Crystal structure and DFT study of benzyl 1-benzyl-2-oxo-1,2-di-hydro-quinoline-4-carboxyl-ate.

In the title quinoline derivative, C24H19NO3, the two benzyl rings are inclined to the quinoline ring mean plane by 74.09 (8) and 89.43 (7)°, and to each other by 63.97 (10)°. The carboxyl-ate group is twisted from the quinoline ring mean plane by 32.2 (2)°. There is a short intra-molecular C-H⋯O contact forming an S(6) ring motif. In the crystal, mol-ecules are linked by bifurcated C-H,H⋯O hydrogen bonds, forming layers parallel to the ac plane. The layers are linked by C-H⋯π inter-actions, forming a supra-molecular three-dimensional structure.

Chemical context

Heterocyclic compounds have paved the way for exceptional achievements in the fight against many life-threatening diseases (Alcaide et al., 2010 ▸). It is therefore no surprise that the development of new methodologies to synthesize biologically active heterocyclic compounds persists as a very important goal in organic chemistry (Jones et al., 2011 ▸). Quinolones and their derivatives have contributed substanti­ally to the evolution of anti­microbial agents. The development of anti­biotic quinolone began in 1962 with the discovery of nalidixic acid, which was used to treat urinary tract infections (Lesher et al., 1962 ▸). Quinolone derivatives are a classical division of organic chemistry; many of these mol­ecules have shown remarkable biological properties, including exceptional anti­bacterial activity (Beena & Rawat, 2013 ▸; Chai et al., 2011 ▸; Hoshino et al., 2008 ▸) and are used as anti-fungal (Musiol et al., 2010 ▸), anti-tumoral (Bergh et al., 1997 ▸) and anti-cancer drugs (Elderfield & LeVon, 1960 ▸). Recently, complexes based on quinoline-4-carb­oxy­lic acid have been reported (Bu et al., 2005 ▸; Xiong et al., 2000 ▸). The present study is a continuation of the synthesis of heterocyclic derivatives performed by our team (Chkirate et al., 2019a ▸,b ▸). It is part of an ongoing structural study of heterocyclic compounds and their utilization as mol­ecular (Faizi et al., 2016 ▸) and fluorescence sensors (Mukherjee et al., 2018 ▸); Kumar et al., 2017 ▸, 2018 ▸). We report herein the synthesis and the mol­ecular and crystal structures of the title compound, benzyl 1-benzyl-2-oxo-1,2-di­hydro­quinoline-4-carboxyl­ate, along with the density functional theory (DFT) calculations.

Structural commentary

The mol­ecular structure of the title compound is illustrated in Fig. 1 ▸. It is composed of two substituted aromatic rings attached to a planar quinolone ring (N1/C9–C17; r.m.s. deviation = 0.017 Å). The attached benzyl rings (C2–C7 and C19–C24) are inclined to the quinolone ring system by 74.09 (8) and 89.43 (7)°, respectively, and to each other by 63.97 (10)°. The carboxyl­ate group is twisted from the quinoline ring system by 32.2 (2)°. The carboxyl­ate group is involved in a short intra­molecular C—H⋯O contact forming an S(6) ring motif (Fig. 1 ▸ and Table 1 ▸).

Figure 1

A view of the mol­ecular structure of the title compound, with the atom labelling. Displacement ellipsoids are drawn at the 40% probability level. The intra­molecular C—H⋯O contact (see Table 1 ▸) is shown as a dashed line.

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C19–C24 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11⋯O2	0.93	2.34	2.962 (2)	124
C6—H6⋯O3i	0.93	2.55	3.184 (3)	126
C22—H22⋯O3ii	0.93	2.56	3.490 (2)	174
C13—H13⋯Cg1iii	0.93	2.91	3.727 (2)	147

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

Supra­molecular features

In the crystal, mol­ecules are linked by bifurcated C—H,H⋯O hydrogen bonds, forming layers lying parallel to the ac plane (Table 1 ▸ and Fig. 2 ▸). The layers are linked by C—H···π inter­actions, so forming a supra­molecular three-dimensional structure (Table 1 ▸ and Fig. 3 ▸).

Figure 2

A view of along the b axis of the crystal packing of the title compound. Hydrogen bonds (see Table 1 ▸) are shown as dashed lines. For clarity, only H atoms H6 and H22 have been included.

Figure 3

A view of along the c axis of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines and the C—H⋯π inter­actions as blue arrows (see Table 1 ▸). For clarity, only H atoms H6, H22 and H13 have been included (as grey balls).

Frontier mol­ecular orbital analysis

The highest occupied mol­ecular orbitals (HOMOs) and the lowest unoccupied mol­ecular orbitals (LUMOs) are named as frontier mol­ecular orbitals (FMOs). The FMOs play an important role in the optical and electric properties, as well as in quantum chemistry and UV–Vis spectra. The frontier orbital gap helps characterize the chemical reactivity and the kinetic stability of the mol­ecule. A mol­ecule with a small frontier orbital gap is generally associated with a high chemical reactivity, low kinetic stability and is also termed a soft mol­ecule. DFT quantum-chemical calculations for the title compound were performed at the B3LYP/6–311 G(d,p) level (Becke, 1993 ▸) as implemented in GAUSSIAN09 (Frisch et al., 2009 ▸). DFT structure optimization was performed starting from the X-ray geometry and the values compared with experimental values of bond lengths and bond angles matching with theoretical values. The basis set 6-311G(d,p) is well suited in its approach to the experimental data. The DFT study shows that the HOMO and LUMO are localized in the plane extending from the whole tetra-substituted benzene ring. The electron distribution of the HOMO-1, HOMO, LUMO and the LUMO+1 energy levels are shown in Fig. 4 ▸. The HOMO mol­ecular orbital exhibits both σ and π character, whereas HOMO-1 is dominated by π-orbital density. The LUMO is mainly composed of π-density while LUMO+1 has both σ and π electronic density. The HOMO–LUMO gap is found to be 0.15223 a.u. and the frontier mol­ecular orbital energies, E HOMO and E LUMO are −0.22932 and −0.07709 a.u., respectively.

Figure 4

Electron distribution of the HOMO-1, HOMO, LUMO and the LUMO+1 energy levels for the title compound.

Database survey

A search of the Cambridge Structural Database (CSD, version 5.40, update May 2019; Groom et al., 2016 ▸) for the 1-benzyl­quinolin-2(1H)-one skeleton gave ten hits. The dihedral angle between the benzyl and quinoline rings varies from ca 71.0 to 89.6°, compared to 89.43 (7)° in the title compound. Only two of these compounds have a carboxyl­ate group in position 4 on the quinoline ring, viz. ethyl 1-benzyl-3-hy­droxy-2-oxo-1,2-di­hydro­quinoline-4-carboxyl­ate (CSD refcode ZINHEL; Paterna et al., 2013 ▸) and benzyl 1-benzyl-2-oxo-3-vinyl-1,2-di­hydro­quinoline-4-carboxyl­ate (FAVZEK; Malini et al., 2017 ▸). The latter compound most closely resembles the title compound, with a vinyl substituent in position 3 of the quinoline ring. A view of the structural overlap of FAVZEK and the title compound is given in Fig. 5 ▸. The conformation of the two compounds differs essentially in the orientation of the carboxyl­ate group with respect to the quinoline ring: 85.6 (3)° in FAVZEK compared to 32.2 (2)° in the title compound. This is the result of steric hindrance resulting from the presence of the vinyl substituent in position 3 on the quinoline ring in FAVZEK. In the title compound, the benzyl rings (C19–C24 and C2–C7) are inclined to the quinoline ring by 89.43 (7) and 74.09 (8)°, respectively, while in FAVZEK the corresponding dihedral angles are 88.55 (11) and 76.44 (13)°. The two benzyl rings are inclined to each other by 63.97 (10)° in the title compound compared to 73.38 (16)° in FAVZEK.

Figure 5

The structural overlap (Mercury; Macrae et al., 2008 ▸) of the title compound (blue) and FAVZEK (red: benzyl 1-benzyl-2-oxo-3-vinyl-1,2-di­hydro­quinoline-4-carboxyl­ate; Malini et al., 2017 ▸).

Synthesis and crystallization

A mixture of 2-oxo-1,2-di­hydro­quinoline-4-carb­oxy­lic acid (1 g, 5.29 mmol), K2CO3 (1.46 g, 10.58 mmol), benzyl chloride (1.21 ml, 10.58 mmol) and tetra n-butyl­ammonium bromide as catalyst in DMF (50 ml) was stirred at room temperature for 48 h. The solution was filtered by suction and the solvent was removed under reduced pressure. The residue was chromatographed on a silica-gel column using hexane and ethyl acetate (v/v, 95/5) as eluents to afford the title compound. Colourless prismatic crystals of the title compound were obtained by slow evaporation of a solution in ethanol (yield 53%).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. The C-bound H atoms were placed in calculated positions and included in the refinement in the riding-model approximation: C—H = 0.93–0.97 Å with U iso(H) = 1.2U eq(C).

Table 2

Experimental details

Crystal data
Chemical formula	C24H19NO3
M r	369.40
Crystal system, space group	Monoclinic, P21/n
Temperature (K)	296
a, b, c (Å)	5.6101 (4), 19.5523 (11), 17.2761 (11)
β (°)	96.969 (5)
V (Å3)	1881.0 (2)
Z	4
Radiation type	Mo Kα
μ (mm−1)	0.09
Crystal size (mm)	0.71 × 0.52 × 0.25
Data collection
Diffractometer	STOE IPDS 2
Absorption correction	Integration (X-RED32; Stoe & Cie, 2002 ▸)
T min, T max	0.949, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	15909, 3686, 2270
R int	0.046
(sin θ/λ)max (Å−1)	0.617
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.041, 0.115, 0.95
No. of reflections	3686
No. of parameters	254
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.29, −0.17

Computer programs: X-AREA and X-RED32 (Stoe & Cie, 2002 ▸), SHELXT2018/2 (Sheldrick, 2015a ▸), SHELXL2018/3 (Sheldrick, 2015b ▸), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ▸), Mercury (Macrae et al., 2008 ▸) and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989019007989/su5500sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989019007989/su5500Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989019007989/su5500Isup3.cml

CCDC reference: 1920509

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

C24H19NO3	F(000) = 776
Mr = 369.40	Dx = 1.304 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 5.6101 (4) Å	Cell parameters from 14721 reflections
b = 19.5523 (11) Å	θ = 2.1–30.9°
c = 17.2761 (11) Å	µ = 0.09 mm−1
β = 96.969 (5)°	T = 296 K
V = 1881.0 (2) Å3	Prism, colourless
Z = 4	0.71 × 0.52 × 0.25 mm

STOE IPDS 2 diffractometer	3686 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	2270 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.046
Detector resolution: 6.67 pixels mm-1	θmax = 26.0°, θmin = 2.1°
rotation method scans	h = −6→6
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −24→24
Tmin = 0.949, Tmax = 0.979	l = −21→21
15909 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041	H-atom parameters constrained
wR(F2) = 0.115	w = 1/[σ2(Fo2) + (0.0653P)2] where P = (Fo2 + 2Fc2)/3
S = 0.95	(Δ/σ)max < 0.001
3686 reflections	Δρmax = 0.29 e Å−3
254 parameters	Δρmin = −0.17 e Å−3
0 restraints	Extinction correction: (SHELXL2018/3; Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0160 (19)

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.

	x	y	z	Uiso*/Ueq
O1	0.6381 (2)	0.38420 (8)	0.44614 (6)	0.0805 (4)
O2	0.2849 (3)	0.41941 (9)	0.38836 (8)	0.0926 (5)
O3	1.0727 (3)	0.30369 (9)	0.23941 (8)	0.0974 (5)
N1	0.8617 (2)	0.39351 (7)	0.18321 (7)	0.0571 (4)
C1	0.5448 (4)	0.38554 (13)	0.52105 (10)	0.0808 (6)
H1A	0.423278	0.350492	0.522931	0.097*
H1B	0.473201	0.429694	0.529330	0.097*
C2	0.7519 (3)	0.37265 (9)	0.58196 (9)	0.0603 (4)
C3	0.9437 (4)	0.41769 (11)	0.59339 (12)	0.0802 (6)
H3	0.945035	0.456570	0.562433	0.096*
C4	1.1323 (4)	0.40511 (13)	0.65041 (13)	0.0906 (7)
H4	1.260989	0.435378	0.657408	0.109*
C5	1.1318 (4)	0.34884 (15)	0.69647 (12)	0.0909 (7)
H5	1.260436	0.340420	0.734504	0.109*
C6	0.9439 (4)	0.30506 (12)	0.68696 (12)	0.0835 (6)
H6	0.942364	0.266986	0.719161	0.100*
C7	0.7553 (3)	0.31656 (10)	0.63000 (10)	0.0693 (5)
H7	0.627693	0.285877	0.623838	0.083*
C8	0.4909 (3)	0.40350 (9)	0.38491 (10)	0.0627 (5)
C9	0.6101 (3)	0.40005 (8)	0.31252 (9)	0.0542 (4)
C10	0.5488 (3)	0.44685 (8)	0.24814 (9)	0.0512 (4)
C11	0.3727 (3)	0.49795 (9)	0.24800 (10)	0.0608 (4)
H11	0.284034	0.501326	0.289959	0.073*
C12	0.3296 (3)	0.54270 (9)	0.18732 (11)	0.0704 (5)
H12	0.214571	0.576813	0.188525	0.085*
C13	0.4568 (4)	0.53723 (10)	0.12432 (11)	0.0729 (5)
H13	0.426062	0.567624	0.082904	0.088*
C14	0.6281 (3)	0.48765 (9)	0.12175 (10)	0.0652 (5)
H14	0.710104	0.484076	0.078274	0.078*
C15	0.6801 (3)	0.44252 (8)	0.18394 (9)	0.0526 (4)
C16	0.9158 (3)	0.34674 (10)	0.24281 (10)	0.0669 (5)
C17	0.7823 (3)	0.35337 (10)	0.30827 (9)	0.0660 (5)
H17	0.817545	0.323540	0.350029	0.079*
C18	1.0159 (3)	0.39223 (10)	0.12080 (9)	0.0632 (5)
H18A	1.169995	0.372994	0.141437	0.076*
H18B	1.043763	0.438967	0.105353	0.076*
C19	0.9192 (3)	0.35221 (8)	0.04907 (9)	0.0516 (4)
C20	1.0478 (3)	0.35411 (10)	−0.01382 (10)	0.0647 (5)
H20	1.185150	0.381033	−0.011516	0.078*
C21	0.9761 (4)	0.31666 (11)	−0.08022 (10)	0.0767 (6)
H21	1.066000	0.318117	−0.122010	0.092*
C22	0.7736 (4)	0.27749 (11)	−0.08482 (11)	0.0791 (6)
H22	0.724133	0.252641	−0.129819	0.095*
C23	0.6436 (4)	0.27501 (10)	−0.02272 (12)	0.0784 (6)
H23	0.505989	0.248180	−0.025486	0.094*
C24	0.7161 (3)	0.31221 (10)	0.04413 (10)	0.0644 (5)
H24	0.626799	0.310163	0.086046	0.077*

	U11	U22	U33	U12	U13	U23
O1	0.0716 (8)	0.1257 (12)	0.0459 (6)	0.0180 (8)	0.0138 (6)	0.0066 (7)
O2	0.0757 (9)	0.1299 (13)	0.0751 (9)	0.0236 (9)	0.0211 (7)	0.0157 (9)
O3	0.1090 (11)	0.1200 (12)	0.0646 (8)	0.0597 (10)	0.0158 (7)	0.0014 (8)
N1	0.0554 (8)	0.0715 (9)	0.0438 (7)	0.0039 (7)	0.0038 (6)	−0.0072 (6)
C1	0.0775 (12)	0.1182 (17)	0.0503 (10)	0.0091 (12)	0.0225 (9)	0.0059 (11)
C2	0.0656 (10)	0.0720 (11)	0.0462 (8)	−0.0049 (9)	0.0191 (8)	−0.0062 (8)
C3	0.0999 (15)	0.0716 (12)	0.0756 (13)	−0.0163 (11)	0.0368 (12)	−0.0042 (10)
C4	0.0796 (13)	0.1186 (19)	0.0761 (14)	−0.0394 (13)	0.0196 (12)	−0.0306 (14)
C5	0.0716 (12)	0.147 (2)	0.0550 (11)	−0.0068 (14)	0.0100 (10)	−0.0096 (13)
C6	0.0852 (14)	0.1003 (16)	0.0652 (12)	−0.0016 (12)	0.0099 (10)	0.0125 (11)
C7	0.0771 (12)	0.0755 (12)	0.0564 (10)	−0.0184 (10)	0.0129 (9)	−0.0005 (9)
C8	0.0591 (10)	0.0727 (12)	0.0572 (10)	0.0062 (9)	0.0102 (8)	−0.0003 (8)
C9	0.0546 (9)	0.0624 (10)	0.0448 (8)	0.0017 (8)	0.0031 (7)	−0.0039 (7)
C10	0.0505 (8)	0.0558 (9)	0.0460 (8)	−0.0026 (7)	0.0005 (7)	−0.0083 (7)
C11	0.0606 (10)	0.0634 (10)	0.0574 (9)	0.0047 (8)	0.0031 (8)	−0.0092 (8)
C12	0.0773 (12)	0.0599 (11)	0.0718 (12)	0.0133 (9)	−0.0002 (10)	−0.0007 (9)
C13	0.0873 (13)	0.0644 (12)	0.0652 (11)	0.0039 (10)	0.0016 (10)	0.0111 (9)
C14	0.0729 (11)	0.0687 (11)	0.0545 (9)	−0.0053 (9)	0.0099 (8)	0.0024 (8)
C15	0.0518 (8)	0.0562 (10)	0.0485 (9)	−0.0034 (7)	0.0008 (7)	−0.0062 (7)
C16	0.0697 (11)	0.0811 (12)	0.0483 (9)	0.0213 (10)	0.0014 (8)	−0.0065 (9)
C17	0.0751 (11)	0.0771 (12)	0.0448 (9)	0.0178 (10)	0.0039 (8)	0.0025 (8)
C18	0.0529 (9)	0.0834 (13)	0.0539 (9)	−0.0039 (8)	0.0092 (8)	−0.0107 (9)
C19	0.0493 (8)	0.0602 (10)	0.0450 (8)	0.0077 (7)	0.0049 (7)	0.0009 (7)
C20	0.0618 (10)	0.0778 (12)	0.0558 (10)	0.0031 (9)	0.0125 (8)	0.0002 (9)
C21	0.0878 (13)	0.0937 (15)	0.0506 (10)	0.0169 (12)	0.0167 (9)	−0.0051 (10)
C22	0.0912 (14)	0.0853 (14)	0.0585 (11)	0.0099 (12)	−0.0011 (11)	−0.0193 (10)
C23	0.0741 (12)	0.0816 (14)	0.0764 (13)	−0.0097 (10)	−0.0036 (11)	−0.0154 (11)
C24	0.0603 (10)	0.0794 (12)	0.0543 (9)	−0.0037 (9)	0.0101 (8)	−0.0041 (9)

O1—C8	1.316 (2)	C10—C15	1.406 (2)
O1—C1	1.454 (2)	C11—C12	1.364 (2)
O2—C8	1.205 (2)	C11—H11	0.9300
O3—C16	1.225 (2)	C12—C13	1.376 (3)
N1—C16	1.383 (2)	C12—H12	0.9300
N1—C15	1.400 (2)	C13—C14	1.369 (3)
N1—C18	1.462 (2)	C13—H13	0.9300
C1—C2	1.491 (3)	C14—C15	1.394 (2)
C1—H1A	0.9700	C14—H14	0.9300
C1—H1B	0.9700	C16—C17	1.436 (3)
C2—C7	1.374 (2)	C17—H17	0.9300
C2—C3	1.386 (3)	C18—C19	1.510 (2)
C3—C4	1.378 (3)	C18—H18A	0.9700
C3—H3	0.9300	C18—H18B	0.9700
C4—C5	1.358 (3)	C19—C24	1.376 (2)
C4—H4	0.9300	C19—C20	1.376 (2)
C5—C6	1.352 (3)	C20—C21	1.379 (3)
C5—H5	0.9300	C20—H20	0.9300
C6—C7	1.373 (3)	C21—C22	1.364 (3)
C6—H6	0.9300	C21—H21	0.9300
C7—H7	0.9300	C22—C23	1.369 (3)
C8—C9	1.490 (2)	C22—H22	0.9300
C9—C17	1.338 (2)	C23—C24	1.383 (2)
C9—C10	1.449 (2)	C23—H23	0.9300
C10—C11	1.405 (2)	C24—H24	0.9300
C8—O1—C1	116.85 (14)	C11—C12—H12	120.1
C16—N1—C15	122.69 (14)	C13—C12—H12	120.1
C16—N1—C18	116.21 (14)	C14—C13—C12	120.92 (17)
C15—N1—C18	120.98 (14)	C14—C13—H13	119.5
O1—C1—C2	106.92 (15)	C12—C13—H13	119.5
O1—C1—H1A	110.3	C13—C14—C15	120.37 (17)
C2—C1—H1A	110.3	C13—C14—H14	119.8
O1—C1—H1B	110.3	C15—C14—H14	119.8
C2—C1—H1B	110.3	C14—C15—N1	120.74 (16)
H1A—C1—H1B	108.6	C14—C15—C10	119.28 (15)
C7—C2—C3	117.88 (17)	N1—C15—C10	119.98 (14)
C7—C2—C1	120.90 (17)	O3—C16—N1	120.85 (17)
C3—C2—C1	121.20 (18)	O3—C16—C17	123.13 (17)
C4—C3—C2	120.3 (2)	N1—C16—C17	116.00 (15)
C4—C3—H3	119.9	C9—C17—C16	123.63 (16)
C2—C3—H3	119.9	C9—C17—H17	118.2
C5—C4—C3	120.5 (2)	C16—C17—H17	118.2
C5—C4—H4	119.8	N1—C18—C19	115.36 (13)
C3—C4—H4	119.8	N1—C18—H18A	108.4
C6—C5—C4	119.9 (2)	C19—C18—H18A	108.4
C6—C5—H5	120.0	N1—C18—H18B	108.4
C4—C5—H5	120.0	C19—C18—H18B	108.4
C5—C6—C7	120.3 (2)	H18A—C18—H18B	107.5
C5—C6—H6	119.8	C24—C19—C20	118.42 (16)
C7—C6—H6	119.8	C24—C19—C18	123.92 (15)
C6—C7—C2	121.09 (18)	C20—C19—C18	117.62 (15)
C6—C7—H7	119.5	C19—C20—C21	120.96 (18)
C2—C7—H7	119.5	C19—C20—H20	119.5
O2—C8—O1	123.11 (17)	C21—C20—H20	119.5
O2—C8—C9	125.75 (16)	C22—C21—C20	120.22 (19)
O1—C8—C9	111.09 (14)	C22—C21—H21	119.9
C17—C9—C10	119.64 (15)	C20—C21—H21	119.9
C17—C9—C8	118.55 (15)	C21—C22—C23	119.53 (18)
C10—C9—C8	121.79 (14)	C21—C22—H22	120.2
C11—C10—C15	118.48 (15)	C23—C22—H22	120.2
C11—C10—C9	123.49 (15)	C22—C23—C24	120.35 (19)
C15—C10—C9	117.97 (14)	C22—C23—H23	119.8
C12—C11—C10	121.10 (17)	C24—C23—H23	119.8
C12—C11—H11	119.5	C19—C24—C23	120.51 (18)
C10—C11—H11	119.5	C19—C24—H24	119.7
C11—C12—C13	119.81 (17)	C23—C24—H24	119.7
C8—O1—C1—C2	−171.20 (17)	C16—N1—C15—C14	−178.53 (15)
O1—C1—C2—C7	−118.66 (19)	C18—N1—C15—C14	5.5 (2)
O1—C1—C2—C3	63.1 (2)	C16—N1—C15—C10	1.9 (2)
C7—C2—C3—C4	1.2 (3)	C18—N1—C15—C10	−174.07 (14)
C1—C2—C3—C4	179.46 (18)	C11—C10—C15—C14	−1.5 (2)
C2—C3—C4—C5	−0.6 (3)	C9—C10—C15—C14	−178.87 (14)
C3—C4—C5—C6	−0.6 (3)	C11—C10—C15—N1	178.12 (13)
C4—C5—C6—C7	1.2 (3)	C9—C10—C15—N1	0.7 (2)
C5—C6—C7—C2	−0.5 (3)	C15—N1—C16—O3	178.49 (17)
C3—C2—C7—C6	−0.7 (3)	C18—N1—C16—O3	−5.4 (2)
C1—C2—C7—C6	−178.97 (19)	C15—N1—C16—C17	−3.1 (2)
C1—O1—C8—O2	−2.7 (3)	C18—N1—C16—C17	173.04 (15)
C1—O1—C8—C9	179.62 (17)	C10—C9—C17—C16	0.7 (3)
O2—C8—C9—C17	−147.7 (2)	C8—C9—C17—C16	−177.71 (16)
O1—C8—C9—C17	29.9 (2)	O3—C16—C17—C9	−179.80 (19)
O2—C8—C9—C10	33.9 (3)	N1—C16—C17—C9	1.8 (3)
O1—C8—C9—C10	−148.47 (15)	C16—N1—C18—C19	97.36 (17)
C17—C9—C10—C11	−179.20 (16)	C15—N1—C18—C19	−86.45 (19)
C8—C9—C10—C11	−0.9 (2)	N1—C18—C19—C24	−7.8 (2)
C17—C9—C10—C15	−2.0 (2)	N1—C18—C19—C20	174.72 (15)
C8—C9—C10—C15	176.37 (14)	C24—C19—C20—C21	−0.3 (3)
C15—C10—C11—C12	−0.2 (2)	C18—C19—C20—C21	177.36 (16)
C9—C10—C11—C12	176.97 (15)	C19—C20—C21—C22	0.7 (3)
C10—C11—C12—C13	1.2 (3)	C20—C21—C22—C23	−0.7 (3)
C11—C12—C13—C14	−0.5 (3)	C21—C22—C23—C24	0.3 (3)
C12—C13—C14—C15	−1.3 (3)	C20—C19—C24—C23	−0.1 (3)
C13—C14—C15—N1	−177.34 (16)	C18—C19—C24—C23	−177.59 (17)
C13—C14—C15—C10	2.3 (2)	C22—C23—C24—C19	0.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O2	0.93	2.34	2.962 (2)	124
C6—H6···O3i	0.93	2.55	3.184 (3)	126
C22—H22···O3ii	0.93	2.56	3.490 (2)	174
C13—H13···Cg1iii	0.93	2.91	3.727 (2)	147