Crystal structure of 1-[(2S*,4R*)-6-fluoro-2-methyl-1,2,3,4-tetra­hydro­quinolin-4-yl]pyrrolidin-2-one

In the title compound, the 1,2,3,4-tetra­hydro­pyridine ring of the quinoline moiety adopts a half-chair conformation while the pyrrolidine ring has an envelope conformation. In the crystal, mol­ecules are linked by N—H⋯O and C—H⋯O hydrogen bonds, forming sheets lying parallel to (10), which are linked via C—H⋯F hydrogen bonds and C—H⋯π inter­actions, forming a three-dimensional structure.

Abstract

In the title compound, C₁₄H₁₇FN₂O, the 1,2,3,4-tetra­hydro­pyridine ring of the quinoline moiety adopts a half-chair conformation, while the pyrrolidine ring has an envelope conformation with the central methyl­ene C atom as the flap. The pyrrolidine ring lies in the equatorial plane and its mean plane is normal to the mean plane of the quinoline ring system, with a dihedral angle value of 88.37 (9)°. The bridging N—C bond distance [1.349 (3) Å] is substanti­ally shorter than the sum of the covalent radii (d _cov: C—N = 1.47 Å and C=N = 1.27 Å), which indicates partial double-bond character for this bond, resulting in a certain degree of charge delocalization. In the crystal, mol­ecules are linked by N—H⋯O and C—H⋯O hydrogen bonds, forming sheets lying parallel to (10-1). These two-dimensional networks are linked via C—H⋯F hydrogen bonds and C—H⋯π inter­actions, forming a three-dimensional structure.

Chemical context  

Tetra­hydro­quinolines have been significant synthetic targets due to their ubiquitous distribution in natural products and as medicinal agents (Trost et al., 1991 ▶). They are potential anti­cancer agents and 2-aryl-4-(2-oxopyrrolidin-1-yl)-1,2,3,4-tetra­hydro­quinolines have been reported to be inhibitors of HIV transcription. Furthermore, 2-methyl tetra­hydro­quino­lines have also been found to exhibit high modulating activity in multidrug resistance (MDR) (Hiessbock et al., 1999 ▶). In view of their broad spectrum of medicinal properties and in continuation of our work on new quinoline-based therapeutic agents (Pradeep et al., 2014 ▶), we have synthesized the title compound and report herein on its spectroscopic and crystallographic characterization.

Structural commentary  

The mol­ecular structure of the title mol­ecule is shown in Fig. 1 ▶. The relative configuration of the asymmetric centers is S for atom C2 and R for atom C4.

Figure 1.

A view of the mol­ecular structure of the title mol­ecule, with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

The pyrrolidine ring adopts an envelope conformation with the flap atom C15 deviating by 0.197 (2) Å from the mean plane defined by the atoms N12/C13/C14/C16. The pyrrolidine ring lies in the equatorial plane and its mean plane is perpendicular to the mean plane of the quinoline ring system, as indicated by the dihedral angle of 88.37 (9)°. The N12—C13 distance [1.349 (3) Å] is substanti­ally shorter than the sum of the covalent radii [d _cov: C—N = 1.47 Å and C=N = 1.27 Å; Holleman et al., 2007 ▶], which indicates partial double-bond character for this bond, resulting in a certain degree of charge delocalization. The C13=O1 bond length of 1.235 (3) Å confirms the presence of a keto group in the pyrrolidine moiety.

The tetra­hydro­pyridine ring of the quinoline system adopts a half-chair conformation with atom C10 deviating by 0.285 (2) Å from the mean plane defined by atoms N1/C2–C4/C9. This is confirmed by the puckering amplitude Q = 0.496 (2) Å. Although the quinoline ring system adopts a distorted half-chair conformation, the torsion angles C9—N1—C2—C3 and C2—C3—C4—C10 are −40.8 (2) and −53.0 (2)°, respectively. These differ from the corresponding angles [−47.8 (2) and −45.0 (2)°, respectively] in 6-eth­oxy-1,2,3,4-tetra­hydro-2,2,4-tri­methyl­quinoline (Rybakov et al., 2004 ▶). This can be attributed to the steric hindrance caused by the change in the substituents on the quinoline ring system.

The conformation of the tetra­hydro­pyridine ring and that of the pyrrolidine ring are similar to those observed in, for example, 1-[2-(2-fur­yl)-6-methyl-1,2,3,4-tetra­hydro­quinolin-4-yl]pyrrolidin-2-one (Vizcaya et al., 2012 ▶).

Supra­molecular features  

In the crystal, mol­ecules are linked by N—H⋯O and C—H⋯O hydrogen bonds, forming sheets lying parallel to (10); see Fig. 2 ▶ and Table 1 ▶. These two-dimensional networks are linked via C—H⋯F hydrogen bonds and C—H⋯π inter­actions, forming a three-dimensional structure (Table 1 ▶ and Fig. 3 ▶).

Figure 2.

A viewed along the c axis of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines (see Table 1 ▶ for details; H atoms not involved in hydrogen bonding have been omitted for clarity).

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

Cg1 is the centroid of the C5–C10 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1i	0.84 (3)	2.46 (3)	3.273 (2)	162 (2)
C7—H7⋯O1ii	0.93	2.51	3.351 (3)	150
C15—H15B⋯F1iii	0.97	2.48	3.189 (3)	130
C11—H11C⋯Cg1iv	0.97	2.80	3.748 (3)	168

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

Figure 3.

A viewed along the b axis of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines (see Table 1 ▶ for details; H atoms not involved in hydrogen bonding have been omitted for clarity).

Database survey  

A search of the Cambridge Structural Database (Version 5.35, last update May 2014; Allen et al., 2002 ▶) for the substructure (1,2,3,4-tetra­hydro­quinolin-4-yl)pyrrolidin-2-one yielded seven hits. Two of these crystallized in a chiral space group; P2₁2₁2₁ for the 2-(4-meth­oxy­phen­yl) derivative (refcode: HABXIT; Shen & Ji, 2008 ▶), and P6₁ for the trans diastereomer of the 2-(4-nitro­phen­yl)-5-(5-phenyl-1,2-oxazol-3-yl) derivative (refcode: IKAZEA; Gutierrez et al., 2011a ▶). The crystal structure of the racemic form of the latter has also been reported (refcode: QALCOX; Gutierrez et al., 2011b ▶).

In all seven compounds, the tetra­hydro­pyridine ring has a half-chair conformation, while in three mol­ecules the pyrrolidine ring has an envelope conformation and in another three mol­ecules a twist conformation. The orientation of the pyrrolidine ring with respect to the quinoline ring is very similar if one excludes the two compounds that have a substituent in the 5-position of the quinoline ring (Gutierrez et al., 2011a ▶,b ▶). The two mean planes are inclined to one another by dihedral angles varying from ca 79.98 to 89.59°, compared to 88.37 (9)° in the title compound.

Synthesis and crystallization  

A catalytic amount of SbF₃ (10 mol%) was added to a mixture of 4-flouroaniline (1 equivalent) and N-vinyl­pyrrolidone (2–3 equivalents) in aceto­nitrile (5–10 ml). The reaction mixture was stirred at ambient temperature (292 K) for 20–70 min. After completion of the reaction, as indicated by TLC using ethyl acetate/hexane as eluent, the solvent was removed under vacuo. The crude product was then quenched with water and the catalyst was decomposed by addition of the appropriate amount of sodium bicarbonate solution. It was then extracted with ethyl acetate (10 ml × 5 times), dried and purified by column chromatography using ethyl acetate/hexane as eluent (petroleum ether/ethyl acetate 80:20 v/v). White crystals were obtained by slow evaporation of the solvent.

In the ¹H NMR spectrum of the title compound, the three quadrates at δ 1.60, 2.95 and 3.22 p.p.m. correspond to three protons at C₃—H, C_5′—H and C_4′—H, respectively. A doublet at δ 5.24 p.p.m. corresponds to C₄—H, a singlet at δ 5.62 p.p.m. corresponds to the –NH proton and the number of protons is in accordance with the obtained structure. Additional support to elucidate the structure was obtained from ¹³C NMR (see the archived CIF for more details). The mass spectrum was recorded as additional evidence for the proposed structure: M+1 peak at m/z = 250.1.

Refinement  

Crystal data, data collection and structure refinement details are summarized in Table 2 ▶. The NH H atom was located from a difference Fourier map and freely refined. The C-bound H atoms were fixed geometrically (C—H = 0.93–0.96 Å) and allowed to ride on their parent atoms with U _iso(H) = 1.5U _eq(C) for methyl H atoms and = 1.2U _eq(C) for other H atoms.

Table 2. Experimental details.

Crystal data
Chemical formula	C14H17FN2O
M r	248.30
Crystal system, space group	Monoclinic, P21/n
Temperature (K)	100
a, b, c (Å)	11.3414 (3), 9.1909 (3), 12.6799 (4)
β (°)	111.569 (2)
V (Å3)	1229.17 (7)
Z	4
Radiation type	Cu Kα
μ (mm−1)	0.79
Crystal size (mm)	0.23 × 0.22 × 0.21
Data collection
Diffractometer	Bruker X8 Proteum
Absorption correction	Multi-scan (SADABS; Bruker, 2013 ▶)
T min, T max	0.834, 0.848
No. of measured, independent and observed [I > 2σ(I)] reflections	8574, 2009, 1488
R int	0.071
(sin θ/λ)max (Å−1)	0.585
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.043, 0.122, 1.00
No. of reflections	2009
No. of parameters	168
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.20, −0.22

Computer programs: APEX2 and SAINT (Bruker, 2013 ▶), SHELXS97 and SHELXL97 (Sheldrick, 2008 ▶), PLATON (Spek, 2009 ▶), Mercury (Macrae et al., 2008 ▶) and publCIF (Westrip, 2010 ▶)’.

Supplementary Material

CCDC reference: 1021159

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

supplementary crystallographic information

Crystal data

C14H17FN2O	F(000) = 528
Mr = 248.30	Dx = 1.342 Mg m−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2yn	Cell parameters from 2009 reflections
a = 11.3414 (3) Å	θ = 4.5–64.4°
b = 9.1909 (3) Å	µ = 0.79 mm−1
c = 12.6799 (4) Å	T = 100 K
β = 111.569 (2)°	Block, white
V = 1229.17 (7) Å3	0.23 × 0.22 × 0.21 mm
Z = 4

Data collection

Bruker X8 Proteum diffractometer	2009 independent reflections
Radiation source: Bruker MicroStar microfocus rotating anode	1488 reflections with I > 2σ(I)
Helios multilayer optics monochromator	Rint = 0.071
Detector resolution: 18.4 pixels mm-1	θmax = 64.4°, θmin = 4.5°
φ and ω scans	h = −13→13
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −10→10
Tmin = 0.834, Tmax = 0.848	l = −14→14
8574 measured reflections

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.0682P)2] where P = (Fo2 + 2Fc2)/3
2009 reflections	(Δ/σ)max = 0.049
168 parameters	Δρmax = 0.20 e Å−3
0 restraints	Δρmin = −0.22 e Å−3

Special details

Experimental. 1H NMR was recorded at 400 MHz in Dimethylsulfoxide (DMSO-d6). 13C NMR was recorded at 400 MHz in DMSO-d6. Mass spectra was recorded on a Jeol SX 102=DA-6000 (10 kV) fast atom bombardment (FAB) mass spectrometer. 1H NMR(400 MHz, DMSO-d6): δ = 1.12 (s, 3H), 1.60 (q, J = 12.00 Hz, 1H), 1.72–1.74 (m, 1H), 1.89–1.91 (m, 2H), 2.26–2.28 (m, 2H), 2.95 (q, J = 6.80 Hz, 1H), 3.22 (q, J = 7.20 Hz, 1H), 3.41–3.43 (m, 1H), 5.24 (d, J = 5.60 Hz, 1H), 5.62 (s, 1H), 6.40–6.41 (m, 1H), 6.49–6.50 (m, 1H), 6.74–6.75 (m, 1H) p.p.m..13C NMR (400 MHz, DMSO-d6): δ = 17.6, 21.6, 30.6, 33.2, 41.6, 46.1, 47.2, 11.7, 114.4, 119.2, 142.9, 153.1, 155.4, 174.6 p.p.m..MS (70 eV) m/z (%): 250.1 (M+, 99.63)HPLC Purity = 97.9%.

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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
F1	0.84526 (11)	0.14151 (14)	0.28243 (11)	0.0311 (4)
O1	1.19100 (13)	0.59593 (18)	0.49292 (13)	0.0316 (5)
N1	1.15416 (15)	0.3610 (2)	0.07073 (15)	0.0220 (6)
N12	1.06638 (14)	0.62374 (18)	0.30482 (14)	0.0181 (5)
C2	1.23865 (17)	0.4842 (2)	0.11812 (18)	0.0208 (6)
C3	1.16936 (17)	0.5931 (2)	0.16463 (18)	0.0217 (6)
C4	1.13482 (16)	0.5243 (2)	0.25882 (17)	0.0191 (6)
C5	0.98300 (17)	0.3254 (2)	0.26777 (18)	0.0201 (7)
C6	0.92150 (17)	0.1966 (2)	0.22961 (19)	0.0226 (7)
C7	0.93354 (18)	0.1203 (2)	0.14035 (19)	0.0236 (7)
C8	1.01288 (18)	0.1756 (2)	0.09018 (19)	0.0224 (7)
C9	1.07908 (16)	0.3066 (2)	0.12729 (17)	0.0188 (6)
C10	1.06312 (16)	0.3830 (2)	0.21747 (17)	0.0177 (6)
C11	1.27895 (19)	0.5500 (3)	0.02753 (19)	0.0280 (7)
C13	1.09465 (18)	0.6419 (2)	0.41705 (18)	0.0217 (7)
C14	0.98829 (18)	0.7274 (2)	0.4329 (2)	0.0252 (7)
C15	0.92345 (18)	0.7996 (2)	0.31843 (19)	0.0246 (7)
C16	0.94501 (18)	0.6917 (2)	0.23558 (19)	0.0242 (7)
H1N	1.182 (2)	0.296 (3)	0.039 (2)	0.033 (7)*
H2	1.31410	0.44940	0.18040	0.0250*
H3A	1.09290	0.62550	0.10410	0.0260*
H3B	1.22290	0.67730	0.19400	0.0260*
H4	1.21440	0.49960	0.32060	0.0230*
H5	0.97130	0.37440	0.32730	0.0240*
H7	0.88930	0.03410	0.11480	0.0280*
H8	1.02290	0.12520	0.03040	0.0270*
H11A	1.31770	0.47640	−0.00270	0.0420*
H11B	1.33870	0.62680	0.05990	0.0420*
H11C	1.20600	0.58850	−0.03210	0.0420*
H14A	1.02120	0.79930	0.49250	0.0300*
H14B	0.93040	0.66350	0.45110	0.0300*
H15A	0.96160	0.89310	0.31530	0.0300*
H15B	0.83370	0.81320	0.30230	0.0300*
H16A	0.87740	0.62030	0.21000	0.0290*
H16B	0.95120	0.74120	0.17030	0.0290*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
F1	0.0307 (6)	0.0272 (8)	0.0426 (9)	−0.0022 (5)	0.0220 (6)	0.0062 (6)
O1	0.0320 (8)	0.0396 (11)	0.0193 (9)	0.0119 (7)	0.0048 (7)	0.0021 (7)
N1	0.0231 (8)	0.0223 (11)	0.0230 (11)	−0.0002 (8)	0.0113 (8)	−0.0032 (9)
N12	0.0185 (8)	0.0178 (10)	0.0172 (10)	0.0019 (7)	0.0055 (7)	−0.0011 (8)
C2	0.0169 (9)	0.0252 (12)	0.0189 (12)	−0.0030 (8)	0.0048 (8)	−0.0023 (9)
C3	0.0197 (9)	0.0230 (12)	0.0216 (12)	−0.0038 (8)	0.0066 (9)	−0.0035 (9)
C4	0.0159 (9)	0.0208 (12)	0.0187 (12)	0.0019 (8)	0.0042 (8)	−0.0025 (9)
C5	0.0223 (10)	0.0180 (12)	0.0210 (12)	0.0035 (8)	0.0090 (9)	0.0017 (9)
C6	0.0206 (9)	0.0211 (12)	0.0279 (13)	0.0013 (9)	0.0112 (9)	0.0085 (10)
C7	0.0225 (10)	0.0161 (12)	0.0281 (13)	−0.0008 (8)	0.0046 (9)	0.0019 (10)
C8	0.0254 (10)	0.0178 (12)	0.0226 (12)	0.0018 (9)	0.0073 (9)	−0.0021 (9)
C9	0.0159 (9)	0.0185 (12)	0.0194 (12)	0.0051 (8)	0.0035 (8)	0.0040 (9)
C10	0.0157 (9)	0.0163 (12)	0.0190 (11)	0.0034 (8)	0.0040 (8)	0.0020 (9)
C11	0.0244 (10)	0.0359 (14)	0.0254 (13)	−0.0044 (10)	0.0112 (9)	−0.0019 (11)
C13	0.0256 (10)	0.0194 (12)	0.0213 (12)	−0.0030 (9)	0.0099 (9)	0.0008 (10)
C14	0.0281 (10)	0.0227 (13)	0.0290 (13)	−0.0002 (9)	0.0156 (9)	−0.0012 (10)
C15	0.0221 (10)	0.0215 (12)	0.0298 (13)	0.0024 (9)	0.0090 (9)	−0.0007 (10)
C16	0.0194 (9)	0.0266 (13)	0.0232 (12)	0.0066 (9)	0.0038 (9)	0.0000 (10)

Geometric parameters (Å, º)

F1—C6	1.371 (2)	C14—C15	1.518 (3)
O1—C13	1.235 (3)	C15—C16	1.528 (3)
N1—C2	1.462 (3)	C2—H2	0.9800
N1—C9	1.392 (3)	C3—H3A	0.9700
N12—C4	1.453 (3)	C3—H3B	0.9700
N12—C13	1.349 (3)	C4—H4	0.9800
N12—C16	1.472 (3)	C5—H5	0.9300
N1—H1N	0.84 (3)	C7—H7	0.9300
C2—C11	1.510 (3)	C8—H8	0.9300
C2—C3	1.519 (3)	C11—H11A	0.9600
C3—C4	1.524 (3)	C11—H11B	0.9600
C4—C10	1.520 (3)	C11—H11C	0.9600
C5—C6	1.369 (3)	C14—H14A	0.9700
C5—C10	1.392 (3)	C14—H14B	0.9700
C6—C7	1.380 (3)	C15—H15A	0.9700
C7—C8	1.376 (3)	C15—H15B	0.9700
C8—C9	1.405 (3)	C16—H16A	0.9700
C9—C10	1.409 (3)	C16—H16B	0.9700
C13—C14	1.514 (3)
C2—N1—C9	119.93 (17)	C2—C3—H3B	110.00
C4—N12—C13	123.12 (17)	C4—C3—H3A	110.00
C4—N12—C16	123.22 (16)	C4—C3—H3B	110.00
C13—N12—C16	112.59 (17)	H3A—C3—H3B	108.00
C2—N1—H1N	116.2 (17)	N12—C4—H4	107.00
C9—N1—H1N	113.5 (18)	C3—C4—H4	107.00
C3—C2—C11	112.08 (17)	C10—C4—H4	107.00
N1—C2—C3	108.38 (17)	C6—C5—H5	120.00
N1—C2—C11	109.48 (18)	C10—C5—H5	120.00
C2—C3—C4	110.45 (15)	C6—C7—H7	121.00
N12—C4—C10	112.27 (16)	C8—C7—H7	121.00
C3—C4—C10	110.07 (16)	C7—C8—H8	119.00
N12—C4—C3	112.50 (15)	C9—C8—H8	119.00
C6—C5—C10	120.03 (19)	C2—C11—H11A	109.00
F1—C6—C7	118.91 (17)	C2—C11—H11B	109.00
F1—C6—C5	118.54 (18)	C2—C11—H11C	109.00
C5—C6—C7	122.6 (2)	H11A—C11—H11B	110.00
C6—C7—C8	118.04 (18)	H11A—C11—H11C	109.00
C7—C8—C9	121.42 (19)	H11B—C11—H11C	110.00
N1—C9—C10	121.63 (17)	C13—C14—H14A	111.00
N1—C9—C8	119.20 (18)	C13—C14—H14B	111.00
C8—C9—C10	119.11 (18)	C15—C14—H14A	111.00
C4—C10—C9	119.59 (17)	C15—C14—H14B	111.00
C4—C10—C5	121.56 (17)	H14A—C14—H14B	109.00
C5—C10—C9	118.84 (17)	C14—C15—H15A	111.00
O1—C13—C14	126.5 (2)	C14—C15—H15B	111.00
N12—C13—C14	108.20 (18)	C16—C15—H15A	111.00
O1—C13—N12	125.3 (2)	C16—C15—H15B	111.00
C13—C14—C15	103.28 (18)	H15A—C15—H15B	109.00
C14—C15—C16	103.30 (16)	N12—C16—H16A	111.00
N12—C16—C15	102.49 (17)	N12—C16—H16B	111.00
N1—C2—H2	109.00	C15—C16—H16A	111.00
C3—C2—H2	109.00	C15—C16—H16B	111.00
C11—C2—H2	109.00	H16A—C16—H16B	109.00
C2—C3—H3A	110.00
C9—N1—C2—C3	−40.8 (2)	C3—C4—C10—C5	−156.85 (18)
C9—N1—C2—C11	−163.35 (18)	C3—C4—C10—C9	24.2 (2)
C2—N1—C9—C8	−170.60 (18)	C10—C5—C6—F1	178.75 (18)
C2—N1—C9—C10	12.4 (3)	C10—C5—C6—C7	−1.1 (3)
C13—N12—C4—C3	−133.86 (19)	C6—C5—C10—C4	−178.91 (19)
C13—N12—C4—C10	101.3 (2)	C6—C5—C10—C9	0.1 (3)
C16—N12—C4—C3	58.9 (2)	F1—C6—C7—C8	−178.47 (19)
C16—N12—C4—C10	−66.0 (2)	C5—C6—C7—C8	1.4 (3)
C4—N12—C13—O1	11.8 (3)	C6—C7—C8—C9	−0.7 (3)
C4—N12—C13—C14	−168.15 (17)	C7—C8—C9—N1	−177.40 (19)
C16—N12—C13—O1	−179.74 (19)	C7—C8—C9—C10	−0.3 (3)
C16—N12—C13—C14	0.4 (2)	N1—C9—C10—C4	−3.4 (3)
C4—N12—C16—C15	−172.51 (17)	N1—C9—C10—C5	177.61 (19)
C13—N12—C16—C15	19.0 (2)	C8—C9—C10—C4	179.63 (18)
N1—C2—C3—C4	61.2 (2)	C8—C9—C10—C5	0.6 (3)
C11—C2—C3—C4	−177.83 (17)	O1—C13—C14—C15	160.3 (2)
C2—C3—C4—N12	−179.05 (16)	N12—C13—C14—C15	−19.8 (2)
C2—C3—C4—C10	−53.0 (2)	C13—C14—C15—C16	30.3 (2)
N12—C4—C10—C5	−30.7 (3)	C14—C15—C16—N12	−29.9 (2)
N12—C4—C10—C9	150.31 (18)

Hydrogen-bond geometry (Å, º)

Cg1 is the centroid of the C5–C10 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1i	0.84 (3)	2.46 (3)	3.273 (2)	162 (2)
C7—H7···O1ii	0.93	2.51	3.351 (3)	150
C15—H15B···F1iii	0.97	2.48	3.189 (3)	130
C11—H11C···Cg1iv	0.97	2.80	3.748 (3)	168

Symmetry codes: (i) −x+5/2, y−1/2, −z+1/2; (ii) x−1/2, −y+1/2, z−1/2; (iii) −x+3/2, y+1/2, −z+1/2; (iv) −x+2, −y+1, −z.