6-Chloro-1-phenyl­indoline-2,3-dione: absolute structure, non-linear optical and charge-transport properties

A polycrystalline sample of the title compound exhibits a considerable second-order non-linear optical effect (frequency doubling of 1064 nm light to output 532 nm light). In the crystal, mol­ecules are linked by C—H⋯O hydrogen bonds, generating chains along the [100] direction. Based on a DFT calculation, [100] proves to be the most favourable direction for charge transport and the title crystal could be used as a hole-transport material because of its high hole mobility.

Abstract

In the title compound, C₁₄H₈ClNO₂, the dihedral angle between the isatin moiety (r.m.s. deviation = 0.014 Å) and the phenyl ring is 51.8 (1)°. All mol­ecules have the same ‘frozen chiral’ conformation in the non-centrosymmetric P2₁2₁2₁ space group. A polycrystalline sample of the title compound exhibits a considerable second-order non-linear optical effect (frequency doubling of 1064 nm light to output 532 nm light). In the crystal, mol­ecules are linked by C—H⋯O hydrogen bonds, generating chains along the [100] direction. Based on a DFT calculation, [100] proves to be the most favourable direction for charge transport and the title crystal could be used as a hole-transport material because of its high hole mobility.

Chemical context  

Derivatives of isatin, also called indoline-2,3-dione, have drawn great attention for their biological and pharmacological properties such as anti­convulsant (Prakash et al., 2010 ▸), anti­cancer (Abadi et al., 2006 ▸) and anti-HIV (Bal et al., 2005 ▸) activities. The isatin skeleton can be found in analytical reagents, pesticides and dye inter­mediates. Isatin derivatives are also versatile precursors in the synthesis of a variety of heterocyclic compounds. However, the opto-electronic properties of isatin derivatives are rarely investigated.

The crystal structures of many isatin derivatives have been reported, among the analogues of the title compound are 6-bromo-1-butyl­indoline-2,3-dione (Ji et al., 2009 ▸), 1-ethyl-5-iodo­indoline-2,3-dione (Wang et al., 2014 ▸), 6-chloro­indoline-2,3-dione (Golen & Manke, 2016 ▸), 1-benzyl-5-fluoro­indoline-2,3-dione (Sharmila et al., 2015 ▸) and 1-phenyl­indoline-2,3-dione (Shukla & Rajeswaran, 2011 ▸). The synthesis of the title compound was reported in 2014 (Bergman & Stensland, 2014 ▸). Recently, we prepared this compound by a different method, which involves the use of O₂ in air as oxidant. Herein, we report the crystal structure and some opto-electronic properties of this compound.

Structural commentary  

As shown in Fig. 1 ▸, the isatin unit of the mol­ecule is essentially planar, with a mean deviation of 0.009 (2) Å and a maximum deviation of 0.0870 (8) Å (for atom O1) from the mean plane of the indoline core (C1–C8/N1). As a result of the short intra­molecular contacts (C10⋯C7, C14⋯O1) and the H7⋯H10 steric hindrance, there is a dihedral angle of 51.8 (1)° between the phenyl ring and the mean plane of the indoline core. As a comparison, the dihedral angle of the DFT/b3lyp/6-311++g(2d,p) optimized (see below) title mol­ecule is 60.0°. The sum of the angles surrounding N1 is 359.96°, suggesting that this atom is sp ² hybridized. The C9—N1 bond length [1.4279 (14) Å] is slightly shorter than that [1.436 (2) Å] in the similar compound 1-phenyl­indoline-2,3-dione (Shukla & Rajeswaran, 2011 ▸). The C1—C2 [1.557 (2) Å] bond length is longer than a typical Csp ²—Csp ² bond but it is notable that the geometry optimization gave a length of 1.568 Å for this bond. The C1—C2 length [1.545 (3) Å] in 1-phenyl­indoline-2,3-dione is somewhat shorter (Shukla & Rajeswaran, 2011 ▸).

Figure 1.

The mol­ecular structure of the title compound, with displacement ellipsoids shown at the 50% probability level.

As a result of the P2₁2₁2₁ space group of the crystal, all mol­ecules have the same ‘frozen chiral’ conformation (defined as conformation I). The single conformation of these mol­ecules in this as-tested crystal is confirmed by a Flack parameter x = 0.03 (5) and R ₁ factor of 0.0317. By comparison, an inversion operation to the present structure resulted in an incorrect structure of conformation II with x = 0.97 (5) and R ₁ = 0.0336. 1-Phenyl­indoline-2,3-dione also crystallized in P2₁2₁2₁ (Shukla & Rajeswaran, 2011 ▸) and this space group may be well suited to accommodate this class of mol­ecules.

As shown in Figs. 1 ▸ and 2 ▸, the isoenergic conformations I and II are mirror images and non-superposable one another. The calculated rotation barrier (rotating around the N1—C9 bond to transform from I to II) is 8.74 kcal mol⁻¹, which is much higher than the thermal energy k _B T = 0.596 kcal mol⁻¹ at 300 K. The main hindrance from free rotation may be the H7⋯H10 steric repulsion with a calculated distance of 1.759 Å at the transition state (see Fig. 2 ▸).

Figure 2.

DFT/b3lyp/6–311++g(2 d,p) optimization of series of relaxed conformation with different C8—N1—C9—C14 torsion angles for the title mol­ecule.

Supra­molecular features  

As shown in Fig. 3 ▸, the inter­molecular inter­actions in the a-axis direction are characterized by a C10—H10⋯O1 hydrogen bond (Table 1 ▸) and an O1⋯H11(x − 1, y, z) [2.63 (2) Å] short contact between two side-by-side mol­ecules. The strength of the hydrogen bond can be scaled by the electronic transfer integral (t) between two mol­ecules and it was calculated by equation (3). The t value between the above two adjacent mol­ecules is maximal (t ₁ = 0.196 eV), indicating that a kind of side-by-side one-dimensional chain has formed along the a-axis direction. We believe that this a-directional chain plays an important role in guiding the crystal growth, for the long axis of the bar-shaped crystal was indexed to be in the [100] direction.

Figure 3.

The view along the b axis, showing the chain linkage by the C10ⁱ—H10ⁱ⋯O1 hydrogen bond and the O1⋯H11ⁱ short inter­molecular contacts along the a-axis direction. [Symmetry code: (i) −1 + x, y, z.]

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯O1i	0.956 (17)	2.572 (18)	3.2063 (16)	124.0 (13)

Symmetry code: (i) .

By the 2₁ [010] screw operation, mol­ecules are packed into columns along the b-axis direction involving C2⋯C12(2 − x,  + y,  − z) [3.280 (2) Å] and H10⋯C14(2 − x,  + y,  − z) [2.50 (3) Å] short inter­molecular contacts between two neighboring mol­ecules (see Fig. 4 ▸). The transfer integral between such two face-to-face mol­ecules is somewhat smaller (t ₂ = 0.116 eV) in this direction.

Figure 4.

The view along the a axis, showing the columnar structure and short contacts of C2⋯C12ⁱⁱ and H10⋯C14ⁱⁱ along the b-axis direction, also showing the short contact of H5⋯O2ⁱⁱⁱ along the c direction. [Symmetry codes: (ii) 2 − x,  + y,  − z; (iii)  + x,  − y, 1 − z.]

Along the c-axis direction, there is a H5⋯O2( + x,  − y, 1 − z) [2.69 (2) Å] short inter­molecular contact and the t value between the two mol­ecules is a minimum (t ₃ = 0.0794 eV, see Fig. 4 ▸): thus the inter­molecular inter­actions in this direction are relatively weak.

Calculation and opto-electronic properties  

It is well known that the necessary structural condition for second-order non-linear optical response is non-centrosymmetry, both for mol­ecules and crystals. The P2₁2₁2₁ space group of the crystal prompted us to make a SHG (second harmonic generation) test. When the sample of crystalline powder was irradiated with infrared laser pulses (1064 nm), green light pulses (532 nm) could be observed.

Density functional theory (DFT) calculations for the electronic transfer integral t and the reorganization energy λ, were carried out using the GAUSSIAN03 program (Frisch et al., 2003 ▸) within the framework of b3lyp/6-311g(d).

The charge transport in organic semiconductors can be described by the hopping of an electron between a mol­ecule and a neighbouring cation (hole) or anion shown below

Based on the Marcus electron-transfer theory (Marcus, 1993 ▸), the mobility (μ) in a one-dimensional uniform structure, can be expressed as (Sakanoue et al., 1999 ▸; Fang et al., 2015 ▸)

where d is the distance between two neighbouring mol­ecules and λ is reorganization energy. For the hole transport, λ can be expressed by (Berlin et al., 2003 ▸)

Thus, λ₁ measures the energy difference between the stable mol­ecule and the mol­ecule with the cation geometry and λ₂ measures the energy difference between the stable cation and the cation with the mol­ecule geometry.

The t in equation (1) is the electronic transfer integral, which measures the inter­molecular inter­actions between two neighbouring mol­ecules and can be calculated by (Deng & Goddard, 2004 ▸)

where E _HOMO and E _HOMO-1 are the energy levels of the HOMO (highest occupied mol­ecular orbital) and the HOMO-1 orbital of a two-mol­ecule pair, respectively.

The mol­ecular geometry for the t calculation is based on this X-ray structure without optimization, while the geometries of the mol­ecule and the cation/anion have been optimized for the λ calculation. Since the mol­ecule in the crystal is different from the free mol­ecule, we adopted the cage model (Fang et al., 2015 ▸) in the course of geometry optimization, in which the host (mol­ecule or cation or anion) being optimized is constrained by four guest mol­ecules with fixed X-ray structures (see Fig. 5 ▸).

Figure 5.

The view along the c axis, showing the cage-model for the DFT geometry optimization with one host mol­ecule being surrounded by four guest mol­ecules.

As shown in Table 2 ▸, (i) the hole mobility (μ_h) is one order of magnitude larger than the electron mobility (μ_e), indicating that the title crystal could be used as a hole-transport material rather than an electron-transport material and (ii) both the hole mobility (μ_h) and the electron mobility (μ_e) in the [100] direction (the side-by-side chain direction) are an order of magnitude larger than those in the [010] direction (the face-to-face column direction).

Table 2. Charge-transport properties (eV, cm² V⁻¹ s⁻¹) of the title crystal.

	t	λh (λe)	μh (μe)
side-by-side [100]	0.196	0.319 (0.520)	4.67 (0.524)
face-to-face [010]	0.116	0.319 (0.520)	0.518 (0.058)

In summary, the side-by-side hydrogen bonding in the one-dimensional chain in the [100] direction is stronger than the face-to-face π–π inter­actions in the [010] direction for this crystal, which relates to the non-linear optical and electronic transport properties of the crystal.

Database survey  

A search in the Cambridge Structural Database (WebCSD, Version 1.1.2; last update November 2016), for indoline-2,3-dione derivatives gave 137 hits. Among them, there are nine hits for halogen 6-substituted indoline-2,3-dione derivatives and two hits which contain the substructure of the 1-phenyl­indoline-2,3-dione skeleton. There are four non-centrosymmetric structures and seven centrosymmetric structures among these eleven crystal structures.

Synthesis and crystallization  

We synthesized the title compound by the reaction of 6-chloro­indoline-2-one and phenyl­boronic acid (see Fig. 6 ▸). 6-Chloro­indoline-2-one (0.168 g, 1.00 mmol) was dissolved in DMF (18 ml). Then pyridine (0.05 mL), phenyl­boronic acid (0.244 g, 2.00 mmol) and Cu(OAc)₂·H₂O (0.197 g, 0.99 mmol) were sequentially added into the flask. The mixture was stirred for two h at room temperature in the presence of air. After filtration, the filtrate was poured into 100 ml water and extracted with di­chloro­methane. The organic phase was washed by water and dried by anhydrous Na₂SO₄. The crude product was purified by silica gel chromatography, eluting with a mixture of petroleum ether:ethyl acetate (30:1) to obtain an orange solid (0.096 g, yield 37%). ¹H NMR (400 MHz, CDCl₃) δ 7.64 (d, J = 8.4 Hz, 1H), 7.59 (t, J = 7.6 Hz, 2H), 7.49 (t, J = 7.4 Hz, 1H), 7.40 (d, J = 7.2 Hz, 2H), 7.15 (dd, J = 8.0, 1.6 Hz, 1H), 6.89 (d, J = 1.6 Hz, 1H). As shown in Fig. 7 ▸, the ¹H NMR signals of all protons of the compound are well separated and well characterized. Orange bar-shaped crystals were obtained by slow evaporation of a solution of the title compound in mixed solvents of di­chloro­methane and n-hexane.

Figure 6.

Reaction scheme.

Figure 7.

The ¹H NMR spectra of the title compound.

Refinement  

Crystal data, diffraction data and structure refinement details are summarized in Table 3 ▸. All hydrogen atoms were located from the difference-electron-density maps and refined freely, resulting in C—H lengths ranging from 0.92 (2) to 1.00 (2) Å.

Table 3. Experimental details.

Crystal data
Chemical formula	C14H8ClNO2
M r	257.66
Crystal system, space group	Orthorhombic, P212121
Temperature (K)	294
a, b, c (Å)	6.8190 (3), 7.7062 (3), 21.7492 (9)
V (Å3)	1142.89 (8)
Z	4
Radiation type	Mo Kα
μ (mm−1)	0.33
Crystal size (mm)	0.58 × 0.24 × 0.18
Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005 ▸)
T min, T max	0.834, 0.943
No. of measured, independent and observed [I > 2σ(I)] reflections	21380, 3784, 3513
R int	0.021
(sin θ/λ)max (Å−1)	0.741
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.032, 0.090, 1.04
No. of reflections	3784
No. of parameters	191
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.21, −0.23
Absolute structure	Flack (1983 ▸), 1583 Friedel pairs
Absolute structure parameter	0.03 (5)

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

Supplementary Material

CCDC reference: 1528555

Additional supporting information: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Crystal data

C14H8ClNO2	Dx = 1.497 Mg m−3
Mr = 257.66	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 9992 reflections
a = 6.8190 (3) Å	θ = 2.8–31.0°
b = 7.7062 (3) Å	µ = 0.33 mm−1
c = 21.7492 (9) Å	T = 294 K
V = 1142.89 (8) Å3	Bar, orange
Z = 4	0.58 × 0.24 × 0.18 mm
F(000) = 528

Data collection

Bruker APEXII CCD diffractometer	3784 independent reflections
Radiation source: fine-focus sealed tube	3513 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
Detector resolution: 8.3 pixels mm-1	θmax = 31.8°, θmin = 1.9°
ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −10→11
Tmin = 0.834, Tmax = 0.943	l = −32→28
21380 measured reflections

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.090	w = 1/[σ2(Fo2) + (0.0575P)2 + 0.0865P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
3784 reflections	Δρmax = 0.21 e Å−3
191 parameters	Δρmin = −0.23 e Å−3
0 restraints	Absolute structure: Flack (1983), 1583 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (5)

Special details

Experimental. Scan width 0.5° ω , Crystal to detector distance 5.96 cm, exposure time 15s, 10 hours and 36 minutes for data collection, with scale. 6-run at 2theta equal -28, -28, -35,-36,-36,-38, respectively.

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.

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 > 2sigma(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
Cl1	1.36000 (5)	0.40110 (5)	0.561115 (17)	0.05229 (11)
C7	1.10733 (16)	0.54301 (15)	0.64149 (5)	0.0323 (2)
O2	0.48463 (15)	0.81725 (15)	0.61436 (5)	0.0514 (3)
O1	0.58784 (14)	0.83661 (15)	0.74488 (5)	0.0466 (2)
C5	1.0114 (2)	0.5438 (2)	0.53283 (6)	0.0423 (3)
C6	1.14176 (18)	0.50392 (15)	0.57981 (5)	0.0355 (2)
C8	0.93314 (16)	0.62745 (14)	0.65401 (5)	0.0298 (2)
N1	0.86151 (14)	0.68187 (13)	0.71209 (4)	0.03287 (18)
C9	0.95746 (17)	0.65986 (15)	0.76993 (5)	0.0309 (2)
C14	0.8529 (2)	0.58710 (17)	0.81830 (6)	0.0400 (3)
C13	0.9437 (3)	0.5724 (2)	0.87499 (6)	0.0502 (3)
H13	0.8757	0.5247	0.9080	0.060*
C12	1.1351 (3)	0.6281 (2)	0.88297 (6)	0.0539 (4)
C3	0.79945 (17)	0.66972 (16)	0.60753 (5)	0.0339 (2)
C4	0.8377 (2)	0.62747 (18)	0.54664 (6)	0.0417 (3)
C2	0.63341 (17)	0.75880 (16)	0.63578 (6)	0.0366 (2)
C1	0.68398 (16)	0.76703 (16)	0.70553 (6)	0.0348 (2)
C11	1.2390 (2)	0.6983 (2)	0.83442 (6)	0.0456 (3)
C10	1.15006 (18)	0.71514 (15)	0.77716 (5)	0.0350 (2)
H5	1.042 (3)	0.510 (2)	0.4916 (9)	0.056 (5)*
H4	0.739 (3)	0.659 (2)	0.5147 (9)	0.050 (5)*
H10	1.219 (3)	0.768 (2)	0.7437 (8)	0.041 (4)*
H11	1.369 (3)	0.735 (2)	0.8379 (9)	0.054 (5)*
H12	1.195 (4)	0.618 (3)	0.9210 (11)	0.081 (7)*
H14	0.724 (3)	0.548 (3)	0.8112 (9)	0.056 (5)*
H7	1.195 (3)	0.509 (2)	0.6711 (8)	0.038 (4)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.04536 (17)	0.0669 (2)	0.04463 (17)	0.01248 (15)	0.01136 (13)	−0.00487 (15)
C7	0.0316 (5)	0.0373 (5)	0.0281 (4)	0.0001 (4)	0.0017 (4)	0.0021 (4)
O2	0.0373 (4)	0.0633 (6)	0.0536 (6)	0.0104 (4)	−0.0091 (4)	−0.0017 (5)
O1	0.0361 (4)	0.0589 (6)	0.0448 (5)	0.0057 (4)	0.0071 (4)	−0.0055 (4)
C5	0.0491 (7)	0.0514 (7)	0.0263 (5)	0.0011 (5)	0.0025 (4)	−0.0016 (5)
C6	0.0352 (5)	0.0391 (5)	0.0324 (5)	0.0011 (4)	0.0071 (4)	−0.0003 (4)
C8	0.0299 (4)	0.0330 (5)	0.0265 (4)	−0.0031 (4)	0.0022 (3)	0.0008 (4)
N1	0.0281 (4)	0.0435 (5)	0.0270 (4)	0.0015 (4)	0.0026 (3)	−0.0012 (3)
C9	0.0354 (5)	0.0315 (5)	0.0260 (4)	0.0013 (4)	0.0026 (4)	−0.0002 (4)
C14	0.0468 (7)	0.0381 (5)	0.0353 (5)	−0.0017 (5)	0.0102 (5)	0.0016 (4)
C13	0.0712 (9)	0.0490 (7)	0.0305 (6)	0.0122 (7)	0.0121 (6)	0.0080 (5)
C12	0.0714 (9)	0.0600 (8)	0.0303 (5)	0.0256 (8)	−0.0083 (6)	−0.0015 (5)
C3	0.0328 (5)	0.0384 (5)	0.0305 (5)	−0.0006 (4)	−0.0017 (4)	0.0013 (4)
C4	0.0463 (6)	0.0490 (6)	0.0299 (5)	0.0021 (5)	−0.0053 (5)	0.0005 (5)
C2	0.0313 (5)	0.0400 (5)	0.0385 (5)	−0.0019 (4)	−0.0019 (4)	0.0001 (4)
C1	0.0280 (5)	0.0393 (5)	0.0372 (5)	−0.0014 (4)	0.0017 (4)	−0.0001 (4)
C11	0.0453 (7)	0.0527 (7)	0.0388 (6)	0.0106 (6)	−0.0109 (5)	−0.0067 (6)
C10	0.0343 (5)	0.0381 (5)	0.0327 (5)	0.0017 (4)	−0.0004 (4)	−0.0005 (4)

Geometric parameters (Å, º)

Cl1—C6	1.7343 (12)	C9—C10	1.3896 (16)
C7—C8	1.3815 (16)	C14—C13	1.384 (2)
C7—C6	1.3948 (15)	C14—H14	0.94 (2)
C7—H7	0.916 (17)	C13—C12	1.385 (3)
O2—C2	1.2039 (16)	C13—H13	0.9300
O1—C1	1.2040 (15)	C12—C11	1.382 (2)
C5—C4	1.3816 (19)	C12—H12	0.93 (2)
C5—C6	1.3889 (18)	C3—C4	1.3884 (17)
C5—H5	0.96 (2)	C3—C2	1.4597 (17)
C8—C3	1.3996 (15)	C4—H4	1.00 (2)
C8—N1	1.4179 (13)	C2—C1	1.5570 (17)
N1—C1	1.3844 (14)	C11—C10	1.3916 (17)
N1—C9	1.4279 (14)	C11—H11	0.93 (2)
C9—C14	1.3892 (16)	C10—H10	0.956 (17)
C8—C7—C6	115.85 (11)	C12—C13—H13	119.7
C8—C7—H7	123.8 (11)	C11—C12—C13	120.60 (13)
C6—C7—H7	120.3 (11)	C11—C12—H12	119.1 (16)
C4—C5—C6	119.46 (11)	C13—C12—H12	120.3 (16)
C4—C5—H5	121.2 (12)	C4—C3—C8	120.79 (11)
C6—C5—H5	119.3 (12)	C4—C3—C2	131.11 (11)
C5—C6—C7	123.52 (11)	C8—C3—C2	108.10 (10)
C5—C6—Cl1	118.54 (9)	C5—C4—C3	118.56 (11)
C7—C6—Cl1	117.94 (10)	C5—C4—H4	122.6 (11)
C7—C8—C3	121.83 (10)	C3—C4—H4	118.8 (11)
C7—C8—N1	127.67 (10)	O2—C2—C3	131.81 (12)
C3—C8—N1	110.50 (10)	O2—C2—C1	123.27 (12)
C1—N1—C8	110.46 (9)	C3—C2—C1	104.92 (10)
C1—N1—C9	123.21 (9)	O1—C1—N1	127.88 (12)
C8—N1—C9	126.29 (9)	O1—C1—C2	126.16 (11)
C14—C9—C10	121.55 (11)	N1—C1—C2	105.95 (10)
C14—C9—N1	118.68 (11)	C12—C11—C10	119.78 (14)
C10—C9—N1	119.75 (10)	C12—C11—H11	122.9 (12)
C13—C14—C9	118.54 (14)	C10—C11—H11	117.3 (12)
C13—C14—H14	122.6 (12)	C9—C10—C11	119.00 (12)
C9—C14—H14	118.8 (12)	C9—C10—H10	120.5 (10)
C14—C13—C12	120.52 (13)	C11—C10—H10	120.5 (11)
C14—C13—H13	119.7
C4—C5—C6—C7	0.4 (2)	N1—C8—C3—C2	1.03 (13)
C4—C5—C6—Cl1	−179.26 (11)	C6—C5—C4—C3	0.2 (2)
C8—C7—C6—C5	−0.69 (19)	C8—C3—C4—C5	−0.45 (19)
C8—C7—C6—Cl1	178.95 (8)	C2—C3—C4—C5	178.98 (13)
C6—C7—C8—C3	0.44 (17)	C4—C3—C2—O2	1.2 (2)
C6—C7—C8—N1	179.89 (11)	C8—C3—C2—O2	−179.36 (14)
C7—C8—N1—C1	178.11 (11)	C4—C3—C2—C1	−178.96 (13)
C3—C8—N1—C1	−2.38 (13)	C8—C3—C2—C1	0.52 (13)
C7—C8—N1—C9	0.14 (18)	C8—N1—C1—O1	−176.24 (13)
C3—C8—N1—C9	179.64 (11)	C9—N1—C1—O1	1.80 (19)
C1—N1—C9—C14	52.94 (16)	C8—N1—C1—C2	2.58 (12)
C8—N1—C9—C14	−129.33 (12)	C9—N1—C1—C2	−179.37 (10)
C1—N1—C9—C10	−125.42 (12)	O2—C2—C1—O1	−3.1 (2)
C8—N1—C9—C10	52.31 (16)	C3—C2—C1—O1	176.95 (12)
C10—C9—C14—C13	0.92 (19)	O2—C2—C1—N1	178.00 (12)
N1—C9—C14—C13	−177.41 (11)	C3—C2—C1—N1	−1.90 (12)
C9—C14—C13—C12	−0.4 (2)	C13—C12—C11—C10	0.8 (2)
C14—C13—C12—C11	−0.4 (2)	C14—C9—C10—C11	−0.56 (18)
C7—C8—C3—C4	0.11 (18)	N1—C9—C10—C11	177.75 (11)
N1—C8—C3—C4	−179.42 (11)	C12—C11—C10—C9	−0.30 (19)
C7—C8—C3—C2	−179.43 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···O1i	0.956 (17)	2.572 (18)	3.2063 (16)	124.0 (13)

Symmetry code: (i) x+1, y, z.