Methyl 4-(4-fluoro-anilino)-1,2,6-tris-(4-fluoro-phen-yl)-1,2,5,6-tetra-hydro-pyri-dine-3-carboxyl-ate.

In the title mol-ecule, C31H24F4N2O2, the tetra-hydro-pyridine ring adopts a distorted boat conformation. An intra-molecular N-H⋯O hydrogen bond is formed by the amino group and ccarboxyl C=O atom. The crystal structure features weak C-H⋯F and C-H⋯O inter-actions.

Related literature

For biological activity of functionalized piperidine derivatives, see: Zhou et al. (2007 ▶); Misra et al. (2009 ▶); Bin et al. (2001 ▶); Agrawal & Somani (2009 ▶); Jaen et al. (1988 ▶). For general background to functionalized n class="Chemical">piperidines, see: Kamei et al. (2005 ▶). For related structures, see: Sambyal et al. (2011 ▶); Brahmachari & Das (2012 ▶); Khan et al. (2010 ▶); Anthal et al. (2013 ▶). For asymmetry parameters, see: Duax et al. (1975 ▶).

Experimental

Crystal data

C31H24F4N2O2

M = 532.52

Triclinic,

a = 9.7990 (2) Å

b = 10.7316 (4) Å

c = 13.7395 (4) Å

α = 110.797 (3)°

β = 100.338 (2)°

γ = 96.323 (2)°

V = 1304.81 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.10 mm−1

T = 293 K

0.30 × 0.20 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 ▶) T min = 0.899, T max = 1.000

42990 measured reflections

5413 independent reflections

3730 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.118

S = 1.05

5413 reflections

353 parameters

H-atom parameters constrained

Δρmax = 0.17 e Å−3

Δρmin = −0.20 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681300370X/gk2551sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681300370X/gk2551Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S160053681300370X/gk2551Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C31H24F4N2O2	Z = 2
Mr = 532.52	F(000) = 552
Triclinic, P1	Dx = 1.355 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.7990 (2) Å	Cell parameters from 14371 reflections
b = 10.7316 (4) Å	θ = 3.5–29.0°
c = 13.7395 (4) Å	µ = 0.10 mm−1
α = 110.797 (3)°	T = 293 K
β = 100.338 (2)°	Block, white
γ = 96.323 (2)°	0.30 × 0.20 × 0.20 mm
V = 1304.81 (7) Å3

Oxford Diffraction Xcalibur Sapphire3 diffractometer	5413 independent reflections
Radiation source: fine-focus sealed tube	3730 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
Detector resolution: 16.1049 pixels mm-1	θmax = 26.5°, θmin = 3.5°
ω scans	h = −12→12
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	k = −13→13
Tmin = 0.899, Tmax = 1.000	l = −17→17
42990 measured reflections

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0523P)2 + 0.1709P] where P = (Fo2 + 2Fc2)/3
5413 reflections	(Δ/σ)max = 0.001
353 parameters	Δρmax = 0.17 e Å−3
0 restraints	Δρmin = −0.20 e Å−3

Experimental. 1H NMR (400 MHz, CDCl3): δH 2.62 (dd, J = 2.4, 15.2 Hz, 1H), 2.78 (dd, J = 5.2, 15 Hz, 1H), 3.91 (s, 3H), 5.04 (br d, 1H), 6.27 (br s, 1H), 6.33–6.39(m, 4H), 6.78 (t, J = 8.8 Hz, 2H), 6.84 (t, J = 8.8 Hz, 2H), 6.93–6.99 (m, 4H), 7.07–7.11 (m, 2H), 7.19–7.25 (m, 2H), 10.17 (br s, 1H). 13C NMR (100 MHz, CDCl3): δC 33.71, 51.19, 55.19, 57.45, 97.64, 113.88, 113.95, 114.98, 115.2, 115.30, 115.51, 115.73, 115.96, 127.88, 127.96, 128.12, 128.20, 133.62, 133.64, 138.05, 138.99, 143.06, 154.10, 156.03, 156.44, 159.67, 160.37, 160.83, 162.12, 162.80, 163.27, 168.38. IR νmax (KBr): 3240, 3065, 2945, 2838, 1653, 1591, 1506, 1450, 1371, 1269, 1229, 1076, 812, 771, 685 cm-1. CrysAlis PRO, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27–08-2010 CrysAlis171. NET) (compiled Aug 27 2010,11:50:40) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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.

	x	y	z	Uiso*/Ueq
O1	0.05599 (13)	0.35453 (13)	−0.02481 (9)	0.0522 (3)
O2	0.25451 (13)	0.51103 (13)	0.02833 (9)	0.0553 (3)
N1	0.38897 (13)	0.47214 (13)	0.29805 (10)	0.0384 (3)
F1	0.16292 (17)	1.01431 (15)	0.51876 (13)	0.1073 (5)
F2	0.97011 (11)	0.61739 (14)	0.44660 (11)	0.0792 (4)
F3	0.36636 (18)	−0.16496 (14)	0.06807 (15)	0.1252 (6)
F4	−0.31258 (16)	−0.11300 (15)	0.23046 (12)	0.1002 (5)
C2	0.30643 (16)	0.54303 (16)	0.24088 (12)	0.0360 (4)
H2	0.3679	0.5755	0.2025	0.043*
C3	0.18153 (16)	0.44415 (16)	0.15708 (12)	0.0367 (4)
C4	0.10236 (16)	0.35791 (16)	0.18759 (12)	0.0372 (4)
C5	0.15506 (16)	0.36802 (17)	0.30004 (12)	0.0395 (4)
H5A	0.1036	0.2934	0.3110	0.047*
H5B	0.1403	0.4525	0.3504	0.047*
C6	0.31341 (16)	0.36283 (16)	0.31870 (12)	0.0361 (4)
H6	0.3484	0.3785	0.3943	0.043*
C7	0.15522 (17)	0.43097 (17)	0.04696 (13)	0.0401 (4)
C8	0.2415 (3)	0.4972 (2)	−0.08105 (16)	0.0754 (7)
H8A	0.2506	0.4070	−0.1235	0.113*
H8B	0.3144	0.5618	−0.0846	0.113*
H8C	0.1507	0.5135	−0.1081	0.113*
N9	−0.01024 (14)	0.26238 (15)	0.12273 (11)	0.0476 (4)
H9	−0.0379	0.2597	0.0589	0.057*
C10	0.26522 (16)	0.66857 (16)	0.31793 (12)	0.0365 (4)
C11	0.15179 (18)	0.72134 (18)	0.28316 (14)	0.0467 (4)
H11	0.0984	0.6782	0.2131	0.056*
C12	0.1167 (2)	0.8370 (2)	0.35088 (17)	0.0586 (5)
H12	0.0396	0.8709	0.3271	0.070*
C13	0.1962 (2)	0.9001 (2)	0.45242 (17)	0.0618 (5)
C14	0.3100 (2)	0.8534 (2)	0.49011 (16)	0.0650 (6)
H14	0.3640	0.8990	0.5598	0.078*
C15	0.3432 (2)	0.73677 (19)	0.42233 (13)	0.0514 (5)
H15	0.4197	0.7033	0.4475	0.062*
C16	0.53521 (16)	0.50829 (16)	0.33293 (12)	0.0358 (4)
C17	0.61195 (17)	0.62124 (18)	0.32556 (14)	0.0461 (4)
H17	0.5643	0.6733	0.2947	0.055*
C18	0.75664 (18)	0.65696 (19)	0.36303 (15)	0.0520 (5)
H18	0.8059	0.7324	0.3575	0.062*
C19	0.82704 (17)	0.5806 (2)	0.40835 (14)	0.0495 (4)
C20	0.75808 (17)	0.46901 (18)	0.41701 (13)	0.0446 (4)
H20	0.8079	0.4179	0.4476	0.053*
C21	0.61273 (17)	0.43295 (17)	0.37959 (12)	0.0395 (4)
H21	0.5653	0.3570	0.3855	0.047*
C22	0.33464 (16)	0.22233 (16)	0.25164 (13)	0.0376 (4)
C23	0.35639 (18)	0.19043 (19)	0.14950 (13)	0.0484 (4)
H23	0.3650	0.2581	0.1223	0.058*
C24	0.3656 (2)	0.0598 (2)	0.08718 (16)	0.0664 (6)
H24	0.3781	0.0386	0.0180	0.080*
C25	0.3560 (2)	−0.0368 (2)	0.1291 (2)	0.0742 (7)
C26	0.3379 (2)	−0.0102 (2)	0.2300 (2)	0.0761 (7)
H26	0.3334	−0.0781	0.2572	0.091*
C27	0.3264 (2)	0.12074 (19)	0.29126 (17)	0.0576 (5)
H27	0.3128	0.1404	0.3601	0.069*
C28	−0.08772 (17)	0.16492 (17)	0.15122 (13)	0.0412 (4)
C29	−0.20066 (19)	0.19542 (19)	0.19642 (14)	0.0507 (4)
H29	−0.2260	0.2797	0.2086	0.061*
C30	−0.2760 (2)	0.1026 (2)	0.22363 (16)	0.0609 (5)
H30	−0.3518	0.1232	0.2547	0.073*
C31	−0.2376 (2)	−0.0200 (2)	0.20425 (16)	0.0609 (5)
C32	−0.1273 (2)	−0.0550 (2)	0.15877 (16)	0.0639 (6)
H32	−0.1042	−0.1403	0.1457	0.077*
C33	−0.0510 (2)	0.0396 (2)	0.13272 (15)	0.0544 (5)
H33	0.0254	0.0187	0.1026	0.065*

	U11	U22	U33	U12	U13	U23
O1	0.0623 (8)	0.0492 (8)	0.0333 (6)	0.0029 (6)	−0.0044 (6)	0.0117 (6)
O2	0.0675 (8)	0.0600 (8)	0.0367 (7)	0.0003 (7)	0.0078 (6)	0.0224 (6)
N1	0.0352 (7)	0.0357 (8)	0.0428 (8)	0.0036 (6)	0.0012 (6)	0.0178 (6)
F1	0.1155 (11)	0.0732 (9)	0.1012 (11)	0.0462 (8)	0.0230 (9)	−0.0112 (8)
F2	0.0355 (6)	0.0991 (10)	0.1020 (10)	0.0026 (6)	0.0006 (6)	0.0478 (8)
F3	0.1320 (14)	0.0455 (8)	0.1517 (15)	0.0252 (8)	0.0197 (11)	−0.0127 (9)
F4	0.1154 (11)	0.0859 (10)	0.1022 (11)	−0.0199 (8)	0.0182 (9)	0.0544 (9)
C2	0.0386 (8)	0.0365 (9)	0.0317 (8)	0.0047 (7)	0.0035 (6)	0.0146 (7)
C3	0.0381 (8)	0.0356 (9)	0.0314 (8)	0.0067 (7)	0.0031 (6)	0.0095 (7)
C4	0.0344 (8)	0.0385 (9)	0.0332 (8)	0.0084 (7)	0.0038 (6)	0.0088 (7)
C5	0.0388 (9)	0.0425 (10)	0.0326 (8)	0.0039 (7)	0.0067 (7)	0.0109 (7)
C6	0.0394 (9)	0.0383 (9)	0.0282 (8)	0.0049 (7)	0.0036 (6)	0.0128 (7)
C7	0.0483 (10)	0.0349 (9)	0.0352 (9)	0.0116 (8)	0.0060 (7)	0.0119 (7)
C8	0.1054 (18)	0.0825 (16)	0.0432 (11)	0.0043 (13)	0.0191 (11)	0.0329 (11)
N9	0.0469 (8)	0.0512 (9)	0.0350 (7)	−0.0055 (7)	−0.0031 (6)	0.0154 (7)
C10	0.0396 (9)	0.0344 (9)	0.0349 (8)	0.0029 (7)	0.0052 (7)	0.0156 (7)
C11	0.0471 (10)	0.0413 (10)	0.0466 (10)	0.0063 (8)	0.0006 (8)	0.0165 (8)
C12	0.0543 (11)	0.0463 (11)	0.0735 (14)	0.0167 (9)	0.0100 (10)	0.0214 (10)
C13	0.0688 (13)	0.0451 (12)	0.0626 (13)	0.0172 (10)	0.0195 (11)	0.0062 (10)
C14	0.0734 (14)	0.0617 (13)	0.0410 (11)	0.0175 (11)	0.0030 (9)	0.0010 (10)
C15	0.0565 (11)	0.0529 (11)	0.0383 (10)	0.0170 (9)	0.0025 (8)	0.0118 (9)
C16	0.0376 (9)	0.0346 (9)	0.0290 (8)	0.0054 (7)	0.0034 (6)	0.0075 (7)
C17	0.0432 (10)	0.0448 (10)	0.0502 (10)	0.0057 (8)	0.0044 (8)	0.0221 (9)
C18	0.0446 (10)	0.0494 (11)	0.0591 (12)	−0.0024 (8)	0.0094 (8)	0.0221 (9)
C19	0.0317 (9)	0.0610 (12)	0.0478 (10)	0.0051 (8)	0.0030 (7)	0.0155 (9)
C20	0.0433 (10)	0.0489 (11)	0.0362 (9)	0.0138 (8)	0.0034 (7)	0.0115 (8)
C21	0.0425 (9)	0.0366 (9)	0.0344 (8)	0.0052 (7)	0.0035 (7)	0.0111 (7)
C22	0.0336 (8)	0.0351 (9)	0.0393 (9)	0.0013 (7)	0.0024 (7)	0.0129 (7)
C23	0.0493 (10)	0.0511 (11)	0.0405 (10)	0.0146 (8)	0.0052 (8)	0.0136 (8)
C24	0.0613 (13)	0.0671 (15)	0.0492 (12)	0.0206 (11)	0.0031 (9)	−0.0010 (11)
C25	0.0605 (13)	0.0387 (12)	0.0953 (19)	0.0088 (10)	0.0072 (12)	−0.0018 (12)
C26	0.0708 (15)	0.0408 (12)	0.124 (2)	0.0070 (10)	0.0310 (14)	0.0373 (14)
C27	0.0602 (12)	0.0484 (12)	0.0743 (14)	0.0096 (9)	0.0254 (10)	0.0309 (11)
C28	0.0390 (9)	0.0409 (10)	0.0343 (9)	0.0006 (7)	0.0009 (7)	0.0094 (7)
C29	0.0530 (11)	0.0451 (11)	0.0495 (10)	0.0103 (8)	0.0117 (8)	0.0128 (9)
C30	0.0555 (12)	0.0673 (14)	0.0609 (12)	0.0068 (10)	0.0203 (10)	0.0239 (11)
C31	0.0667 (13)	0.0560 (13)	0.0542 (12)	−0.0094 (10)	0.0038 (10)	0.0256 (10)
C32	0.0830 (15)	0.0419 (12)	0.0604 (13)	0.0123 (10)	0.0023 (11)	0.0188 (10)
C33	0.0550 (11)	0.0527 (12)	0.0529 (11)	0.0169 (9)	0.0105 (9)	0.0164 (9)

O1—C7	1.2234 (19)	C14—C15	1.382 (2)
O2—C7	1.346 (2)	C14—H14	0.9300
O2—C8	1.437 (2)	C15—H15	0.9300
N1—C16	1.3902 (19)	C16—C17	1.399 (2)
N1—C6	1.4578 (19)	C16—C21	1.404 (2)
N1—C2	1.4771 (19)	C17—C18	1.379 (2)
F1—C13	1.357 (2)	C17—H17	0.9300
F2—C19	1.3652 (19)	C18—C19	1.367 (3)
F3—C25	1.359 (2)	C18—H18	0.9300
F4—C31	1.362 (2)	C19—C20	1.363 (2)
C2—C3	1.513 (2)	C20—C21	1.385 (2)
C2—C10	1.536 (2)	C20—H20	0.9300
C2—H2	0.9800	C21—H21	0.9300
C3—C4	1.367 (2)	C22—C27	1.382 (2)
C3—C7	1.441 (2)	C22—C23	1.383 (2)
C4—N9	1.346 (2)	C23—C24	1.382 (3)
C4—C5	1.499 (2)	C23—H23	0.9300
C5—C6	1.537 (2)	C24—C25	1.355 (3)
C5—H5A	0.9700	C24—H24	0.9300
C5—H5B	0.9700	C25—C26	1.361 (3)
C6—C22	1.522 (2)	C26—C27	1.387 (3)
C6—H6	0.9800	C26—H26	0.9300
C8—H8A	0.9600	C27—H27	0.9300
C8—H8B	0.9600	C28—C29	1.378 (2)
C8—H8C	0.9600	C28—C33	1.378 (2)
N9—C28	1.430 (2)	C29—C30	1.371 (3)
N9—H9	0.8600	C29—H29	0.9300
C10—C15	1.384 (2)	C30—C31	1.357 (3)
C10—C11	1.387 (2)	C30—H30	0.9300
C11—C12	1.383 (3)	C31—C32	1.365 (3)
C11—H11	0.9300	C32—C33	1.380 (3)
C12—C13	1.355 (3)	C32—H32	0.9300
C12—H12	0.9300	C33—H33	0.9300
C13—C14	1.365 (3)
C7—O2—C8	116.47 (15)	C14—C15—H15	119.2
C16—N1—C6	119.96 (12)	C10—C15—H15	119.2
C16—N1—C2	121.58 (13)	N1—C16—C17	122.49 (14)
C6—N1—C2	118.45 (12)	N1—C16—C21	120.70 (14)
N1—C2—C3	110.16 (12)	C17—C16—C21	116.81 (14)
N1—C2—C10	112.28 (12)	C18—C17—C16	121.44 (16)
C3—C2—C10	113.35 (13)	C18—C17—H17	119.3
N1—C2—H2	106.9	C16—C17—H17	119.3
C3—C2—H2	106.9	C19—C18—C17	119.45 (17)
C10—C2—H2	106.9	C19—C18—H18	120.3
C4—C3—C7	120.82 (14)	C17—C18—H18	120.3
C4—C3—C2	117.19 (13)	C20—C19—F2	119.03 (16)
C7—C3—C2	121.68 (14)	C20—C19—C18	121.73 (16)
N9—C4—C3	124.80 (14)	F2—C19—C18	119.24 (17)
N9—C4—C5	119.74 (14)	C19—C20—C21	118.97 (16)
C3—C4—C5	115.31 (13)	C19—C20—H20	120.5
C4—C5—C6	108.80 (12)	C21—C20—H20	120.5
C4—C5—H5A	109.9	C20—C21—C16	121.61 (16)
C6—C5—H5A	109.9	C20—C21—H21	119.2
C4—C5—H5B	109.9	C16—C21—H21	119.2
C6—C5—H5B	109.9	C27—C22—C23	118.21 (17)
H5A—C5—H5B	108.3	C27—C22—C6	119.57 (15)
N1—C6—C22	113.71 (12)	C23—C22—C6	122.17 (15)
N1—C6—C5	109.48 (12)	C22—C23—C24	121.17 (19)
C22—C6—C5	109.88 (12)	C22—C23—H23	119.4
N1—C6—H6	107.9	C24—C23—H23	119.4
C22—C6—H6	107.9	C25—C24—C23	118.6 (2)
C5—C6—H6	107.9	C25—C24—H24	120.7
O1—C7—O2	121.68 (15)	C23—C24—H24	120.7
O1—C7—C3	125.38 (16)	C24—C25—F3	118.5 (3)
O2—C7—C3	112.93 (14)	C24—C25—C26	122.6 (2)
O2—C8—H8A	109.5	F3—C25—C26	118.9 (2)
O2—C8—H8B	109.5	C25—C26—C27	118.4 (2)
H8A—C8—H8B	109.5	C25—C26—H26	120.8
O2—C8—H8C	109.5	C27—C26—H26	120.8
H8A—C8—H8C	109.5	C22—C27—C26	121.0 (2)
H8B—C8—H8C	109.5	C22—C27—H27	119.5
C4—N9—C28	125.43 (14)	C26—C27—H27	119.5
C4—N9—H9	117.3	C29—C28—C33	119.57 (17)
C28—N9—H9	117.3	C29—C28—N9	120.08 (16)
C15—C10—C11	117.64 (15)	C33—C28—N9	120.34 (16)
C15—C10—C2	121.57 (14)	C30—C29—C28	120.60 (18)
C11—C10—C2	120.71 (14)	C30—C29—H29	119.7
C12—C11—C10	121.19 (16)	C28—C29—H29	119.7
C12—C11—H11	119.4	C31—C30—C29	118.48 (19)
C10—C11—H11	119.4	C31—C30—H30	120.8
C13—C12—C11	118.93 (18)	C29—C30—H30	120.8
C13—C12—H12	120.5	C30—C31—F4	118.8 (2)
C11—C12—H12	120.5	C30—C31—C32	122.91 (19)
F1—C13—C12	119.10 (19)	F4—C31—C32	118.3 (2)
F1—C13—C14	118.73 (19)	C31—C32—C33	118.21 (19)
C12—C13—C14	122.17 (18)	C31—C32—H32	120.9
C13—C14—C15	118.48 (18)	C33—C32—H32	120.9
C13—C14—H14	120.8	C28—C33—C32	120.22 (18)
C15—C14—H14	120.8	C28—C33—H33	119.9
C14—C15—C10	121.58 (17)	C32—C33—H33	119.9
C16—N1—C2—C3	144.95 (14)	C2—C10—C15—C14	176.90 (17)
C6—N1—C2—C3	−35.70 (18)	C6—N1—C16—C17	−173.09 (14)
C16—N1—C2—C10	−87.70 (17)	C2—N1—C16—C17	6.3 (2)
C6—N1—C2—C10	91.65 (16)	C6—N1—C16—C21	5.7 (2)
N1—C2—C3—C4	46.48 (19)	C2—N1—C16—C21	−174.97 (14)
C10—C2—C3—C4	−80.28 (17)	N1—C16—C17—C18	178.43 (16)
N1—C2—C3—C7	−127.14 (15)	C21—C16—C17—C18	−0.4 (2)
C10—C2—C3—C7	106.10 (16)	C16—C17—C18—C19	0.0 (3)
C7—C3—C4—N9	−5.0 (2)	C17—C18—C19—C20	0.4 (3)
C2—C3—C4—N9	−178.70 (14)	C17—C18—C19—F2	−179.16 (16)
C7—C3—C4—C5	170.58 (14)	F2—C19—C20—C21	179.08 (15)
C2—C3—C4—C5	−3.1 (2)	C18—C19—C20—C21	−0.5 (3)
N9—C4—C5—C6	126.42 (15)	C19—C20—C21—C16	0.1 (2)
C3—C4—C5—C6	−49.43 (19)	N1—C16—C21—C20	−178.54 (14)
C16—N1—C6—C22	−71.66 (17)	C17—C16—C21—C20	0.3 (2)
C2—N1—C6—C22	108.98 (15)	N1—C6—C22—C27	151.32 (15)
C16—N1—C6—C5	165.02 (13)	C5—C6—C22—C27	−85.58 (18)
C2—N1—C6—C5	−14.34 (17)	N1—C6—C22—C23	−31.4 (2)
C4—C5—C6—N1	57.41 (16)	C5—C6—C22—C23	91.67 (17)
C4—C5—C6—C22	−68.15 (16)	C27—C22—C23—C24	1.9 (3)
C8—O2—C7—O1	−2.9 (2)	C6—C22—C23—C24	−175.43 (16)
C8—O2—C7—C3	175.84 (16)	C22—C23—C24—C25	−1.5 (3)
C4—C3—C7—O1	7.4 (3)	C23—C24—C25—F3	−179.41 (17)
C2—C3—C7—O1	−179.21 (15)	C23—C24—C25—C26	−0.1 (3)
C4—C3—C7—O2	−171.29 (14)	C24—C25—C26—C27	1.2 (3)
C2—C3—C7—O2	2.1 (2)	F3—C25—C26—C27	−179.50 (19)
C3—C4—N9—C28	175.11 (15)	C23—C22—C27—C26	−0.7 (3)
C5—C4—N9—C28	−0.3 (2)	C6—C22—C27—C26	176.63 (17)
N1—C2—C10—C15	25.0 (2)	C25—C26—C27—C22	−0.7 (3)
C3—C2—C10—C15	150.68 (16)	C4—N9—C28—C29	89.3 (2)
N1—C2—C10—C11	−158.12 (14)	C4—N9—C28—C33	−91.4 (2)
C3—C2—C10—C11	−32.5 (2)	C33—C28—C29—C30	0.4 (3)
C15—C10—C11—C12	−0.9 (3)	N9—C28—C29—C30	179.73 (16)
C2—C10—C11—C12	−177.81 (16)	C28—C29—C30—C31	−0.5 (3)
C10—C11—C12—C13	0.9 (3)	C29—C30—C31—F4	−179.58 (17)
C11—C12—C13—F1	179.37 (18)	C29—C30—C31—C32	−0.1 (3)
C11—C12—C13—C14	0.0 (3)	C30—C31—C32—C33	0.8 (3)
F1—C13—C14—C15	179.77 (19)	F4—C31—C32—C33	−179.70 (17)
C12—C13—C14—C15	−0.9 (3)	C29—C28—C33—C32	0.3 (3)
C13—C14—C15—C10	0.9 (3)	N9—C28—C33—C32	−179.00 (16)
C11—C10—C15—C14	0.0 (3)	C31—C32—C33—C28	−0.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N9—H9···O1	0.86	2.05	2.695 (2)	131
C20—H20···F2i	0.93	2.54	3.384 (2)	152
C32—H32···O1ii	0.93	2.47	3.311 (3)	151

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N9—H9⋯O1	0.86	2.05	2.695 (2)	131
C20—H20⋯F2i	0.93	2.54	3.384 (2)	152
C32—H32⋯O1ii	0.93	2.47	3.311 (3)	151

Symmetry codes: (i) ; (ii) .