder sample of (III) when irradiated with 1064 nm laser pulses. However, there was no dete­cta­ble frequency-doubling effect for compounds (I) and (II).

S4. Conclusions

In conclusion, the novelty of compound (III) is its parallel ribbon structure and the polar Aea2 symmetry, which gives rise to a second-order nonlinear optical effect (frequency doubling). The relatively smaller dipole moment of (III) and the larger non-electrostatic inter­molecular inter­actions may be the main reasons for the noncentrosymmetric and polar structure of (III).

Computing details

For all compounds, 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), PLATON (Spek, 2009) and Mercury (Macrae et al., 2006).

Figures

	Fig. 1. The asymmetric unit of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The asymmetric unit of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 3. The asymmetric unit of (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 4. The crystal structure of (I), showing C—H···O hydrogen bonding and π–π interactions. [Symmetry code: (i) -x+1, -y, -z+1; (ii) -x+1/2, y+1/2, z.]
	Fig. 5. The crystal structure of (II), showing C—H···O hydrogen bonding, π–π and interactions and the two-dimensional network structure. [Symmetry code: (i) x-1, -y+1/2, z-1/2; (ii) x, -y+1/2, z-1/2; (iii) x+1, -y+1/2, z+1/2; (iv) x, -y+1/2, z+1/2.]
	Fig. 6. The crystal structure of (III), showing various interactions in a ribbon of the double chain. The two kinds of ribbons can be recognized by the orientations of the C—I bonds, which are along [2.2,0,1] in one kind of ribbon and along [-2.2,0,1] in the other kind of ribbon. [Symmetry code: (i) x+1, y, z; (ii) x+1/2, -y+3/2, z; (iii) x-1/2, -y+3/2, z; (iv) x-1, y, z.]
	Fig. 7. A view along the a axis of the crystal structure of (III), showing the C—H···I and other intermolecular interactions. Two kinds of ribbons, differentiated by their colours, are all extended along the a-axis direction and nested together to form the three-dimensional structure.

(I) 1-Phenylindolin-2-one

Crystal data

C14H11NO	F(000) = 880
Mr = 209.24	Dx = 1.317 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 9992 reflections
a = 13.4478 (2) Å	θ = 3.0–30.6°
b = 7.9458 (1) Å	µ = 0.08 mm^−1
c = 19.7535 (3) Å	T = 130 K
V = 2110.73 (5) Å^3	Prism, colourless
Z = 8	0.52 × 0.43 × 0.21 mm

Data collection

Bruker APEXII CCD diffractometer	3189 independent reflections
Radiation source: fine-focus sealed tube	2826 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: 8.3 pixels mm^-1	θmax = 30.6°, θmin = 2.1°
ϕ and ω scans	h = −19→19
Absorption correction: multi-scan (APEX2; Bruker, 2005)	k = −8→11
Tmin = 0.958, Tmax = 0.983	l = −25→27
28368 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	All H-atom parameters refined
wR(F^2) = 0.121	w = 1/[σ^2(Fo^2) + (0.0783P)^2 + 0.3192P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
3189 reflections	Δρmax = 0.40 e Å^−3
190 parameters	Δρmin = −0.22 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0058 (13)

Special details

Experimental. Scan width 0.5° ω, Crystal to detector distance 5.96 cm,exposure time 10 s, about 10 h for data collection, with scale.

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.41852 (5)	0.03620 (8)	0.40114 (3)	0.02930 (17)
N1	0.38192 (5)	0.32024 (8)	0.40425 (3)	0.02164 (16)
C5	0.35867 (7)	0.64126 (12)	0.56937 (5)	0.0288 (2)
C4	0.37667 (7)	0.46870 (11)	0.57634 (4)	0.02603 (19)
C3	0.38318 (6)	0.37082 (10)	0.51854 (4)	0.02061 (17)
C8	0.37146 (6)	0.44470 (10)	0.45488 (4)	0.02007 (17)
C9	0.37295 (6)	0.35261 (11)	0.33347 (4)	0.02423 (18)
C14	0.45018 (8)	0.31109 (13)	0.28977 (5)	0.0324 (2)
C13	0.44158 (10)	0.35112 (15)	0.22139 (5)	0.0425 (3)
C12	0.35751 (11)	0.43120 (15)	0.19736 (5)	0.0477 (3)
C7	0.35551 (6)	0.61577 (10)	0.44682 (4)	0.02468 (18)
C6	0.34926 (6)	0.71285 (11)	0.50560 (5)	0.02786 (19)
C1	0.40344 (6)	0.16541 (10)	0.43270 (4)	0.02159 (17)
C2	0.40227 (6)	0.18683 (10)	0.50925 (4)	0.02169 (17)
C10	0.28729 (8)	0.42958 (13)	0.30941 (5)	0.0340 (2)
C11	0.28029 (11)	0.46979 (15)	0.24097 (6)	0.0469 (3)
H4	0.3856 (10)	0.4195 (18)	0.6211 (7)	0.036 (3)*
H7	0.3492 (11)	0.6695 (19)	0.4004 (7)	0.043 (4)*
H6	0.3375 (10)	0.8340 (18)	0.5010 (7)	0.038 (3)*
H5	0.3525 (10)	0.7164 (18)	0.6102 (7)	0.037 (3)*
H14	0.5085 (10)	0.2546 (18)	0.3082 (7)	0.039 (3)*
H13	0.4981 (12)	0.323 (2)	0.1920 (9)	0.059 (4)*
H12	0.3515 (12)	0.463 (2)	0.1477 (9)	0.055 (4)*
H11	0.2188 (13)	0.525 (2)	0.2242 (9)	0.064 (5)*
H10	0.2319 (12)	0.4564 (18)	0.3404 (8)	0.048 (4)*
H2A	0.4653 (9)	0.1472 (17)	0.5272 (6)	0.031 (3)*
H2B	0.3487 (9)	0.1183 (17)	0.5279 (6)	0.030 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0390 (4)	0.0212 (3)	0.0276 (3)	0.0046 (2)	0.0001 (3)	−0.0034 (2)
N1	0.0271 (3)	0.0192 (3)	0.0186 (3)	0.0021 (2)	0.0006 (2)	0.0006 (2)
C5	0.0271 (4)	0.0269 (4)	0.0325 (4)	0.0009 (3)	−0.0015 (3)	−0.0096 (3)
C4	0.0267 (4)	0.0277 (4)	0.0237 (4)	0.0010 (3)	−0.0010 (3)	−0.0041 (3)
C3	0.0199 (3)	0.0200 (3)	0.0219 (4)	−0.0002 (3)	0.0004 (3)	−0.0003 (3)
C8	0.0198 (3)	0.0180 (3)	0.0224 (4)	−0.0006 (2)	0.0010 (3)	−0.0005 (3)
C9	0.0315 (4)	0.0222 (4)	0.0190 (4)	−0.0009 (3)	0.0001 (3)	0.0012 (3)
C14	0.0350 (5)	0.0364 (5)	0.0259 (4)	−0.0023 (4)	0.0048 (3)	−0.0026 (3)
C13	0.0590 (7)	0.0445 (6)	0.0241 (4)	−0.0093 (5)	0.0113 (4)	−0.0029 (4)
C12	0.0836 (9)	0.0388 (6)	0.0207 (4)	−0.0035 (5)	−0.0034 (5)	0.0034 (4)
C7	0.0252 (4)	0.0187 (3)	0.0302 (4)	0.0004 (3)	0.0013 (3)	0.0021 (3)
C6	0.0245 (4)	0.0190 (3)	0.0401 (5)	−0.0001 (3)	0.0004 (3)	−0.0044 (3)
C1	0.0228 (4)	0.0188 (3)	0.0231 (4)	0.0009 (3)	0.0001 (3)	0.0009 (3)
C2	0.0250 (4)	0.0192 (3)	0.0208 (3)	0.0014 (3)	−0.0001 (3)	0.0022 (3)
C10	0.0418 (5)	0.0346 (5)	0.0255 (4)	0.0090 (4)	−0.0044 (4)	0.0005 (3)
C11	0.0705 (8)	0.0413 (6)	0.0288 (5)	0.0136 (5)	−0.0152 (5)	0.0025 (4)

Geometric parameters (Å, º)

O1—C1	1.2181 (10)	C14—H14	0.974 (14)
N1—C1	1.3831 (10)	C13—C12	1.3814 (19)
N1—C8	1.4134 (10)	C13—H13	0.983 (17)
N1—C9	1.4268 (10)	C12—C11	1.3837 (19)
C5—C6	1.3881 (14)	C12—H12	1.016 (17)
C5—C4	1.3992 (13)	C7—C6	1.3965 (12)
C5—H5	1.007 (14)	C7—H7	1.016 (15)
C4—C3	1.3842 (11)	C6—H6	0.979 (14)
C4—H4	0.974 (14)	C1—C2	1.5216 (11)
C3—C8	1.3967 (11)	C2—H2A	0.971 (13)
C3—C2	1.4956 (11)	C2—H2B	0.975 (13)
C8—C7	1.3853 (11)	C10—C11	1.3923 (14)
C9—C10	1.3882 (13)	C10—H10	0.988 (16)
C9—C14	1.3902 (12)	C11—H11	0.992 (18)
C14—C13	1.3923 (14)
C1—N1—C8	110.83 (7)	C13—C12—C11	120.15 (9)
C1—N1—C9	125.18 (7)	C13—C12—H12	120.8 (9)
C8—N1—C9	123.98 (7)	C11—C12—H12	119.1 (9)
C6—C5—C4	120.44 (8)	C8—C7—C6	117.11 (8)
C6—C5—H5	118.5 (8)	C8—C7—H7	122.0 (8)
C4—C5—H5	121.1 (8)	C6—C7—H7	120.9 (8)
C3—C4—C5	118.72 (8)	C5—C6—C7	121.52 (8)
C3—C4—H4	121.0 (8)	C5—C6—H6	120.0 (8)
C5—C4—H4	120.2 (8)	C7—C6—H6	118.4 (8)
C4—C3—C8	119.95 (8)	O1—C1—N1	125.21 (8)
C4—C3—C2	131.40 (8)	O1—C1—C2	127.20 (7)
C8—C3—C2	108.65 (7)	N1—C1—C2	107.58 (7)
C7—C8—C3	122.23 (7)	C3—C2—C1	103.48 (6)
C7—C8—N1	128.36 (7)	C3—C2—H2A	115.0 (8)
C3—C8—N1	109.37 (7)	C1—C2—H2A	108.5 (7)
C10—C9—C14	120.79 (8)	C3—C2—H2B	111.9 (8)
C10—C9—N1	119.02 (8)	C1—C2—H2B	108.7 (7)
C14—C9—N1	120.18 (8)	H2A—C2—H2B	109.0 (10)
C9—C14—C13	119.08 (10)	C9—C10—C11	119.32 (10)
C9—C14—H14	118.5 (8)	C9—C10—H10	120.6 (9)
C13—C14—H14	122.4 (8)	C11—C10—H10	120.1 (9)
C12—C13—C14	120.44 (10)	C12—C11—C10	120.19 (11)
C12—C13—H13	122.4 (10)	C12—C11—H11	121.0 (10)
C14—C13—H13	117.1 (10)	C10—C11—H11	118.8 (10)
C6—C5—C4—C3	−1.07 (13)	C14—C13—C12—C11	−1.10 (18)
C5—C4—C3—C8	−0.25 (12)	C3—C8—C7—C6	−1.40 (12)
C5—C4—C3—C2	179.39 (8)	N1—C8—C7—C6	−179.07 (8)
C4—C3—C8—C7	1.53 (12)	C4—C5—C6—C7	1.19 (14)
C2—C3—C8—C7	−178.19 (7)	C8—C7—C6—C5	0.04 (13)
C4—C3—C8—N1	179.59 (7)	C8—N1—C1—O1	−178.29 (8)
C2—C3—C8—N1	−0.12 (9)	C9—N1—C1—O1	0.69 (13)
C1—N1—C8—C7	176.08 (8)	C8—N1—C1—C2	2.96 (9)
C9—N1—C8—C7	−2.92 (13)	C9—N1—C1—C2	−178.06 (7)
C1—N1—C8—C3	−1.84 (9)	C4—C3—C2—C1	−177.88 (8)
C9—N1—C8—C3	179.17 (7)	C8—C3—C2—C1	1.79 (8)
C1—N1—C9—C10	126.50 (10)	O1—C1—C2—C3	178.42 (8)
C8—N1—C9—C10	−54.64 (12)	N1—C1—C2—C3	−2.85 (8)
C1—N1—C9—C14	−55.05 (12)	C14—C9—C10—C11	−1.88 (15)
C8—N1—C9—C14	123.80 (9)	N1—C9—C10—C11	176.55 (9)
C10—C9—C14—C13	1.41 (14)	C13—C12—C11—C10	0.62 (19)
N1—C9—C14—C13	−177.01 (9)	C9—C10—C11—C12	0.86 (18)
C9—C14—C13—C12	0.09 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O1^i	0.971 (13)	2.563 (13)	3.4760 (10)	156.7 (10)
C10—H10···O1^ii	0.988 (16)	2.436 (16)	3.4148 (13)	171.1 (12)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1/2, y+1/2, z.

(II) 5-Bromo-1-phenylindolin-2-one

Crystal data

C14H10BrNO	F(000) = 576
Mr = 288.14	Dx = 1.705 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9935 reflections
a = 3.9581 (1) Å	θ = 2.4–29.8°
b = 21.5740 (7) Å	µ = 3.64 mm^−1
c = 13.2045 (4) Å	T = 135 K
β = 95.287 (2)°	Bar, colourless
V = 1122.76 (6) Å^3	0.29 × 0.09 × 0.08 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer	3536 independent reflections
Radiation source: fine-focus sealed tube	2936 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
Detector resolution: 8.3 pixels mm^-1	θmax = 31.1°, θmin = 1.9°
ω scans	h = −5→5
Absorption correction: multi-scan (APEX2; Bruker, 2005)	k = −30→31
Tmin = 0.414, Tmax = 0.757	l = −18→18
32332 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.028	Hydrogen site location: difference Fourier map
wR(F^2) = 0.067	All H-atom parameters refined
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0333P)^2 + 0.4409P] where P = (Fo^2 + 2Fc^2)/3
3536 reflections	(Δ/σ)max = 0.002
195 parameters	Δρmax = 0.41 e Å^−3
0 restraints	Δρmin = −0.36 e Å^−3

Special details

Experimental. Scan width 0.3° ω, Crystal to detector distance 5.96 cm,exposure time 25 s, about 41 h for data collection, with scale. The results of the refinement can be slightly improved by adding the following twin-law to the INS file: TWIN 1 0 0 0 - 1 0 0 0 - 1. The BASF parameter has been refined to 0.00078.

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 (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.37477 (4)	0.494214 (7)	0.768791 (14)	0.02916 (6)
C10	0.9050 (4)	0.16924 (8)	1.05243 (12)	0.0250 (3)
O1	1.3208 (3)	0.27438 (6)	1.15503 (9)	0.0324 (3)
C5	0.5615 (4)	0.42292 (7)	0.83804 (12)	0.0217 (3)
C6	0.5340 (4)	0.36616 (7)	0.78970 (12)	0.0215 (3)
C7	0.6758 (4)	0.31344 (7)	0.83820 (11)	0.0204 (3)
C8	0.8377 (4)	0.32013 (7)	0.93496 (11)	0.0183 (3)
N1	0.9999 (3)	0.27481 (6)	0.99938 (9)	0.0200 (2)
C9	1.0081 (4)	0.20973 (7)	0.97955 (11)	0.0199 (3)
C14	1.1206 (4)	0.18732 (8)	0.88999 (12)	0.0239 (3)
C13	1.1338 (5)	0.12373 (8)	0.87464 (13)	0.0295 (3)
C12	1.0362 (5)	0.08316 (8)	0.94771 (15)	0.0335 (4)
C1	1.1453 (4)	0.30112 (7)	1.08848 (12)	0.0231 (3)
C2	1.0482 (4)	0.36947 (7)	1.08668 (12)	0.0247 (3)
C3	0.8620 (4)	0.37773 (7)	0.98350 (11)	0.0203 (3)
C4	0.7246 (4)	0.42993 (7)	0.93550 (12)	0.0230 (3)
C11	0.9206 (5)	0.10593 (8)	1.03598 (14)	0.0318 (4)
H4	0.737 (5)	0.4683 (10)	0.9667 (15)	0.027 (5)*
H7	0.657 (5)	0.2743 (9)	0.8035 (14)	0.027 (5)*
H6	0.422 (5)	0.3607 (9)	0.7230 (16)	0.032 (5)*
H14	1.182 (5)	0.2152 (9)	0.8382 (14)	0.024 (5)*
H10	0.812 (5)	0.1878 (9)	1.1141 (15)	0.031 (5)*
H11	0.845 (5)	0.0771 (9)	1.0878 (16)	0.036 (6)*
H12	1.050 (5)	0.0401 (11)	0.9387 (16)	0.038 (6)*
H13	1.207 (5)	0.1086 (9)	0.8123 (15)	0.029 (5)*
H2A	1.256 (5)	0.3938 (9)	1.1002 (15)	0.033 (5)*
H2B	0.912 (5)	0.3760 (9)	1.1410 (15)	0.027 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.02857 (9)	0.02264 (9)	0.03505 (11)	0.00304 (6)	−0.00356 (7)	0.00598 (6)
C10	0.0296 (8)	0.0262 (8)	0.0192 (8)	0.0010 (6)	0.0027 (6)	0.0033 (6)
O1	0.0390 (7)	0.0361 (7)	0.0202 (6)	0.0103 (5)	−0.0074 (5)	−0.0015 (5)
C5	0.0195 (7)	0.0211 (7)	0.0242 (8)	0.0013 (5)	0.0008 (5)	0.0043 (6)
C6	0.0210 (7)	0.0250 (7)	0.0181 (7)	−0.0018 (5)	−0.0005 (5)	0.0008 (6)
C7	0.0239 (7)	0.0193 (7)	0.0179 (7)	−0.0026 (5)	0.0006 (5)	−0.0004 (5)
C8	0.0190 (6)	0.0193 (6)	0.0169 (7)	−0.0009 (5)	0.0026 (5)	0.0013 (5)
N1	0.0248 (6)	0.0195 (6)	0.0155 (6)	0.0011 (4)	−0.0001 (5)	0.0007 (4)
C9	0.0216 (7)	0.0205 (7)	0.0172 (7)	0.0012 (5)	−0.0001 (5)	0.0007 (5)
C14	0.0273 (8)	0.0255 (8)	0.0188 (7)	0.0006 (6)	0.0015 (6)	0.0010 (6)
C13	0.0372 (9)	0.0275 (8)	0.0229 (9)	0.0057 (7)	−0.0022 (7)	−0.0048 (6)
C12	0.0458 (11)	0.0210 (8)	0.0314 (10)	0.0035 (7)	−0.0083 (8)	−0.0014 (7)
C1	0.0250 (7)	0.0272 (7)	0.0171 (7)	0.0027 (6)	0.0015 (6)	−0.0016 (6)
C2	0.0274 (8)	0.0263 (8)	0.0192 (8)	0.0026 (6)	−0.0031 (6)	−0.0053 (6)
C3	0.0196 (7)	0.0228 (7)	0.0184 (7)	−0.0003 (5)	0.0006 (5)	−0.0018 (5)
C4	0.0230 (7)	0.0196 (7)	0.0262 (8)	0.0004 (5)	0.0007 (6)	−0.0026 (6)
C11	0.0405 (10)	0.0259 (8)	0.0279 (9)	−0.0015 (7)	−0.0033 (7)	0.0082 (7)

Geometric parameters (Å, º)

Br1—C5	1.9036 (15)	C9—C14	1.388 (2)
C10—C11	1.385 (2)	C14—C13	1.388 (2)
C10—C9	1.388 (2)	C14—H14	0.958 (19)
C10—H10	1.01 (2)	C13—C12	1.384 (3)
O1—C1	1.2146 (19)	C13—H13	0.96 (2)
C5—C6	1.381 (2)	C12—C11	1.381 (3)
C5—C4	1.394 (2)	C12—H12	0.94 (2)
C6—C7	1.397 (2)	C1—C2	1.524 (2)
C6—H6	0.96 (2)	C2—C3	1.499 (2)
C7—C8	1.383 (2)	C2—H2A	0.98 (2)
C7—H7	0.961 (19)	C2—H2B	0.947 (19)
C8—C3	1.397 (2)	C3—C4	1.379 (2)
C8—N1	1.4110 (18)	C4—H4	0.92 (2)
N1—C1	1.3830 (19)	C11—H11	0.99 (2)
N1—C9	1.429 (2)
C11—C10—C9	119.44 (15)	C12—C13—C14	120.43 (16)
C11—C10—H10	123.0 (12)	C12—C13—H13	120.7 (12)
C9—C10—H10	117.5 (12)	C14—C13—H13	118.8 (12)
C6—C5—C4	122.22 (14)	C11—C12—C13	119.93 (16)
C6—C5—Br1	118.95 (12)	C11—C12—H12	119.1 (13)
C4—C5—Br1	118.82 (11)	C13—C12—H12	120.9 (13)
C5—C6—C7	119.93 (15)	O1—C1—N1	125.88 (15)
C5—C6—H6	123.1 (12)	O1—C1—C2	126.70 (15)
C7—C6—H6	117.0 (12)	N1—C1—C2	107.41 (13)
C8—C7—C6	118.09 (14)	C3—C2—C1	103.38 (12)
C8—C7—H7	122.8 (11)	C3—C2—H2A	115.9 (12)
C6—C7—H7	119.1 (12)	C1—C2—H2A	108.0 (12)
C7—C8—C3	121.53 (14)	C3—C2—H2B	113.8 (12)
C7—C8—N1	129.13 (13)	C1—C2—H2B	107.0 (12)
C3—C8—N1	109.35 (13)	H2A—C2—H2B	108.2 (16)
C1—N1—C8	111.05 (13)	C4—C3—C8	120.52 (14)
C1—N1—C9	122.97 (12)	C4—C3—C2	130.90 (14)
C8—N1—C9	125.94 (12)	C8—C3—C2	108.58 (13)
C14—C9—C10	120.60 (15)	C3—C4—C5	117.72 (14)
C14—C9—N1	120.84 (13)	C3—C4—H4	121.7 (12)
C10—C9—N1	118.55 (13)	C5—C4—H4	120.6 (12)
C9—C14—C13	119.19 (15)	C12—C11—C10	120.39 (16)
C9—C14—H14	120.8 (11)	C12—C11—H11	120.2 (12)
C13—C14—H14	120.0 (11)	C10—C11—H11	119.4 (12)
C4—C5—C6—C7	−0.8 (2)	C8—N1—C1—O1	−174.69 (16)
Br1—C5—C6—C7	178.57 (11)	C9—N1—C1—O1	7.3 (2)
C5—C6—C7—C8	0.8 (2)	C8—N1—C1—C2	4.63 (16)
C6—C7—C8—C3	−0.3 (2)	C9—N1—C1—C2	−173.37 (13)
C6—C7—C8—N1	−179.91 (14)	O1—C1—C2—C3	174.56 (16)
C7—C8—N1—C1	177.07 (15)	N1—C1—C2—C3	−4.74 (16)
C3—C8—N1—C1	−2.56 (16)	C7—C8—C3—C4	−0.2 (2)
C7—C8—N1—C9	−5.0 (2)	N1—C8—C3—C4	179.46 (13)
C3—C8—N1—C9	175.36 (13)	C7—C8—C3—C2	179.64 (14)
C11—C10—C9—C14	1.1 (2)	N1—C8—C3—C2	−0.70 (16)
C11—C10—C9—N1	−178.11 (14)	C1—C2—C3—C4	−176.90 (16)
C1—N1—C9—C14	−128.40 (16)	C1—C2—C3—C8	3.28 (17)
C8—N1—C9—C14	53.9 (2)	C8—C3—C4—C5	0.2 (2)
C1—N1—C9—C10	50.8 (2)	C2—C3—C4—C5	−179.55 (15)
C8—N1—C9—C10	−126.88 (16)	C6—C5—C4—C3	0.2 (2)
C10—C9—C14—C13	−0.9 (2)	Br1—C5—C4—C3	−179.10 (11)
N1—C9—C14—C13	178.25 (14)	C13—C12—C11—C10	−0.7 (3)
C9—C14—C13—C12	−0.1 (3)	C9—C10—C11—C12	−0.3 (3)
C14—C13—C12—C11	0.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1^i	0.961 (19)	2.496 (19)	3.2845 (19)	139.2 (15)
C14—H14···O1^ii	0.958 (19)	2.540 (18)	3.375 (2)	145.7 (15)

Symmetry codes: (i) x−1, −y+1/2, z−1/2; (ii) x, −y+1/2, z−1/2.

(III) 5-Iodo-1-phenylindolin-2-one

Crystal data

C14H10INO	F(000) = 1296
Mr = 335.13	Dx = 1.799 Mg m^−3
Orthorhombic, Aea2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: A2 -2ac	Cell parameters from 6666 reflections
a = 8.1164 (3) Å	θ = 3.0–30.3°
b = 13.3844 (5) Å	µ = 2.57 mm^−1
c = 22.7824 (8) Å	T = 90 K
V = 2474.92 (16) Å^3	Plate, colourless
Z = 8	0.29 × 0.22 × 0.03 mm

Data collection

Bruker APEX-II CCD diffractometer	3810 independent reflections
Radiation source: fine-focus sealed tube	3256 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
Detector resolution: 8.3 pixels mm^-1	θmax = 31.0°, θmin = 3.0°
ω scans	h = −11→11
Absorption correction: multi-scan APEX2 Software Suite (Bruker, 2005)	k = −18→19
Tmin = 0.527, Tmax = 0.922	l = −32→31
16830 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.072	w = 1/[σ^2(Fo^2) + (0.0409P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.002
3810 reflections	Δρmax = 1.36 e Å^−3
186 parameters	Δρmin = −0.68 e Å^−3
1 restraint	Absolute structure: Flack (1983), 1820 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (2)

Special details

Experimental. Scan with 0.3° ω, Crystal to detector distance 5.964 cm, exposure time 18 s, 16 h for data collection, with scale

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 (Ų)

	x	y	z	Uiso*/Ueq
I1	0.78014 (2)	0.630345 (11)	1.000222 (11)	0.02962 (7)
O1	0.0035 (3)	0.61392 (15)	0.79284 (12)	0.0278 (5)
N1	0.2876 (3)	0.62319 (17)	0.79048 (14)	0.0204 (5)
C5	0.6211 (4)	0.63158 (18)	0.92710 (15)	0.0218 (6)
C6	0.6875 (4)	0.6369 (2)	0.87116 (16)	0.0224 (6)
C7	0.5839 (4)	0.63509 (19)	0.82181 (16)	0.0222 (6)
C8	0.4170 (4)	0.62912 (18)	0.83209 (15)	0.0202 (6)
C9	0.3060 (4)	0.6243 (2)	0.72802 (18)	0.0251 (7)
C14	0.2323 (5)	0.5487 (3)	0.69486 (17)	0.0321 (7)
C13	0.2464 (5)	0.5503 (3)	0.6342 (2)	0.0416 (9)
C12	0.3350 (9)	0.6256 (4)	0.6079 (3)	0.0424 (15)
H12	0.3464	0.6259	0.5664	0.051*
C4	0.4521 (4)	0.62420 (18)	0.93701 (15)	0.0219 (6)
H4	0.4082	0.6202	0.9756	0.026*
C3	0.3516 (4)	0.62299 (18)	0.88827 (15)	0.0214 (6)
C1	0.1358 (4)	0.6154 (2)	0.81831 (15)	0.0228 (6)
C2	0.1672 (7)	0.6113 (4)	0.8841 (2)	0.0245 (9)
C10	0.3923 (4)	0.7003 (2)	0.70028 (14)	0.0283 (7)
C11	0.4070 (5)	0.6998 (3)	0.63984 (16)	0.0384 (8)
H13	0.200 (5)	0.492 (3)	0.6116 (18)	0.042 (11)*
H14	0.193 (5)	0.495 (3)	0.7130 (15)	0.026 (9)*
H7	0.632 (6)	0.636 (2)	0.7812 (19)	0.027 (11)*
H6	0.802 (7)	0.641 (3)	0.864 (3)	0.045 (15)*
H10	0.433 (5)	0.751 (2)	0.7223 (15)	0.024 (9)*
H11	0.469 (6)	0.748 (2)	0.6225 (19)	0.035 (10)*
H2A	0.128 (5)	0.548 (3)	0.8977 (14)	0.023 (8)*
H2B	0.106 (5)	0.668 (3)	0.9044 (16)	0.026 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.02834 (10)	0.03506 (10)	0.02546 (10)	−0.00460 (6)	−0.00272 (17)	0.0029 (2)
O1	0.0196 (11)	0.0305 (11)	0.0332 (13)	−0.0019 (9)	−0.0004 (9)	−0.0022 (9)
N1	0.0172 (14)	0.0239 (13)	0.0202 (14)	−0.0022 (9)	0.0022 (10)	−0.0025 (8)
C5	0.0221 (16)	0.0183 (12)	0.0249 (16)	−0.0003 (10)	−0.0010 (11)	0.0012 (10)
C6	0.0207 (16)	0.0196 (12)	0.0269 (17)	−0.0023 (10)	0.0031 (11)	−0.0018 (11)
C7	0.0181 (15)	0.0206 (12)	0.0279 (16)	−0.0007 (10)	0.0036 (11)	−0.0029 (11)
C8	0.0175 (15)	0.0177 (12)	0.0254 (16)	−0.0005 (9)	0.0025 (11)	−0.0015 (10)
C9	0.0207 (17)	0.0294 (16)	0.0253 (19)	0.0039 (11)	−0.0006 (13)	−0.0023 (11)
C14	0.0248 (17)	0.0352 (17)	0.036 (2)	−0.0026 (14)	0.0007 (14)	−0.0079 (14)
C13	0.029 (2)	0.057 (2)	0.039 (2)	−0.0020 (17)	0.0009 (15)	−0.0174 (18)
C12	0.033 (3)	0.069 (4)	0.026 (2)	0.009 (2)	0.001 (2)	−0.007 (2)
C4	0.0233 (16)	0.0165 (12)	0.0258 (16)	−0.0008 (10)	0.0055 (11)	0.0022 (10)
C3	0.0202 (15)	0.0189 (12)	0.0251 (16)	0.0016 (10)	0.0062 (12)	0.0019 (10)
C1	0.0177 (15)	0.0212 (13)	0.0295 (17)	−0.0009 (11)	0.0047 (11)	0.0004 (10)
C2	0.0198 (19)	0.0212 (15)	0.032 (3)	0.0023 (14)	0.0046 (16)	0.0044 (15)
C10	0.0232 (16)	0.0330 (15)	0.0287 (17)	−0.0043 (12)	−0.0005 (12)	−0.0020 (12)
C11	0.0272 (19)	0.054 (2)	0.034 (2)	−0.0008 (16)	0.0019 (14)	0.0058 (16)

Geometric parameters (Å, º)

I1—C5	2.107 (3)	C14—H14	0.89 (4)
O1—C1	1.221 (4)	C13—C12	1.375 (8)
N1—C1	1.389 (4)	C13—H13	1.01 (4)
N1—C8	1.417 (4)	C12—C11	1.364 (8)
N1—C9	1.431 (5)	C12—H12	0.9500
C5—C6	1.385 (5)	C4—C3	1.378 (5)
C5—C4	1.394 (5)	C4—H4	0.9500
C6—C7	1.404 (5)	C3—C2	1.508 (6)
C6—H6	0.94 (6)	C1—C2	1.522 (7)
C7—C8	1.378 (5)	C2—H2A	0.96 (3)
C7—H7	1.00 (4)	C2—H2B	1.02 (4)
C8—C3	1.388 (5)	C10—C11	1.382 (5)
C9—C10	1.387 (5)	C10—H10	0.91 (3)
C9—C14	1.397 (5)	C11—H11	0.90 (4)
C14—C13	1.388 (5)
C1—N1—C8	110.8 (3)	C11—C12—C13	121.7 (6)
C1—N1—C9	123.2 (3)	C11—C12—H12	119.2
C8—N1—C9	126.0 (3)	C13—C12—H12	119.2
C6—C5—C4	122.4 (3)	C3—C4—C5	116.9 (3)
C6—C5—I1	119.3 (2)	C3—C4—H4	121.5
C4—C5—I1	118.3 (3)	C5—C4—H4	121.5
C5—C6—C7	120.2 (3)	C4—C3—C8	121.1 (3)
C5—C6—H6	123 (4)	C4—C3—C2	129.8 (3)
C7—C6—H6	117 (4)	C8—C3—C2	109.1 (3)
C8—C7—C6	117.0 (3)	O1—C1—N1	124.3 (3)
C8—C7—H7	123 (3)	O1—C1—C2	127.9 (3)
C6—C7—H7	120 (3)	N1—C1—C2	107.7 (3)
C7—C8—C3	122.4 (3)	C3—C2—C1	102.9 (3)
C7—C8—N1	128.2 (3)	C3—C2—H2A	113 (2)
C3—C8—N1	109.3 (3)	C1—C2—H2A	107 (2)
C10—C9—C14	120.1 (4)	C3—C2—H2B	112 (2)
C10—C9—N1	120.9 (3)	C1—C2—H2B	110 (2)
C14—C9—N1	119.0 (3)	H2A—C2—H2B	111 (3)
C13—C14—C9	119.5 (4)	C11—C10—C9	119.6 (3)
C13—C14—H14	120 (2)	C11—C10—H10	121 (2)
C9—C14—H14	119 (2)	C9—C10—H10	119 (2)
C12—C13—C14	119.3 (4)	C12—C11—C10	119.9 (4)
C12—C13—H13	123 (2)	C12—C11—H11	121 (3)
C14—C13—H13	118 (2)	C10—C11—H11	119 (3)
C4—C5—C6—C7	0.1 (4)	C5—C4—C3—C8	−0.1 (4)
I1—C5—C6—C7	178.29 (19)	C5—C4—C3—C2	177.0 (3)
C5—C6—C7—C8	0.7 (4)	C7—C8—C3—C4	1.0 (4)
C6—C7—C8—C3	−1.3 (4)	N1—C8—C3—C4	178.2 (2)
C6—C7—C8—N1	−177.9 (2)	C7—C8—C3—C2	−176.7 (3)
C1—N1—C8—C7	178.3 (3)	N1—C8—C3—C2	0.5 (3)
C9—N1—C8—C7	−1.3 (4)	C8—N1—C1—O1	176.4 (3)
C1—N1—C8—C3	1.3 (3)	C9—N1—C1—O1	−3.9 (4)
C9—N1—C8—C3	−178.3 (3)	C8—N1—C1—C2	−2.6 (3)
C1—N1—C9—C10	126.7 (3)	C9—N1—C1—C2	177.1 (3)
C8—N1—C9—C10	−53.7 (4)	C4—C3—C2—C1	−179.4 (3)
C1—N1—C9—C14	−51.7 (4)	C8—C3—C2—C1	−2.0 (4)
C8—N1—C9—C14	127.9 (3)	O1—C1—C2—C3	−176.2 (3)
C10—C9—C14—C13	0.1 (6)	N1—C1—C2—C3	2.7 (4)
N1—C9—C14—C13	178.6 (3)	C14—C9—C10—C11	−1.1 (5)
C9—C14—C13—C12	1.0 (7)	N1—C9—C10—C11	−179.5 (3)
C14—C13—C12—C11	−1.2 (8)	C13—C12—C11—C10	0.3 (8)
C6—C5—C4—C3	−0.4 (4)	C9—C10—C11—C12	0.9 (6)
I1—C5—C4—C3	−178.61 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O1^i	0.94 (6)	2.34 (6)	3.140 (4)	143 (5)
C10—H10···O1^ii	0.91 (3)	2.48 (3)	3.383 (4)	171 (3)

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