Crystal structure, DFT study and Hirshfeld surface analysis of 1-nonyl-2,3-di-hydro-1H-indole-2,3-dione.

In the title mol-ecule, C17H23NO2, the di-hydro-indole portion is planar (r.m.s. deviation = 0.0157 Å) and the nonyl substituent is in an 'extended' conformation. In the crystal, the nonyl chains inter-calate and the di-hydro-indole-dione units are associated through C-H⋯O hydrogen bonds to form micellar blocks. Based on the Hirshfeld surface analysis, the most important inter-molecular inter-action is the H⋯H inter-action.

Chemical context

Indoline-2,3-dione or n class="Chemical">indole-1H-2,3-dione, commonly known as isatin, is a well-known natural product found in plants of genus Isatis and in Couropita guianancis aubl (Da Silva et al., 2001 ▸). It has also been isolated as a metabolic derivative of adrenaline in humans (Almeida et al., 2010 ▸). It was first obtained as an oxidation product of indigo in the early 19th century, and its current structure was proposed by Kekulé (1869 ▸). Isatin is a core constituent of many alkaloids (Trost et al., 2009 ▸) and drugs (Aboul-Fadl et al., 2010 ▸) as well as dyes (Doménech et al., 2009 ▸), pesticides and analytical reagents. Isatin derivatives possess diverse activities such as anti­bacterial (Kassab et al., 2010 ▸), anti­viral (Jarrahpour et al., 2007 ▸), anti-HIV (Sriram et al., 2006 ▸), anti­cancer (Gürsoy et al., 2003 ▸) and anti-inflammatory (Sridhar et al., 2001 ▸) activities. As a continuation of our research work devoted to the development of isatin derivatives (Ben-Yahia et al., 2018 ▸; Rayni et al., 2019 ▸), we report in this work the synthesis and the Hirshfeld surface analysis of a new indoline-2,3-dione derivative obtained by the action of nonyl bromide on isatin under phase-transfer catalysis conditions.

Structural commentary

The mol­ecular structure of the title compound is shown in Fig. 1 ▸. The di­hydro­indole skeleton is planar to within 0.0286 (8) Å (r.m.s. deviation of the fitted atoms = 0.0157 Å) with Cl being the furthest from the mean plane. The nonyl chain is in an ‘extended’ conformation and is well out of the mean plane of the di­hydro­indole unit, as indicated by the C1—N1—C9—n class="Gene">C10 torsion angle of −69.94 (12)°.

Figure 1

The title mol­ecule with the labelling scheme and 50% probability ellipsoids.

Supra­molecular features

In the crystal, the mol­ecules pack in a typical micellar manner with the di­hydro­indoldione head groups associated through C2—H2⋯O2i, C3—H3⋯O1ii and C9—H9B⋯O1i hydrogen bonds (Table 1 ▸) and the nonyl ‘tails’ inter­calating and aided by paired n class="Gene">C17—H17B⋯O2iii hydrogen bonds (Table 1 ▸ and Fig. 2 ▸). The micellar blocks are associated through π-stacking inter­actions between inversion-related C1–C6 rings [centroid–centroid distance = 3.6470 (7) Å; Figs. 2 ▸ and 3 ▸].

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O2i	0.992 (13)	2.412 (13)	3.3737 (13)	163.3 (10)
C3—H3⋯O1ii	0.997 (14)	2.454 (15)	3.2734 (14)	139.0 (11)
C9—H9B⋯O1i	0.994 (13)	2.546 (13)	3.5012 (13)	161.0 (10)
C17—H17B⋯O2iii	0.98 (2)	2.49 (2)	3.3941 (17)	153.3 (15)

Symmetry codes: (i) ; (ii) ; (iii) .

Figure 2

Detail of the inter­molecular inter­actions. C—H⋯O hydrogen bonds and π-stacking inter­actions are shown, respectively, by black and orange dashed lines. H atoms not involved in hydrogen bonds are omitted for clarity.

Figure 3

Packing viewed along the b-axis direction with inter­molecular inter­actions depicted as in Fig. 2 ▸. H atoms not involved in hydrogen bonds are omitted for clarity.

Database survey

A search of the Cambridge Crystallographic Database (Version 5.40 updated to April 2019; Groom et al., 2016 ▸) provided structures of 11 derivatives of the di­hydro­indole-2,3-dione skeleton having a saturated carbon chain of at least three atoms bound to nitro­gen. Thus, in place of the n-nonyl chain (R) in the title compound, there are ones with R = 3-bromo­propyl (AKOBIn class="Chemical">N; Qachchachi et al., 2016a ▸), n-propyl (AKOCOU; Qachchachi et al., 2016b ▸), n-octyl (CIQDOX; Qachchachi et al., 2013 ▸), 2,3-di­benzoyl­ethane (FUBLIZ; Žari et al., 2015 ▸), n-dodecyl (GITTEK; Qachchachi et al., 2014a ▸), cyclo­pentyl (JOWSOF; Mironova et al., 2015 ▸), 3-carb­oxy­methyl­propane (JOWSUL; Mironova et al., 2015 ▸), 2-cyano­ethane (LIVSIU; Qachchachi et al., 2014b ▸), n-tetra­decyl (TUPSIH; Mamari et al., 2010a ▸) and n-decyl (TUPSON; Mamari et al., 2010b ▸). In addition, there is one structure with two di­hydro­indole-2,3-dione moieties connected by a –(CH2)6– linkage (OJIGOF; Qachchachi et al., 2016c ▸). In all of these compounds, the di­hydro­indole-2,3-dione skeleton is planar and the first two carbon atoms from the nitro­gen are rotated so that the N–C–C plane is nearly perpendicular to the plane of the di­hydro­indole-2,3-dione. Additionally, the C—C distances corresponding to the C7—C8 distance in the title structure [1.5554 (15) Å] are in the range 1.543 (4)–1.563 (6) Å. Generally, the carbon chains are in an ‘extended’ conformation.

Calculation of the electronic structure

The structure in the gas phase of the title compound was optimized by means of density functional theory. The DFT calculation was performed using the hybrid B3n class="Gene">LYP method, which is based on the idea of Becke and considers a mixture of the exact (HF) and DFT exchange utilizing the B3 functional, together with the LYP correlation functional (Becke, 1993 ▸; Lee et al., 1988 ▸; Miehlich et al., 1989 ▸). The B3LYP calculation was performed in conjunction with the def2-SVP basis set (Weigend & Ahlrichs, 2005 ▸). After obtaining the converged geometry, the harmonic vibrational frequencies were calculated on the same theoretical level to confirm that the number of imaginary frequencies is zero for the stationary point. Both the geometry optimization and the harmonic vibrational frequency analysis of the title compound were performed using the Gaussian 16 program (Frisch et al., 2016 ▸). The result of the B3LYP geometry optimization for the title compound (shown in Fig. 4 ▸) was compared to that of the crystallographic study with selected geometric parameters for the gas-phase and solid-phase structures summarized in Table 2 ▸. This shows that there is a clear discrepancy between the B3LYP-optimized geometry and the X-ray geometry. To qu­antify this, the openBabel program was then used to convert the experimental CIF file to a Gaussian .gjf input file (O’Boyle et al., 2011 ▸). The structure compared built in the ChemCraft program (graphical software for visualization of quantum chemistry computations; https://www.chemcraftprog.com) was finally used to obtain a weighted r.m.s. deviation of 0.5808 Å with r.m.s.d. values of of 0.6297, 0.5213, 0.2231, and 0.5977 Å, respectively, for the H, C, N and O atoms.

Figure 4

The B3LYP-optimized geometry of the title compound (bond lengths in Å, bond angles in °; carbon in gray, nitro­gen in blue, oxygen in red and hydrogen in white). please improve resolution

Table 2

The B3LYP-optimized and X-ray structural parameters (Å, °) for the title compound

	B3LYP	X-ray
C1—C2	1.394	1.3806 (13)
C2—C3	1.404	1.3899 (16)
C3—C4	1.402	1.3868 (16)
C4—C5	1.400	1.3871 (16)
C5—C6	1.393	1.3862 (15)
C6—C7	1.473	1.4599 (13)
C6—C1	1.413	1.4009 (13)
C7—C8	1.568	1.5554 (15)
C8—N1	1.390	1.3603 (13)
N1—C1	1.404	1.4127 (13)
C7—O1	1.206	1.2126 (12)
C8—O2	1.206	1.2106 (13)
N1—C9	1.454	1.4606 (13)
N1—C8—C7	105.9	106.20 (8)

Hirshfeld surface analysis

Both the definition of a mol­ecule in a condensed phase and the recognition of distinct entities in mol­ecular liquids and crystals are fundamental concepts in chemistry. Based on Hirshfeld’s partitioning scheme, Spackman et al. (1997 ▸) proposed a method to divide the electron distribution in a crystalline phase into mol­ecular fragments (Spackman & Byrom, 1997 ▸; McKinnon et al., 2004 ▸; Spackman & Jayatilaka, 2009 ▸). Their proposed method partitioned the crystal into regions where the electron distribution of a sum of spherical atoms for the mol­ecule dominates over the corresponding sum of the crystal. In this study, the Hirshfeld surface analysis of the title compound was performed utilizing the CrystalExplorer program (Turner et al., 2017 ▸). The standard resolution mol­ecular Hirshfeld surface (d norm) of the title compound is depicted in Fig. 5 ▸. This surface can be used to identify very close inter­molecular inter­actions. The value of d norm is negative (positive) when inter­molecular contacts are shorter (longer) than the van der Waals radii. The d norm value is mapped onto the Hirshfeld surface using red, white or blue colours. The red regions represent closer contacts with a negative d norm value while the blue regions represent longer contacts with a positive d norm value. The white regions represent contacts equal to the van der Waals separation and have a d norm value of zero. As depicted in Fig. 5 ▸, important inter­actions in the title compound are H⋯O and H⋯n class="Chemical">N hydrogen bonds. The two-dimensional fingerprint plots (Fig. 6 ▸) highlight particular atom-pair contacts and enable the separation of contributions from different inter­action types that overlap in the full fingerprint. The most important inter­actions involving the hydrogen atoms in the title compound are the H⋯H contactso. The H⋯H, H⋯O/O⋯H and H⋯N/N⋯H contacts make contribututions of 61.9, 21.8 and 0.9%, respectively, to the Hirshfeld surface.

Figure 5

The d norm Hirshfeld surface of the title compound (red: negative, white: zero, blue: positive; scale: −0.2101 to 1.3375 a.u.).

Figure 6

Fingerprint plots for the title compound: (a) full and delineated into (b) H⋯O/O⋯H, (c) H⋯N/N⋯H and (d) H⋯H contacts.

Synthesis and crystallization

To a solution of isatin (0.5 g, 3.4 mmol) dissolved in 25 ml of n class="Chemical">N,N-di­methyl­formamide, 1-bromo­octane (0.7 ml, 3.4 mmol), potassium carbonate (0.61 g, 4.4 mmol) and a catalytic amount of tetra-n-butyl­ammonium bromide (0.1 g, 0.4 mmol) were added. The mixture was stirred for 48 h and the reaction monitored by thin layer chromatography. The mixture was filtered and the solvent removed under vacuum. The solid obtained was recrystallized from ethanol to afford the title compound as orange–red crystals.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸.

Table 3

Experimental details

Crystal data
Chemical formula	C17H23NO2
M r	273.36
Crystal system, space group	Monoclinic, P21/c
Temperature (K)	150
a, b, c (Å)	16.2512 (4), 7.6859 (2), 13.0989 (3)
β (°)	106.640 (1)
V (Å3)	1567.60 (7)
Z	4
Radiation type	Cu Kα
μ (mm−1)	0.59
Crystal size (mm)	0.24 × 0.20 × 0.14
Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 ▸)
T min, T max	0.82, 0.92
No. of measured, independent and observed [I > 2σ(I)] reflections	11594, 3128, 2879
R int	0.029
(sin θ/λ)max (Å−1)	0.625
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.035, 0.096, 1.05
No. of reflections	3128
No. of parameters	274
H-atom treatment	All H-atom parameters refined
Δρmax, Δρmin (e Å−3)	0.22, −0.14

Computer programs: APEX3 and SAINT (Bruker, 2016 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL2018 (Sheldrick, 2015b ▸), DIAMOND (Brandenburg & Putz, 2012 ▸) and SHELXTL (Sheldrick, 2008).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989019009691/vm2219sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989019009691/vm2219Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989019009691/vm2219Isup3.cdx

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989019009691/vm2219Isup4.cml

CCDC reference: 1938997

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

C17H23NO2	F(000) = 592
Mr = 273.36	Dx = 1.158 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
a = 16.2512 (4) Å	Cell parameters from 9962 reflections
b = 7.6859 (2) Å	θ = 5.1–74.4°
c = 13.0989 (3) Å	µ = 0.59 mm−1
β = 106.640 (1)°	T = 150 K
V = 1567.60 (7) Å3	Block, orange-red
Z = 4	0.24 × 0.20 × 0.14 mm

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	3128 independent reflections
Radiation source: INCOATEC IµS micro–focus source	2879 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.029
Detector resolution: 10.4167 pixels mm-1	θmax = 74.4°, θmin = 6.4°
ω scans	h = −18→19
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −9→8
Tmin = 0.82, Tmax = 0.92	l = −16→15
11594 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035	All H-atom parameters refined
wR(F2) = 0.096	w = 1/[σ2(Fo2) + (0.0474P)2 + 0.2775P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
3128 reflections	Δρmax = 0.22 e Å−3
274 parameters	Δρmin = −0.14 e Å−3
0 restraints	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0114 (9)

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.

	x	y	z	Uiso*/Ueq
O1	0.08032 (5)	0.55941 (11)	0.77294 (5)	0.0450 (2)
O2	0.17619 (6)	0.85773 (11)	0.72453 (7)	0.0545 (3)
N1	0.16664 (5)	0.69895 (11)	0.57210 (6)	0.0326 (2)
C1	0.13290 (6)	0.53470 (13)	0.53302 (7)	0.0295 (2)
C2	0.13301 (6)	0.45892 (14)	0.43750 (8)	0.0351 (2)
H2	0.1570 (8)	0.5200 (17)	0.3857 (10)	0.045 (3)*
C3	0.09707 (7)	0.29390 (15)	0.41701 (9)	0.0418 (3)
H3	0.0954 (9)	0.2350 (19)	0.3486 (11)	0.052 (4)*
C4	0.06188 (8)	0.20883 (15)	0.48797 (10)	0.0443 (3)
H4	0.0372 (9)	0.094 (2)	0.4688 (11)	0.059 (4)*
C5	0.05985 (7)	0.28781 (14)	0.58244 (9)	0.0389 (3)
H5	0.0330 (9)	0.2317 (19)	0.6319 (11)	0.052 (4)*
C6	0.09576 (6)	0.45211 (13)	0.60433 (7)	0.0314 (2)
C7	0.10401 (6)	0.57137 (14)	0.69345 (7)	0.0341 (2)
C8	0.15339 (7)	0.73151 (14)	0.66825 (8)	0.0365 (2)
C9	0.21591 (7)	0.80831 (14)	0.51971 (9)	0.0363 (2)
H9A	0.2192 (8)	0.9233 (18)	0.5546 (10)	0.046 (3)*
H9B	0.1825 (8)	0.8201 (16)	0.4435 (10)	0.039 (3)*
C10	0.30417 (7)	0.73223 (15)	0.52814 (9)	0.0373 (2)
H10A	0.3406 (9)	0.7374 (18)	0.6044 (12)	0.051 (4)*
H10B	0.2979 (8)	0.6044 (19)	0.5107 (10)	0.044 (3)*
C11	0.34813 (7)	0.82187 (15)	0.45444 (9)	0.0386 (3)
H11A	0.3578 (9)	0.946 (2)	0.4751 (11)	0.051 (4)*
H11B	0.3094 (8)	0.8199 (17)	0.3812 (11)	0.046 (3)*
C12	0.43166 (7)	0.73437 (15)	0.45297 (9)	0.0395 (3)
H12A	0.4735 (9)	0.7357 (19)	0.5258 (11)	0.052 (4)*
H12B	0.4207 (9)	0.611 (2)	0.4372 (11)	0.052 (4)*
C13	0.47345 (7)	0.81285 (16)	0.37372 (9)	0.0405 (3)
H13A	0.4834 (9)	0.940 (2)	0.3898 (11)	0.056 (4)*
H13B	0.4323 (9)	0.8053 (17)	0.3010 (11)	0.049 (4)*
C14	0.55597 (7)	0.72275 (16)	0.37127 (9)	0.0405 (3)
H14A	0.5991 (9)	0.7303 (19)	0.4437 (12)	0.056 (4)*
H14B	0.5448 (9)	0.595 (2)	0.3575 (12)	0.057 (4)*
C15	0.59615 (7)	0.79507 (16)	0.28902 (9)	0.0403 (3)
H15A	0.6056 (9)	0.921 (2)	0.3018 (11)	0.059 (4)*
H15B	0.5542 (9)	0.7861 (17)	0.2165 (11)	0.048 (3)*
C16	0.67845 (8)	0.70487 (17)	0.28662 (10)	0.0448 (3)
H16A	0.7217 (10)	0.725 (2)	0.3567 (13)	0.064 (4)*
H16B	0.6688 (10)	0.575 (2)	0.2808 (13)	0.068 (4)*
C17	0.71335 (9)	0.76729 (19)	0.19762 (11)	0.0494 (3)
H17A	0.6695 (11)	0.753 (2)	0.1291 (14)	0.070 (5)*
H17B	0.7272 (12)	0.892 (3)	0.2051 (14)	0.081 (5)*
H17C	0.7687 (12)	0.699 (2)	0.1952 (14)	0.076 (5)*

	U11	U22	U33	U12	U13	U23
O1	0.0578 (5)	0.0554 (5)	0.0250 (4)	0.0034 (4)	0.0169 (3)	0.0028 (3)
O2	0.0739 (6)	0.0483 (5)	0.0427 (5)	−0.0124 (4)	0.0191 (4)	−0.0180 (4)
N1	0.0383 (5)	0.0331 (4)	0.0272 (4)	−0.0027 (3)	0.0110 (3)	−0.0016 (3)
C1	0.0299 (5)	0.0327 (5)	0.0254 (4)	0.0014 (4)	0.0072 (3)	−0.0003 (3)
C2	0.0360 (5)	0.0430 (6)	0.0286 (5)	−0.0006 (4)	0.0129 (4)	−0.0041 (4)
C3	0.0421 (6)	0.0468 (6)	0.0384 (6)	−0.0016 (5)	0.0148 (4)	−0.0141 (5)
C4	0.0477 (6)	0.0365 (6)	0.0510 (7)	−0.0068 (5)	0.0178 (5)	−0.0096 (5)
C5	0.0418 (6)	0.0376 (6)	0.0394 (6)	−0.0019 (4)	0.0149 (4)	0.0029 (4)
C6	0.0338 (5)	0.0353 (5)	0.0251 (4)	0.0021 (4)	0.0086 (3)	0.0016 (4)
C7	0.0385 (5)	0.0408 (5)	0.0222 (4)	0.0039 (4)	0.0076 (4)	0.0020 (4)
C8	0.0426 (6)	0.0390 (5)	0.0270 (5)	0.0006 (4)	0.0083 (4)	−0.0035 (4)
C9	0.0394 (6)	0.0341 (5)	0.0360 (5)	−0.0014 (4)	0.0113 (4)	0.0058 (4)
C10	0.0365 (5)	0.0390 (6)	0.0357 (5)	−0.0010 (4)	0.0092 (4)	0.0072 (4)
C11	0.0375 (5)	0.0393 (6)	0.0381 (5)	−0.0022 (4)	0.0095 (4)	0.0080 (4)
C12	0.0367 (6)	0.0422 (6)	0.0387 (6)	−0.0016 (4)	0.0094 (4)	0.0068 (4)
C13	0.0371 (6)	0.0461 (6)	0.0370 (6)	−0.0011 (4)	0.0086 (4)	0.0070 (5)
C14	0.0368 (6)	0.0457 (6)	0.0378 (6)	−0.0014 (4)	0.0088 (4)	0.0058 (4)
C15	0.0384 (6)	0.0450 (6)	0.0364 (5)	−0.0016 (4)	0.0090 (4)	0.0052 (4)
C16	0.0388 (6)	0.0523 (7)	0.0435 (6)	−0.0006 (5)	0.0118 (5)	0.0066 (5)
C17	0.0496 (7)	0.0541 (7)	0.0486 (7)	−0.0067 (6)	0.0205 (6)	−0.0001 (6)

O1—C7	1.2126 (12)	C10—H10B	1.007 (14)
O2—C8	1.2106 (13)	C11—C12	1.5200 (16)
N1—C8	1.3603 (13)	C11—H11A	0.989 (15)
N1—C1	1.4127 (13)	C11—H11B	0.986 (14)
N1—C9	1.4606 (13)	C12—C13	1.5186 (15)
C1—C2	1.3806 (13)	C12—H12A	1.000 (14)
C1—C6	1.4009 (13)	C12—H12B	0.979 (16)
C2—C3	1.3899 (16)	C13—C14	1.5178 (16)
C2—H2	0.992 (13)	C13—H13A	1.007 (16)
C3—C4	1.3868 (16)	C13—H13B	0.997 (14)
C3—H3	0.997 (14)	C14—C15	1.5163 (15)
C4—C5	1.3871 (16)	C14—H14A	1.007 (15)
C4—H4	0.971 (16)	C14—H14B	1.002 (16)
C5—C6	1.3862 (15)	C15—C16	1.5147 (17)
C5—H5	0.980 (14)	C15—H15A	0.986 (17)
C6—C7	1.4599 (13)	C15—H15B	1.000 (14)
C7—C8	1.5554 (15)	C16—C17	1.5132 (16)
C9—C10	1.5233 (15)	C16—H16A	0.995 (17)
C9—H9A	0.989 (14)	C16—H16B	1.011 (18)
C9—H9B	0.994 (13)	C17—H17A	0.979 (18)
C10—C11	1.5204 (14)	C17—H17B	0.98 (2)
C10—H10A	1.006 (15)	C17—H17C	1.050 (18)
C8—N1—C1	110.61 (8)	C10—C11—H11A	109.2 (8)
C8—N1—C9	125.63 (9)	C12—C11—H11B	107.8 (8)
C1—N1—C9	123.52 (8)	C10—C11—H11B	109.0 (8)
C2—C1—C6	121.72 (9)	H11A—C11—H11B	106.7 (11)
C2—C1—N1	127.18 (9)	C13—C12—C11	114.13 (9)
C6—C1—N1	111.09 (8)	C13—C12—H12A	109.5 (8)
C1—C2—C3	116.77 (9)	C11—C12—H12A	110.4 (8)
C1—C2—H2	121.5 (8)	C13—C12—H12B	109.4 (8)
C3—C2—H2	121.7 (8)	C11—C12—H12B	108.8 (8)
C4—C3—C2	122.14 (10)	H12A—C12—H12B	104.1 (12)
C4—C3—H3	118.6 (8)	C14—C13—C12	113.83 (9)
C2—C3—H3	119.3 (8)	C14—C13—H13A	111.1 (8)
C3—C4—C5	120.75 (10)	C12—C13—H13A	108.6 (8)
C3—C4—H4	118.3 (8)	C14—C13—H13B	108.0 (8)
C5—C4—H4	120.9 (8)	C12—C13—H13B	108.7 (8)
C6—C5—C4	117.84 (10)	H13A—C13—H13B	106.3 (11)
C6—C5—H5	120.4 (8)	C15—C14—C13	114.24 (9)
C4—C5—H5	121.8 (9)	C15—C14—H14A	108.8 (8)
C5—C6—C1	120.73 (9)	C13—C14—H14A	109.6 (8)
C5—C6—C7	132.39 (9)	C15—C14—H14B	108.9 (8)
C1—C6—C7	106.87 (8)	C13—C14—H14B	109.5 (8)
O1—C7—C6	131.29 (10)	H14A—C14—H14B	105.5 (12)
O1—C7—C8	123.52 (9)	C16—C15—C14	114.17 (10)
C6—C7—C8	105.19 (8)	C16—C15—H15A	110.9 (9)
O2—C8—N1	127.53 (10)	C14—C15—H15A	108.5 (8)
O2—C8—C7	126.26 (9)	C16—C15—H15B	108.3 (8)
N1—C8—C7	106.20 (8)	C14—C15—H15B	109.5 (8)
N1—C9—C10	112.12 (8)	H15A—C15—H15B	105.0 (11)
N1—C9—H9A	105.1 (8)	C17—C16—C15	113.51 (10)
C10—C9—H9A	112.6 (8)	C17—C16—H16A	109.9 (9)
N1—C9—H9B	108.0 (7)	C15—C16—H16A	107.7 (9)
C10—C9—H9B	109.9 (7)	C17—C16—H16B	109.9 (9)
H9A—C9—H9B	108.9 (10)	C15—C16—H16B	109.6 (9)
C11—C10—C9	112.57 (9)	H16A—C16—H16B	105.9 (13)
C11—C10—H10A	111.3 (8)	C16—C17—H17A	109.7 (10)
C9—C10—H10A	109.3 (8)	C16—C17—H17B	111.0 (10)
C11—C10—H10B	109.4 (7)	H17A—C17—H17B	106.5 (15)
C9—C10—H10B	109.0 (7)	C16—C17—H17C	112.2 (9)
H10A—C10—H10B	104.9 (11)	H17A—C17—H17C	108.7 (14)
C12—C11—C10	113.04 (9)	H17B—C17—H17C	108.6 (14)
C12—C11—H11A	110.9 (8)
C8—N1—C1—C2	178.81 (10)	C1—C6—C7—C8	−1.98 (10)
C9—N1—C1—C2	−6.62 (15)	C1—N1—C8—O2	177.89 (11)
C8—N1—C1—C6	−0.19 (11)	C9—N1—C8—O2	3.47 (18)
C9—N1—C1—C6	174.37 (9)	C1—N1—C8—C7	−1.07 (11)
C6—C1—C2—C3	−2.13 (15)	C9—N1—C8—C7	−175.49 (9)
N1—C1—C2—C3	178.96 (9)	O1—C7—C8—O2	2.55 (17)
C1—C2—C3—C4	0.59 (16)	C6—C7—C8—O2	−177.09 (11)
C2—C3—C4—C5	1.19 (18)	O1—C7—C8—N1	−178.47 (10)
C3—C4—C5—C6	−1.41 (17)	C6—C7—C8—N1	1.89 (11)
C4—C5—C6—C1	−0.11 (15)	C8—N1—C9—C10	103.80 (12)
C4—C5—C6—C7	179.33 (11)	C1—N1—C9—C10	−69.94 (12)
C2—C1—C6—C5	1.95 (15)	N1—C9—C10—C11	167.45 (9)
N1—C1—C6—C5	−178.98 (9)	C9—C10—C11—C12	−173.60 (9)
C2—C1—C6—C7	−177.62 (9)	C10—C11—C12—C13	175.57 (9)
N1—C1—C6—C7	1.45 (11)	C11—C12—C13—C14	−178.95 (10)
C5—C6—C7—O1	−1.08 (19)	C12—C13—C14—C15	177.47 (10)
C1—C6—C7—O1	178.42 (11)	C13—C14—C15—C16	−179.94 (10)
C5—C6—C7—C8	178.52 (11)	C14—C15—C16—C17	174.71 (10)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2i	0.992 (13)	2.412 (13)	3.3737 (13)	163.3 (10)
C3—H3···O1ii	0.997 (14)	2.454 (15)	3.2734 (14)	139.0 (11)
C9—H9B···O1i	0.994 (13)	2.546 (13)	3.5012 (13)	161.0 (10)
C17—H17B···O2iii	0.98 (2)	2.49 (2)	3.3941 (17)	153.3 (15)