Syntheses, crystal structures and Hirshfeld surface analyses of (3aR,4S,7R,7aS)-2-(perfluoro­pyridin-4-yl)-3a,4,7,7a-tetra­hydro-4,7-methano­iso­indole-1,3-dione and (3aR,4S,7R,7aS)-2-[(perfluoro­pyridin-4-yl)­oxy]-3a,4,7,7a-tetra­hydro-4,7-methano­iso­indole-1,3-dione

Peloquin, A.J.; Balaich, G.J.; Iacono, S.T.

doi:10.1107/S2056989019009769

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 75| Part 8| August 2019| Pages 1153-1157

https://doi.org/10.1107/S2056989019009769

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Syntheses, crystal structures and Hirshfeld surface analyses of (3aR,4S,7R,7aS)-2-(perfluoropyridin-4-yl)-3a,4,7,7a-tetrahydro-4,7-methanoisoindole-1,3-dione and (3aR,4S,7R,7aS)-2-[(perfluoropyridin-4-yl)oxy]-3a,4,7,7a-tetrahydro-4,7-methanoisoindole-1,3-dione

Andrew J. Peloquin,^a Gary J. Balaich ^a and Scott T. Iacono ^a ^*

^aDepartment of Chemistry & Chemistry Research Center, United States Air Force, Academy, Colorado Springs, CO 80840, USA
^*Correspondence e-mail: scott.iacono@usafa.edu

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 7 June 2019; accepted 8 July 2019; online 12 July 2019)

The syntheses and crystal structures of the title compounds, C₁₄H₈F₄N₂O₂ and C₁₄H₈F₄N₂O₃, are reported. In each crystal, the packing is driven by C—H⋯F intertactions, along with a variety of C—H⋯O, C—O⋯π, and C—F⋯π contacts. Hirshfeld surface analysis was conducted to aid in the visualization of these various influences on the packing: they showed that the largest contributions to the surface contacts arise from H⋯F/F⋯H interactions, followed by H⋯H and O⋯H/H⋯O.

Keywords: crystal structure; perfluoropyridine; norbornene.

CCDC references: 1879244; 1885019

1. Chemical context

Polynorbornenes (PNBs), derived from ring-opening metathesis polymerization reactions, are numerous, owing to their relative ease of synthesis, tolerance of diverse functional groups and high-molecular weights with good processability (Isono et al., 2018 ). The use of dicarboxyimide-substituted norbornenes allows synthetic control of the substituents on the norbornene ring system, and this feature has been exploited for polymer light-emitting diodes (Zeng et al., 2018 ) and gas-separation membranes (Yu et al., 2016 ). With its predictable substitution chemistry (Baker & Muir, 2010 ; Chambers et al., 1988 ), perfluoropyridine was added to two dicarboxyimide-norbornene systems, and the resulting crystal structures are herein reported.

2. Structural commentary

Compound I crystallizes in the triclinic space group P $[\overline{1}]$ with two molecules, A and B, per asymmetric unit, and compound II in the monoclinic space group P2₁/n with one molecule per asymmetric unit (Fig. 1). The synthesis of both compounds is conducted using endo starting materials, and the same configuration is observed in the resulting crystal structures. In I, steric interactions between the ortho-fluorine atoms and the carbonyl oxygen atoms prevents free rotation about the nitrogen–ipso-carbon bond (C3—N2 and C17—N4 in the crystal): this is evidenced by separate ¹⁹F NMR peaks in solution for the ortho-F atoms (F2/F7 and F3/F6 in the crystal). In molecule A, the N1/C1–C5 plane is rotated by 58.05 (5)° relative to the N2/C6/C7/C12/C13 plane and the corresponding dihedral angle for molecule B is 61.65 (7)°. The addition of an oxygen atom between N2 and C3 in II alleviates this steric restriction and only one ¹⁹F NMR peak in solution is observed for the ortho-F atoms; even so, the dihedral angle between the N1/C1–C5 and N2/C6/C7/C12/C13 planes in the crystal of II of 84.01 (5)° is larger than those found in I.

Figure 1
The molecular structures of (a) I and (b) II. Displacement ellipsoids are shown at the 50% probability level.

3. Supramolecular features and Hirshfeld surface analysis

The main directional interactions in the crystal structures of I and II are of the type C—H⋯O, C—H⋯F, C—O⋯π, and C—F⋯π (Tables 1 and 2). In both compounds, weak hydrogen-bonding interactions are observed for the hydrogen atom(s) α to the carbonyl groups (C7—H6⋯O1ⁱ, C12—H12⋯F2ⁱⁱⁱ, C21—H21⋯F7ⁱⁱⁱ, C21—H21⋯O3^iv and C26—H26⋯O4^v in I; C7—H7⋯O2ⁱ in II) and the olefinic hydrogen atoms (C9—H9⋯F4ⁱⁱ in I; C9—H9⋯O3ⁱⁱ in II). A weak interaction is also observed for a bridge hydrogen atom in II, C14—H14B⋯F4ⁱⁱⁱ. The packing is further aided by π-interactions with the pyridine ring (C6—O1⋯Cgⁱ, C13—O2⋯Cg^vi and C27—O4⋯Cgⁱⁱ in I; C5—F4⋯Cg^iv and C13—O3⋯Cg^v in II).

Table 1
Contact geometry (Å, °) for I

Cg1 and Cg2 are the centroids of the N1/C1–C5 and N3/C15–C19 rings, respectively.

Y—X⋯A	Y—X	X⋯A	Y⋯A	Y—X⋯A
C7—H7⋯O1ⁱ	1.00	2.58	3.347 (2)	133
C9—H9⋯F4ⁱⁱ	0.95	2.49	3.348(20	150
C12—H12⋯F2ⁱⁱⁱ	1.00	2.30	3.1903 (18)	147
C21—H21⋯F7ⁱⁱⁱ	1.00	2.55	3.3855 (17)	141
C21—H21.·O3^iv	1.00	2.51	3.2764 (18)	133
C26—H26⋯O4^v	1.00	2.51	3.3299 (18)	139
C6—O1⋯Cg1ⁱ	1.2075 (17)	3.0462 (14)	4.022 (16)	135.86 (10)
C13—O2⋯Cg2^vi	1.2028 (16)	3.1839 (14)	4.0238 (17)	126.98 (9)
C27—O4⋯Cg2ⁱⁱ	1.2102 (16)	3.2978 (14)	4.0644 (16)	121.58 (9)
Symmetry codes: (i) 1 − x, 1 − y, 2 − z; (ii) −x, 1 − y, 2 − z; (iii) 1 + x, y, z; (iv) 2 − x, 1 − y, 1 − z; (v) 2 − x, 2 − y, 1 − z; (iv) x, y, z.

Table 2
Contact geometry (Å, °) for II

Cg1 is the centroid of the N1/C1–C5 ring.

Y—X⋯A	Y—X	X⋯A	Y⋯A	Y—X⋯A
C7—H7⋯O2ⁱ	1.00	2.58	3.347 (2)	133
C9—H9⋯O3ⁱⁱ	0.95	2.49	3.348(20	150
C14—H14B⋯F4ⁱⁱⁱ	1.00	2.30	3.1903 (18)	147
C5—F4⋯Cg1^iv	1.3234 (13)	3.1543 (18)	3.892 (2)	114.36 (7)
C13—O3⋯Cg1^v	1.2060 (14)	3.3224 (19)	4.231 (2)	132.8 (8)
Symmetry codes: (i) $[{1\over 2}]$ − x, $[{1\over 2}]$ + y, $[{3\over 2}]$ − z; (ii) x, −1 + y, z; (iii) 1 − x, 1 − y, 1 − z; (iv) $[{3\over 2}]$ − x, − $[{1\over 2}]$ + y, $[{3\over 2}]$ − z; (v) x, 1 + y, z.

Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ) was used to investigate the presence of hydrogen bonds and other intermolecular interactions in the crystal structures. The analyses and associated two-dimensional fingerprint plots (Fig. 3) (Spackman & McKinnon, 2002 ) were generated with CrystalExplorer17.5 (Turner et al., 2017 ) using a standard surface resolution with the three-dimensional d_norm surfaces plotted over a fixed color scale of −0.02500 (red) to 1.3800 (blue) a.u. The pale-red spots symbolize short contacts and negative d_norm values on the corresponding surface plots shown in Fig. 2, associated with their relative contributions to the Hirshfeld surface.

Figure 3
The overall two-dimensional fingerprint plots for (a) I and (b) II.

Figure 2
Hirshfeld surfaces of (a) I and (b) II mapped with d_norm.

The largest contribution to the overall crystal packing in both compounds is from F⋯H/H⋯F interactions (36.5% in I; 39.2% in II; Table 3). The F⋯H/H⋯F contacts appear as a pair of characteristic tips in the fingerprint plots at 0.95 Å < (d_i + d_e) < 1.25 Å in I and 1.10 Å < (d_i + d_e) < 1.35 Å in II. H⋯H contacts make the second largest contribution (20.2% in I and 14.1% in II), shown in the middle region 1.10 Å < (d_i + d_e) < 1.18 Å in I and II. The third largest contribution is from O⋯H/H⋯O contacts. In I, the corresponding spike is partially overlapped with the spike representing F⋯H/H⋯F contacts, appearing at 1.05 Å < (d_i + d_e) < 1.40 Å. The O⋯H/H⋯O spike is clearly visible in the fingerprint plot of II, shown in the region of 1.10 Å < (d_i + d_e) < 1.40 Å.

Table 3
Percentage contribution of inter-atomic contacts to the Hirshfeld surfaces for I and II

Contact	Percentage contribution to I	Percentage contribution to II
F⋯H/H⋯F	36.5	39.2
H⋯H	20.2	14.1
O⋯H/H⋯O	13.0	14.0
O⋯C/C⋯O	6.2	6.2
N⋯H/H⋯N	5.3	0.1
F⋯F	5.1	2.1
F⋯C/C⋯F	3.6	4.9
F⋯N/N⋯F	2.4	4.4
O⋯N/N⋯O	0.6	4.1
C⋯H/H⋯C	3.8	3.2
F⋯O/O⋯F	2.4	2.7
O⋯O	1.2	2.7
N⋯C/C⋯N	0.0	2.4

4. Database survey

A search of the November 2018 release of the Cambridge Structure Database (Groom et al., 2016 ), with updates through May 2019, was performed using the program ConQuest (Bruno et al., 2002 ). The search was limited to organic structures with R ≤ 0.1. A search for tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione-based compounds with an aromatic substituent on the nitrogen atom yielded 58 results. The dihedral angle between the aromatic ring plane and the succinimide plane is bimodally distributed between 43 and 90°, with peaks near 60 and 75°.

5. Synthesis and crystallization

Synthesis of (I): pentafluoropyridine (2.68 ml, 24.5 mmol), (3aR,4S,7R,7aS)-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione (4.0 g, 24.5 mmol), and triethylamine (8.56 ml, 61.2 mmol) were combined in DMF (150 ml). The resulting solution was stirred at room temperature for 24 h. Diethyl ether (150 ml) and saturated aqueous ammonium chloride (100 ml) were added and the biphasic solution stirred vigorously for 2 h. The organic layer was separated and the remaining aqueous portion extracted with diethyl ether (2 × 150 ml). The combined organic fractions were washed with water (2 × 1 l) and brine (2 × 300 ml), dried over MgSO₄, and the solvent removed via rotary evaporation. The resulting off-white solid was dissolved in refluxing EtOH (20 ml) and cooled to 278 K for 12 h. Vacuum filtration, washing with cold EtOH (20 ml), and vacuum drying afforded the target compound as a white, crystalline solid (6.18 g, 81%). ¹H NMR (500 MHz, CDCl₃): 6.28 (s, 2H), 3.58 (s, 2H), 3.54 (s, 2H), 1.74 (dd, 2H, J = 96, 9.0 Hz).¹⁹F NMR (471 MHz, CDCl₃): −90.5 (2F), −141.7 (1F), −143.1 (1F).

Synthesis of (II): to a stirred solution of potassium carbonate (1 M, 140 ml), (3aR,4S,7R,7aS)-2-hydroxy-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione (10.0 g, 55.9 mmol), pentafluoropyridine (6.1 ml, 56 mmol), and 140 ml of DMF were added. The resulting solution was stirred at room temperature for 24 h. Diethyl ether (150 ml) and saturated aqueous ammonium chloride (100 ml) were added and the biphasic solution stirred vigorously for 2 h. The organic layer was separated and the remaining aqueous portion extracted with diethyl ether (2 × 150 ml). The combined organic fractions were washed with water (2 × 1 l) and brine (2 × 300 ml), dried over MgSO₄, and the solvent removed via rotary evaporation. The resulting off-white solid was dissolved in refluxing EtOH (50 ml) and cooled to 278 K for 12 h. Vacuum filtration, washing with cold EtOH (20 ml) and vacuum drying afforded the target compound as a white, crystalline solid (12.04 g, 66%). ¹H NMR (500 MHz, CDCl₃): 6.23 (s, 2H), 3.50 (s, 2H), 3.34 (s, 2H), 1.68 (dd, 2H, J = 142, 9.0 Hz).¹⁹F NMR (471 MHz, CDCl₃): −87.4 (2F), −156.3 (2F).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. H atoms were positioned geometrically and refined using a riding model with C—H = 0.95–1.0Å and U_iso(H) = 1.2U_eq(C).

Table 4
Experimental details

	I	II
Crystal data
Chemical formula	C₁₄H₈F₄N₂O₂	C₁₄H₈F₄N₂O₃
M_r	312.22	328.22
Crystal system, space group	Triclinic, P $[\overline{1}]$	Monoclinic, P2₁/n
Temperature (K)	100	100
a, b, c (Å)	7.0347 (15), 10.256 (2), 18.129 (4)	12.285 (6), 5.945 (3), 17.888 (8)
α, β, γ (°)	78.844 (10), 80.165 (10), 87.242 (10)	90, 93.44 (3), 90
V (Å³)	1264.2 (5)	1304.1 (10)
Z	4	4
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	0.15	0.16
Crystal size (mm)	0.26 × 0.23 × 0.20	0.55 × 0.40 × 0.36

Data collection
Diffractometer	Bruker SMART APEX CCD	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2017 )	Multi-scan (SADABS; Bruker, 2017)
T_min, T_max	0.89, 0.97	0.80, 0.95
No. of measured, independent and observed [I > 2σ(I)] reflections	72226, 7674, 6373	18507, 3823, 3443
R_int	0.034	0.025
(sin θ/λ)_max (Å⁻¹)	0.714	0.704

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.126, 1.02	0.038, 0.105, 1.04
No. of reflections	7674	3823
No. of parameters	397	208
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.77, −0.41	0.47, −0.25
Computer programs: APEX3 and SAINT (Bruker, 2017), SHELXT (Sheldrick, 2015a ), SHELXL2016 (Sheldrick, 2015b ), Mercury (Macrae et al., 2008 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 1879244; 1885019

Crystal structure: contains datablocks global, I, II. DOI: https://doi.org/10.1107/S2056989019009769/hb7832sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019009769/hb7832Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989019009769/hb7832IIsup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989019009769/hb7832Isup4.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989019009769/hb7832IIsup5.cml

checkCIF report

Computing details top

For both structures, data collection: APEX3 (Bruker, 2017); cell refinement: SAINT (Bruker, 2017); data reduction: SAINT (Bruker, 2017); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

(I) top

Crystal data top

C₁₄H₈F₄N₂O₂	Z = 4
M_r = 312.22	F(000) = 632
Triclinic, P1	D_x = 1.640 Mg m⁻³
a = 7.0347 (15) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.256 (2) Å	Cell parameters from 9823 reflections
c = 18.129 (4) Å	θ = 2.5–30.7°
α = 78.844 (10)°	µ = 0.15 mm⁻¹
β = 80.165 (10)°	T = 100 K
γ = 87.242 (10)°	Rectangular prism, clear colourless
V = 1264.2 (5) Å³	0.26 × 0.23 × 0.20 mm

Data collection top

Bruker SMART APEX CCD diffractometer	7674 independent reflections
Radiation source: fine focus sealed tube	6373 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 8.3333 pixels mm^-1	θ_max = 30.5°, θ_min = 2.0°
ω Scans scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2017)	k = −14→14
T_min = 0.89, T_max = 0.97	l = −25→25
72226 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.045	H-atom parameters constrained
wR(F²) = 0.126	w = 1/[σ²(F_o²) + (0.0625P)² + 0.7892P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
7674 reflections	Δρ_max = 1.77 e Å⁻³
397 parameters	Δρ_min = −0.41 e Å⁻³
0 restraints

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
F1	−0.32163 (13)	0.66535 (9)	0.80280 (6)	0.0299 (2)
F2	−0.04925 (12)	0.46899 (8)	0.81310 (5)	0.02556 (18)
F3	0.29897 (13)	0.74112 (9)	0.92385 (5)	0.02742 (19)
F4	0.01062 (15)	0.92480 (9)	0.90912 (6)	0.0340 (2)
F5	0.40224 (14)	0.92684 (9)	0.76901 (5)	0.02754 (19)
F6	0.72380 (12)	0.90629 (9)	0.66496 (5)	0.02446 (18)
F7	0.34503 (12)	0.67973 (9)	0.53929 (5)	0.02272 (17)
F8	0.04320 (12)	0.70789 (9)	0.64982 (5)	0.02795 (19)
O1	0.27798 (16)	0.45448 (11)	1.00080 (6)	0.0269 (2)
O2	0.34535 (16)	0.50335 (10)	0.74150 (6)	0.0233 (2)
O3	0.71312 (14)	0.54609 (9)	0.56707 (6)	0.02119 (19)
O4	0.75913 (15)	0.99783 (9)	0.49291 (6)	0.02099 (19)
N1	−0.15423 (18)	0.79402 (12)	0.85635 (7)	0.0235 (2)
N2	0.28410 (16)	0.50134 (11)	0.87085 (6)	0.0178 (2)
N3	0.22520 (17)	0.81750 (11)	0.70839 (7)	0.0208 (2)
N4	0.70733 (15)	0.77544 (10)	0.54298 (6)	0.0154 (2)
C1	−0.16515 (19)	0.68212 (14)	0.83262 (8)	0.0214 (3)
C2	−0.02687 (19)	0.58195 (13)	0.83713 (8)	0.0192 (2)
C3	0.13494 (18)	0.59829 (13)	0.86851 (7)	0.0172 (2)
C4	0.1460 (2)	0.71642 (14)	0.89443 (7)	0.0204 (2)
C5	−0.0016 (2)	0.80966 (14)	0.88622 (8)	0.0237 (3)
C6	0.3481 (2)	0.43565 (14)	0.93807 (7)	0.0201 (2)
C7	0.5095 (2)	0.34170 (14)	0.91564 (8)	0.0214 (3)
H7	0.632591	0.364803	0.930317	0.026*
C8	0.4631 (3)	0.19043 (16)	0.94528 (9)	0.0332 (3)
H8	0.479722	0.15207	0.998913	0.04*
C9	0.2739 (3)	0.16766 (17)	0.92242 (10)	0.0355 (4)
H9	0.157787	0.146875	0.9574	0.043*
C10	0.2883 (3)	0.17988 (17)	0.84872 (10)	0.0335 (3)
H10	0.188245	0.170573	0.821019	0.04*
C11	0.4917 (2)	0.21108 (14)	0.81733 (9)	0.0269 (3)
H11	0.535408	0.194148	0.764515	0.032*
C12	0.52885 (19)	0.35524 (13)	0.82814 (8)	0.0191 (2)
H12	0.661556	0.384198	0.802588	0.023*
C13	0.38067 (19)	0.45892 (13)	0.80420 (7)	0.0176 (2)
C14	0.6008 (3)	0.13049 (17)	0.87797 (12)	0.0400 (4)
H14A	0.737652	0.155649	0.871307	0.048*
H14B	0.5897	0.033186	0.88305	0.048*
C15	0.3933 (2)	0.86501 (13)	0.71103 (7)	0.0201 (2)
C16	0.55752 (19)	0.85513 (13)	0.65845 (7)	0.0181 (2)
C17	0.54593 (18)	0.79044 (12)	0.59868 (7)	0.0157 (2)
C18	0.36863 (19)	0.73991 (12)	0.59592 (7)	0.0169 (2)
C19	0.21476 (19)	0.75621 (13)	0.65218 (8)	0.0195 (2)
C20	0.77807 (18)	0.64904 (12)	0.52953 (7)	0.0164 (2)
C21	0.93999 (18)	0.67181 (12)	0.46283 (7)	0.0167 (2)
H21	1.0639	0.631685	0.477318	0.02*
C22	0.8943 (2)	0.62467 (13)	0.39011 (7)	0.0197 (2)
H22	0.919783	0.528529	0.388159	0.024*
C23	0.6930 (2)	0.67662 (14)	0.38012 (8)	0.0225 (3)
H23	0.580506	0.624899	0.387553	0.027*
C24	0.7034 (2)	0.80880 (14)	0.35888 (8)	0.0235 (3)
H24	0.598626	0.867847	0.348918	0.028*
C25	0.9114 (2)	0.84821 (13)	0.35344 (8)	0.0223 (3)
H25	0.950085	0.936047	0.320653	0.027*
C26	0.95440 (19)	0.82471 (12)	0.43732 (7)	0.0176 (2)
H26	1.085803	0.856148	0.438844	0.021*
C27	0.80172 (18)	0.88246 (12)	0.49164 (7)	0.0164 (2)
C28	1.0183 (2)	0.72422 (15)	0.32846 (8)	0.0263 (3)
H28A	1.004935	0.715936	0.276088	0.032*
H28B	1.156118	0.719809	0.334083	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0193 (4)	0.0288 (5)	0.0432 (5)	−0.0001 (3)	−0.0118 (4)	−0.0050 (4)
F2	0.0233 (4)	0.0211 (4)	0.0368 (5)	−0.0025 (3)	−0.0098 (3)	−0.0115 (3)
F3	0.0301 (5)	0.0295 (4)	0.0273 (4)	−0.0059 (4)	−0.0112 (4)	−0.0099 (4)
F4	0.0406 (5)	0.0235 (4)	0.0406 (5)	−0.0017 (4)	−0.0029 (4)	−0.0158 (4)
F5	0.0396 (5)	0.0255 (4)	0.0190 (4)	−0.0009 (4)	−0.0005 (3)	−0.0116 (3)
F6	0.0252 (4)	0.0264 (4)	0.0253 (4)	−0.0041 (3)	−0.0062 (3)	−0.0109 (3)
F7	0.0219 (4)	0.0269 (4)	0.0230 (4)	−0.0013 (3)	−0.0059 (3)	−0.0114 (3)
F8	0.0181 (4)	0.0307 (5)	0.0352 (5)	−0.0019 (3)	−0.0016 (3)	−0.0086 (4)
O1	0.0308 (5)	0.0333 (6)	0.0160 (4)	−0.0034 (4)	−0.0036 (4)	−0.0031 (4)
O2	0.0312 (5)	0.0217 (5)	0.0169 (4)	0.0030 (4)	−0.0050 (4)	−0.0036 (4)
O3	0.0229 (5)	0.0152 (4)	0.0238 (5)	0.0005 (3)	−0.0014 (4)	−0.0020 (4)
O4	0.0255 (5)	0.0145 (4)	0.0242 (5)	0.0000 (3)	−0.0055 (4)	−0.0054 (4)
N1	0.0226 (6)	0.0203 (5)	0.0254 (6)	−0.0001 (4)	0.0005 (4)	−0.0031 (4)
N2	0.0188 (5)	0.0197 (5)	0.0148 (5)	−0.0010 (4)	−0.0036 (4)	−0.0025 (4)
N3	0.0246 (6)	0.0153 (5)	0.0201 (5)	0.0027 (4)	0.0003 (4)	−0.0017 (4)
N4	0.0174 (5)	0.0132 (4)	0.0161 (5)	0.0007 (4)	−0.0024 (4)	−0.0043 (4)
C1	0.0169 (6)	0.0224 (6)	0.0241 (6)	−0.0026 (5)	−0.0020 (5)	−0.0027 (5)
C2	0.0194 (6)	0.0184 (6)	0.0202 (6)	−0.0034 (4)	−0.0024 (5)	−0.0049 (5)
C3	0.0173 (6)	0.0189 (6)	0.0147 (5)	−0.0018 (4)	−0.0013 (4)	−0.0021 (4)
C4	0.0220 (6)	0.0234 (6)	0.0166 (5)	−0.0042 (5)	−0.0025 (5)	−0.0053 (5)
C5	0.0276 (7)	0.0197 (6)	0.0236 (6)	−0.0025 (5)	0.0008 (5)	−0.0075 (5)
C6	0.0221 (6)	0.0218 (6)	0.0172 (5)	−0.0057 (5)	−0.0063 (5)	−0.0012 (5)
C7	0.0242 (6)	0.0210 (6)	0.0207 (6)	−0.0008 (5)	−0.0099 (5)	−0.0024 (5)
C8	0.0500 (10)	0.0231 (7)	0.0274 (7)	−0.0034 (6)	−0.0171 (7)	0.0037 (6)
C9	0.0504 (10)	0.0253 (7)	0.0336 (8)	−0.0101 (7)	−0.0105 (7)	−0.0069 (6)
C10	0.0407 (9)	0.0289 (8)	0.0327 (8)	−0.0103 (7)	−0.0069 (7)	−0.0072 (6)
C11	0.0374 (8)	0.0175 (6)	0.0303 (7)	0.0006 (5)	−0.0164 (6)	−0.0064 (5)
C12	0.0197 (6)	0.0179 (6)	0.0213 (6)	−0.0004 (4)	−0.0067 (5)	−0.0048 (5)
C13	0.0194 (6)	0.0167 (5)	0.0172 (5)	−0.0037 (4)	−0.0024 (4)	−0.0039 (4)
C14	0.0480 (10)	0.0213 (7)	0.0546 (11)	0.0049 (7)	−0.0255 (9)	−0.0033 (7)
C15	0.0297 (7)	0.0146 (5)	0.0160 (5)	0.0019 (5)	−0.0026 (5)	−0.0047 (4)
C16	0.0220 (6)	0.0155 (5)	0.0181 (5)	0.0002 (4)	−0.0055 (5)	−0.0042 (4)
C17	0.0188 (6)	0.0128 (5)	0.0151 (5)	0.0021 (4)	−0.0029 (4)	−0.0025 (4)
C18	0.0201 (6)	0.0147 (5)	0.0168 (5)	0.0020 (4)	−0.0047 (4)	−0.0041 (4)
C19	0.0191 (6)	0.0163 (5)	0.0220 (6)	0.0010 (4)	−0.0027 (5)	−0.0018 (5)
C20	0.0176 (5)	0.0149 (5)	0.0184 (5)	0.0019 (4)	−0.0059 (4)	−0.0051 (4)
C21	0.0168 (5)	0.0147 (5)	0.0195 (5)	0.0010 (4)	−0.0029 (4)	−0.0059 (4)
C22	0.0254 (6)	0.0161 (5)	0.0187 (6)	0.0002 (5)	−0.0029 (5)	−0.0065 (5)
C23	0.0275 (7)	0.0226 (6)	0.0204 (6)	−0.0013 (5)	−0.0081 (5)	−0.0079 (5)
C24	0.0314 (7)	0.0227 (6)	0.0187 (6)	0.0019 (5)	−0.0098 (5)	−0.0052 (5)
C25	0.0305 (7)	0.0170 (6)	0.0176 (6)	−0.0016 (5)	−0.0002 (5)	−0.0021 (5)
C26	0.0188 (6)	0.0148 (5)	0.0195 (6)	−0.0010 (4)	−0.0018 (4)	−0.0050 (4)
C27	0.0184 (5)	0.0158 (5)	0.0167 (5)	−0.0011 (4)	−0.0056 (4)	−0.0047 (4)
C28	0.0332 (8)	0.0245 (7)	0.0199 (6)	−0.0012 (6)	0.0023 (5)	−0.0069 (5)

Geometric parameters (Å, º) top

F1—C1	1.3384 (16)	C9—C10	1.304 (2)
F2—C2	1.3390 (15)	C9—H9	0.95
F3—C4	1.3343 (16)	C10—C11	1.473 (2)
F4—C5	1.3364 (16)	C10—H10	0.95
F5—C15	1.3398 (15)	C11—C14	1.535 (2)
F6—C16	1.3370 (15)	C11—C12	1.5683 (19)
F7—C18	1.3325 (14)	C11—H11	1.0
F8—C19	1.3370 (16)	C12—C13	1.5084 (18)
O1—C6	1.2075 (17)	C12—H12	1.0
O2—C13	1.2028 (16)	C14—H14A	0.99
O3—C20	1.2038 (16)	C14—H14B	0.99
O4—C27	1.2102 (16)	C15—C16	1.3794 (19)
N1—C1	1.3111 (18)	C16—C17	1.3909 (17)
N1—C5	1.312 (2)	C17—C18	1.3858 (18)
N2—C6	1.4077 (17)	C18—C19	1.3825 (18)
N2—C3	1.4107 (17)	C20—C21	1.5033 (18)
N2—C13	1.4161 (17)	C21—C26	1.5499 (18)
N3—C19	1.3103 (18)	C21—C22	1.5753 (18)
N3—C15	1.3125 (19)	C21—H21	1.0
N4—C27	1.4056 (17)	C22—C23	1.516 (2)
N4—C17	1.4086 (16)	C22—C28	1.537 (2)
N4—C20	1.4165 (16)	C22—H22	1.0
C1—C2	1.3809 (19)	C23—C24	1.338 (2)
C2—C3	1.3871 (18)	C23—H23	0.95
C3—C4	1.3917 (18)	C24—C25	1.519 (2)
C4—C5	1.385 (2)	C24—H24	0.95
C6—C7	1.507 (2)	C25—C28	1.550 (2)
C7—C12	1.5482 (19)	C25—C26	1.5717 (19)
C7—C8	1.571 (2)	C25—H25	1.0
C7—H7	1.0	C26—C27	1.5091 (18)
C8—C9	1.501 (3)	C26—H26	1.0
C8—C14	1.623 (3)	C28—H28A	0.99
C8—H8	1.0	C28—H28B	0.99

C1—N1—C5	116.94 (12)	C8—C14—H14A	113.4
C6—N2—C3	124.33 (11)	C11—C14—H14B	113.4
C6—N2—C13	113.71 (11)	C8—C14—H14B	113.4
C3—N2—C13	121.94 (11)	H14A—C14—H14B	110.7
C19—N3—C15	117.26 (12)	N3—C15—F5	116.65 (12)
C27—N4—C17	123.69 (10)	N3—C15—C16	124.23 (12)
C27—N4—C20	113.87 (11)	F5—C15—C16	119.11 (12)
C17—N4—C20	122.21 (11)	F6—C16—C15	120.74 (11)
N1—C1—F1	117.06 (12)	F6—C16—C17	120.86 (12)
N1—C1—C2	124.07 (13)	C15—C16—C17	118.40 (12)
F1—C1—C2	118.87 (12)	C18—C17—C16	117.45 (12)
F2—C2—C1	120.87 (12)	C18—C17—N4	120.70 (11)
F2—C2—C3	119.96 (12)	C16—C17—N4	121.85 (12)
C1—C2—C3	119.15 (12)	F7—C18—C19	120.46 (12)
C2—C3—C4	116.92 (12)	F7—C18—C17	120.92 (11)
C2—C3—N2	121.00 (11)	C19—C18—C17	118.60 (12)
C4—C3—N2	122.02 (12)	N3—C19—F8	117.01 (12)
F3—C4—C5	120.87 (12)	N3—C19—C18	124.05 (13)
F3—C4—C3	120.66 (12)	F8—C19—C18	118.94 (12)
C5—C4—C3	118.42 (12)	O3—C20—N4	123.24 (12)
N1—C5—F4	116.75 (13)	O3—C20—C21	129.39 (12)
N1—C5—C4	124.49 (13)	N4—C20—C21	107.37 (10)
F4—C5—C4	118.75 (13)	C20—C21—C26	105.67 (10)
O1—C6—N2	123.41 (13)	C20—C21—C22	113.60 (11)
O1—C6—C7	129.08 (13)	C26—C21—C22	103.31 (10)
N2—C6—C7	107.50 (11)	C20—C21—H21	111.3
C6—C7—C12	105.79 (11)	C26—C21—H21	111.3
C6—C7—C8	114.60 (13)	C22—C21—H21	111.3
C12—C7—C8	102.66 (11)	C23—C22—C28	100.97 (11)
C6—C7—H7	111.1	C23—C22—C21	106.32 (10)
C12—C7—H7	111.1	C28—C22—C21	98.84 (11)
C8—C7—H7	111.1	C23—C22—H22	116.1
C9—C8—C7	106.69 (13)	C28—C22—H22	116.1
C9—C8—C14	97.02 (13)	C21—C22—H22	116.1
C7—C8—C14	98.55 (13)	C24—C23—C22	107.28 (13)
C9—C8—H8	117.1	C24—C23—H23	126.4
C7—C8—H8	117.1	C22—C23—H23	126.4
C14—C8—H8	117.1	C23—C24—C25	108.23 (13)
C10—C9—C8	111.81 (17)	C23—C24—H24	125.9
C10—C9—H9	124.1	C25—C24—H24	125.9
C8—C9—H9	124.1	C24—C25—C28	100.25 (11)
C9—C10—C11	105.78 (16)	C24—C25—C26	106.61 (11)
C9—C10—H10	127.1	C28—C25—C26	98.57 (11)
C11—C10—H10	127.1	C24—C25—H25	116.3
C10—C11—C14	103.19 (15)	C28—C25—H25	116.3
C10—C11—C12	107.98 (13)	C26—C25—H25	116.3
C14—C11—C12	99.67 (12)	C27—C26—C21	105.73 (10)
C10—C11—H11	114.8	C27—C26—C25	113.65 (11)
C14—C11—H11	114.8	C21—C26—C25	102.89 (10)
C12—C11—H11	114.8	C27—C26—H26	111.4
C13—C12—C7	105.61 (11)	C21—C26—H26	111.4
C13—C12—C11	115.44 (11)	C25—C26—H26	111.4
C7—C12—C11	103.66 (11)	O4—C27—N4	123.64 (12)
C13—C12—H12	110.6	O4—C27—C26	128.99 (12)
C7—C12—H12	110.6	N4—C27—C26	107.35 (10)
C11—C12—H12	110.6	C22—C28—C25	94.29 (11)
O2—C13—N2	123.30 (12)	C22—C28—H28A	112.9
O2—C13—C12	129.34 (12)	C25—C28—H28A	112.9
N2—C13—C12	107.35 (11)	C22—C28—H28B	112.9
C11—C14—C8	91.50 (13)	C25—C28—H28B	112.9
C11—C14—H14A	113.4	H28A—C28—H28B	110.3

C5—N1—C1—F1	179.36 (12)	C19—N3—C15—F5	−179.67 (11)
C5—N1—C1—C2	−0.2 (2)	C19—N3—C15—C16	0.4 (2)
N1—C1—C2—F2	178.68 (13)	N3—C15—C16—F6	179.92 (12)
F1—C1—C2—F2	−0.9 (2)	F5—C15—C16—F6	0.03 (19)
N1—C1—C2—C3	0.0 (2)	N3—C15—C16—C17	−0.2 (2)
F1—C1—C2—C3	−179.51 (12)	F5—C15—C16—C17	179.89 (11)
F2—C2—C3—C4	−178.07 (11)	F6—C16—C17—C18	179.90 (11)
C1—C2—C3—C4	0.57 (19)	C15—C16—C17—C18	0.04 (18)
F2—C2—C3—N2	4.45 (19)	F6—C16—C17—N4	0.29 (19)
C1—C2—C3—N2	−176.90 (12)	C15—C16—C17—N4	−179.57 (11)
C6—N2—C3—C2	−122.28 (14)	C27—N4—C17—C18	115.77 (14)
C13—N2—C3—C2	56.10 (17)	C20—N4—C17—C18	−58.41 (16)
C6—N2—C3—C4	60.38 (18)	C27—N4—C17—C16	−64.63 (17)
C13—N2—C3—C4	−121.24 (14)	C20—N4—C17—C16	121.18 (13)
C2—C3—C4—F3	−178.53 (12)	C16—C17—C18—F7	178.24 (11)
N2—C3—C4—F3	−1.08 (19)	N4—C17—C18—F7	−2.15 (18)
C2—C3—C4—C5	−1.01 (19)	C16—C17—C18—C19	−0.10 (18)
N2—C3—C4—C5	176.44 (12)	N4—C17—C18—C19	179.52 (11)
C1—N1—C5—F4	178.87 (12)	C15—N3—C19—F8	179.93 (11)
C1—N1—C5—C4	−0.3 (2)	C15—N3—C19—C18	−0.5 (2)
F3—C4—C5—N1	178.43 (13)	F7—C18—C19—N3	−178.00 (12)
C3—C4—C5—N1	0.9 (2)	C17—C18—C19—N3	0.3 (2)
F3—C4—C5—F4	−0.7 (2)	F7—C18—C19—F8	1.56 (19)
C3—C4—C5—F4	−178.23 (12)	C17—C18—C19—F8	179.90 (11)
C3—N2—C6—O1	1.5 (2)	C27—N4—C20—O3	−178.97 (12)
C13—N2—C6—O1	−176.98 (13)	C17—N4—C20—O3	−4.26 (19)
C3—N2—C6—C7	−179.43 (11)	C27—N4—C20—C21	1.03 (14)
C13—N2—C6—C7	2.06 (15)	C17—N4—C20—C21	175.74 (11)
O1—C6—C7—C12	176.95 (14)	O3—C20—C21—C26	178.83 (13)
N2—C6—C7—C12	−2.02 (14)	N4—C20—C21—C26	−1.17 (13)
O1—C6—C7—C8	64.62 (19)	O3—C20—C21—C22	66.28 (17)
N2—C6—C7—C8	−114.36 (13)	N4—C20—C21—C22	−113.72 (11)
C6—C7—C8—C9	51.32 (17)	C20—C21—C22—C23	46.18 (14)
C12—C7—C8—C9	−62.86 (16)	C26—C21—C22—C23	−67.79 (13)
C6—C7—C8—C14	151.35 (12)	C20—C21—C22—C28	150.43 (11)
C12—C7—C8—C14	37.17 (14)	C26—C21—C22—C28	36.46 (12)
C7—C8—C9—C10	68.24 (19)	C28—C22—C23—C24	−33.15 (14)
C14—C8—C9—C10	−32.91 (18)	C21—C22—C23—C24	69.55 (14)
C8—C9—C10—C11	0.42 (19)	C22—C23—C24—C25	0.53 (15)
C9—C10—C11—C14	35.12 (18)	C23—C24—C25—C28	31.90 (14)
C9—C10—C11—C12	−69.79 (17)	C23—C24—C25—C26	−70.35 (14)
C6—C7—C12—C13	1.33 (14)	C20—C21—C26—C27	0.93 (13)
C8—C7—C12—C13	121.79 (12)	C22—C21—C26—C27	120.51 (11)
C6—C7—C12—C11	−120.46 (12)	C20—C21—C26—C25	−118.55 (11)
C8—C7—C12—C11	−0.01 (14)	C22—C21—C26—C25	1.04 (12)
C10—C11—C12—C13	−47.45 (16)	C24—C25—C26—C27	−48.17 (14)
C14—C11—C12—C13	−154.82 (14)	C28—C25—C26—C27	−151.64 (11)
C10—C11—C12—C7	67.53 (14)	C24—C25—C26—C21	65.64 (12)
C14—C11—C12—C7	−39.85 (15)	C28—C25—C26—C21	−37.82 (12)
C6—N2—C13—O2	179.80 (12)	C17—N4—C27—O4	3.78 (19)
C3—N2—C13—O2	1.3 (2)	C20—N4—C27—O4	178.40 (12)
C6—N2—C13—C12	−1.18 (15)	C17—N4—C27—C26	−175.04 (11)
C3—N2—C13—C12	−179.73 (11)	C20—N4—C27—C26	−0.41 (14)
C7—C12—C13—O2	178.76 (14)	C21—C26—C27—O4	−179.08 (13)
C11—C12—C13—O2	−67.39 (19)	C25—C26—C27—O4	−66.97 (17)
C7—C12—C13—N2	−0.18 (14)	C21—C26—C27—N4	−0.35 (13)
C11—C12—C13—N2	113.68 (13)	C25—C26—C27—N4	111.75 (12)
C10—C11—C14—C8	−50.81 (14)	C23—C22—C28—C25	49.19 (12)
C12—C11—C14—C8	60.38 (14)	C21—C22—C28—C25	−59.46 (12)
C9—C8—C14—C11	47.84 (14)	C24—C25—C28—C22	−48.49 (12)
C7—C8—C14—C11	−60.29 (13)	C26—C25—C28—C22	60.24 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1ⁱ	1.00	2.58	3.3467 (18)	133
C12—H12···F2ⁱⁱ	1.00	2.30	3.1902 (17)	147
C21—H21···F7ⁱⁱ	1.00	2.55	3.3855 (16)	141
C21—H21···O3ⁱⁱⁱ	1.00	2.51	3.2765 (16)	133
C26—H26···O4^iv	1.00	2.51	3.3299 (17)	139
C6—O1···Cg1^v		3.05 (1)	4.0022 (16)	136 (1)
C13—O2···Cg2		3.18 (1)	4.0238 (17)	127 (1)
C27—O4···Cg2^vi		3.30 (1)	4.0644 (16)	122 (1)

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x+1, y, z; (iii) −x+2, −y+1, −z+1; (iv) −x+2, −y+2, −z+1; (v) −x, −y+1, −z+2; (vi) −x+1, −y+2, −z+1.

(II) top

Crystal data top

C₁₄H₈F₄N₂O₃	F(000) = 664
M_r = 328.22	D_x = 1.672 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.285 (6) Å	Cell parameters from 5752 reflections
b = 5.945 (3) Å	θ = 3.3–30.5°
c = 17.888 (8) Å	µ = 0.16 mm⁻¹
β = 93.44 (3)°	T = 100 K
V = 1304.1 (10) Å³	Rectangular prism, clear colourless
Z = 4	0.55 × 0.40 × 0.36 mm

Data collection top

Bruker SMART APEX CCD diffractometer	3823 independent reflections
Radiation source: fine focus sealed tube	3443 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
Detector resolution: 8.3333 pixels mm^-1	θ_max = 30.0°, θ_min = 2.0°
ω Scans scans	h = −16→17
Absorption correction: multi-scan (SADABS; Bruker, 2017)	k = −8→8
T_min = 0.80, T_max = 0.95	l = −25→25
18507 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.105	w = 1/[σ²(F_o²) + (0.0563P)² + 0.5528P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
3823 reflections	Δρ_max = 0.47 e Å⁻³
208 parameters	Δρ_min = −0.25 e Å⁻³
0 restraints

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
F1	0.61173 (7)	0.22134 (14)	0.90365 (4)	0.03327 (19)
F2	0.48454 (5)	0.59673 (13)	0.88542 (4)	0.02357 (16)
F3	0.59308 (6)	0.63688 (13)	0.63887 (4)	0.02478 (16)
F4	0.71117 (6)	0.25516 (14)	0.66738 (4)	0.02993 (18)
O1	0.47406 (6)	0.82103 (13)	0.75548 (4)	0.01844 (16)
O2	0.30179 (7)	0.51138 (14)	0.73480 (4)	0.02086 (17)
O3	0.45672 (7)	1.14224 (14)	0.64230 (5)	0.02420 (18)
N1	0.66094 (8)	0.24215 (17)	0.78498 (6)	0.0230 (2)
N2	0.39641 (7)	0.81650 (15)	0.69490 (5)	0.01503 (17)
C1	0.60565 (9)	0.3286 (2)	0.83821 (6)	0.0215 (2)
C2	0.54134 (8)	0.51817 (19)	0.82990 (6)	0.0178 (2)
C3	0.53515 (8)	0.62643 (17)	0.76138 (6)	0.01569 (19)
C4	0.59438 (8)	0.53864 (18)	0.70529 (6)	0.0178 (2)
C5	0.65454 (9)	0.3444 (2)	0.72060 (6)	0.0208 (2)
C6	0.30836 (8)	0.66728 (17)	0.69255 (6)	0.01506 (18)
C7	0.23148 (8)	0.74245 (16)	0.62858 (5)	0.01440 (18)
H7	0.156899	0.76892	0.646338	0.017*
C8	0.22529 (9)	0.59170 (17)	0.55743 (6)	0.01733 (19)
H8	0.178143	0.454959	0.559446	0.021*
C9	0.34224 (9)	0.55197 (19)	0.53633 (6)	0.0201 (2)
H9	0.381115	0.413986	0.540679	0.024*
C10	0.38003 (9)	0.74523 (19)	0.51076 (6)	0.0204 (2)
H10	0.450329	0.769546	0.49285	0.024*
C11	0.29036 (9)	0.92015 (18)	0.51536 (6)	0.01784 (19)
H11	0.296331	1.055951	0.482876	0.021*
C12	0.28051 (8)	0.96515 (17)	0.60041 (6)	0.01497 (18)
H12	0.230305	1.094276	0.608299	0.018*
C13	0.38855 (8)	0.99715 (17)	0.64552 (6)	0.01595 (19)
C14	0.18776 (9)	0.77180 (18)	0.49978 (6)	0.0193 (2)
H14A	0.119519	0.847875	0.512318	0.023*
H14B	0.180981	0.713441	0.447871	0.023*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0372 (4)	0.0362 (4)	0.0258 (4)	0.0035 (3)	−0.0029 (3)	0.0160 (3)
F2	0.0194 (3)	0.0364 (4)	0.0149 (3)	−0.0003 (3)	0.0015 (2)	0.0005 (3)
F3	0.0241 (3)	0.0353 (4)	0.0149 (3)	0.0052 (3)	0.0016 (2)	0.0048 (3)
F4	0.0248 (4)	0.0381 (4)	0.0268 (4)	0.0120 (3)	0.0013 (3)	−0.0068 (3)
O1	0.0189 (3)	0.0198 (4)	0.0157 (3)	0.0032 (3)	−0.0064 (3)	−0.0024 (3)
O2	0.0214 (4)	0.0224 (4)	0.0189 (4)	−0.0009 (3)	0.0014 (3)	0.0074 (3)
O3	0.0243 (4)	0.0187 (4)	0.0289 (4)	−0.0060 (3)	−0.0042 (3)	0.0032 (3)
N1	0.0184 (4)	0.0233 (5)	0.0265 (5)	0.0023 (3)	−0.0049 (4)	0.0021 (4)
N2	0.0135 (4)	0.0177 (4)	0.0134 (4)	−0.0001 (3)	−0.0031 (3)	0.0017 (3)
C1	0.0195 (5)	0.0242 (5)	0.0202 (5)	−0.0011 (4)	−0.0039 (4)	0.0067 (4)
C2	0.0139 (4)	0.0242 (5)	0.0150 (4)	−0.0023 (4)	−0.0013 (3)	0.0013 (4)
C3	0.0122 (4)	0.0182 (4)	0.0162 (4)	−0.0008 (3)	−0.0029 (3)	0.0006 (3)
C4	0.0151 (4)	0.0231 (5)	0.0148 (4)	0.0003 (4)	−0.0018 (3)	0.0016 (4)
C5	0.0151 (4)	0.0248 (5)	0.0220 (5)	0.0024 (4)	−0.0020 (4)	−0.0032 (4)
C6	0.0138 (4)	0.0170 (4)	0.0146 (4)	0.0005 (3)	0.0021 (3)	0.0000 (3)
C7	0.0135 (4)	0.0155 (4)	0.0141 (4)	0.0004 (3)	−0.0003 (3)	0.0010 (3)
C8	0.0197 (5)	0.0151 (4)	0.0168 (4)	−0.0006 (3)	−0.0020 (3)	−0.0007 (3)
C9	0.0235 (5)	0.0196 (5)	0.0172 (5)	0.0056 (4)	0.0004 (4)	−0.0035 (4)
C10	0.0207 (5)	0.0256 (5)	0.0152 (5)	0.0027 (4)	0.0031 (4)	−0.0012 (4)
C11	0.0217 (5)	0.0180 (4)	0.0136 (4)	0.0009 (4)	−0.0006 (3)	0.0027 (3)
C12	0.0153 (4)	0.0140 (4)	0.0153 (4)	0.0014 (3)	−0.0014 (3)	0.0011 (3)
C13	0.0180 (4)	0.0141 (4)	0.0156 (4)	0.0019 (3)	−0.0001 (3)	−0.0002 (3)
C14	0.0209 (5)	0.0209 (5)	0.0155 (4)	0.0015 (4)	−0.0042 (4)	0.0000 (4)

Geometric parameters (Å, º) top

F1—C1	1.3312 (14)	C7—C12	1.5511 (15)
F2—C2	1.3323 (13)	C7—C8	1.5547 (15)
F3—C4	1.3231 (13)	C7—H7	1.0
F4—C5	1.3234 (13)	C8—C9	1.5256 (16)
O1—C3	1.3796 (13)	C8—C14	1.5380 (15)
O1—N2	1.4004 (12)	C8—H8	1.0
O2—C6	1.2017 (13)	C9—C10	1.3305 (17)
O3—C13	1.2060 (14)	C9—H9	0.95
N1—C5	1.3005 (16)	C10—C11	1.5207 (16)
N1—C1	1.3076 (16)	C10—H10	0.95
N2—C13	1.3901 (14)	C11—C14	1.5499 (16)
N2—C6	1.3975 (14)	C11—C12	1.5565 (16)
C1—C2	1.3791 (16)	C11—H11	1.0
C2—C3	1.3824 (15)	C12—C13	1.5233 (15)
C3—C4	1.3769 (15)	C12—H12	1.0
C4—C5	1.3891 (16)	C14—H14A	0.99
C6—C7	1.5071 (15)	C14—H14B	0.99

C3—O1—N2	112.66 (8)	C14—C8—C7	98.38 (9)
C5—N1—C1	117.04 (10)	C9—C8—H8	116.0
C13—N2—C6	116.56 (9)	C14—C8—H8	116.0
C13—N2—O1	119.66 (8)	C7—C8—H8	116.0
C6—N2—O1	121.70 (8)	C10—C9—C8	107.73 (9)
N1—C1—F1	116.61 (11)	C10—C9—H9	126.1
N1—C1—C2	124.18 (10)	C8—C9—H9	126.1
F1—C1—C2	119.20 (11)	C9—C10—C11	107.64 (10)
F2—C2—C1	121.89 (10)	C9—C10—H10	126.2
F2—C2—C3	119.63 (10)	C11—C10—H10	126.2
C1—C2—C3	118.47 (10)	C10—C11—C14	100.67 (9)
C4—C3—O1	124.82 (9)	C10—C11—C12	105.64 (8)
C4—C3—C2	117.79 (10)	C14—C11—C12	99.41 (8)
O1—C3—C2	117.32 (9)	C10—C11—H11	116.2
F3—C4—C3	120.56 (10)	C14—C11—H11	116.2
F3—C4—C5	121.43 (10)	C12—C11—H11	116.2
C3—C4—C5	118.00 (10)	C13—C12—C7	106.11 (8)
N1—C5—F4	116.30 (10)	C13—C12—C11	115.01 (9)
N1—C5—C4	124.49 (10)	C7—C12—C11	103.02 (8)
F4—C5—C4	119.20 (10)	C13—C12—H12	110.8
O2—C6—N2	123.48 (10)	C7—C12—H12	110.8
O2—C6—C7	130.06 (10)	C11—C12—H12	110.8
N2—C6—C7	106.45 (9)	O3—C13—N2	124.12 (10)
C6—C7—C12	105.18 (8)	O3—C13—C12	130.51 (10)
C6—C7—C8	116.63 (9)	N2—C13—C12	105.38 (8)
C12—C7—C8	103.12 (8)	C8—C14—C11	93.88 (8)
C6—C7—H7	110.5	C8—C14—H14A	112.9
C12—C7—H7	110.5	C11—C14—H14A	112.9
C8—C7—H7	110.5	C8—C14—H14B	112.9
C9—C8—C14	101.00 (9)	C11—C14—H14B	112.9
C9—C8—C7	106.93 (8)	H14A—C14—H14B	110.4

C3—O1—N2—C13	−130.66 (10)	N2—C6—C7—C8	107.89 (10)
C3—O1—N2—C6	66.28 (12)	C6—C7—C8—C9	−50.39 (11)
C5—N1—C1—F1	179.27 (10)	C12—C7—C8—C9	64.30 (10)
C5—N1—C1—C2	0.48 (17)	C6—C7—C8—C14	−154.65 (9)
N1—C1—C2—F2	178.42 (10)	C12—C7—C8—C14	−39.97 (9)
F1—C1—C2—F2	−0.34 (16)	C14—C8—C9—C10	31.98 (11)
N1—C1—C2—C3	−0.67 (17)	C7—C8—C9—C10	−70.39 (11)
F1—C1—C2—C3	−179.43 (10)	C8—C9—C10—C11	1.02 (12)
N2—O1—C3—C4	55.79 (13)	C9—C10—C11—C14	−33.35 (11)
N2—O1—C3—C2	−127.50 (10)	C9—C10—C11—C12	69.69 (11)
F2—C2—C3—C4	−179.44 (9)	C6—C7—C12—C13	4.58 (10)
C1—C2—C3—C4	−0.33 (15)	C8—C7—C12—C13	−118.12 (9)
F2—C2—C3—O1	3.61 (14)	C6—C7—C12—C11	125.81 (8)
C1—C2—C3—O1	−177.28 (9)	C8—C7—C12—C11	3.12 (9)
O1—C3—C4—F3	−2.24 (16)	C10—C11—C12—C13	45.57 (11)
C2—C3—C4—F3	−178.94 (9)	C14—C11—C12—C13	149.54 (9)
O1—C3—C4—C5	178.10 (9)	C10—C11—C12—C7	−69.40 (10)
C2—C3—C4—C5	1.40 (15)	C14—C11—C12—C7	34.56 (9)
C1—N1—C5—F4	179.84 (10)	C6—N2—C13—O3	178.19 (10)
C1—N1—C5—C4	0.74 (17)	O1—N2—C13—O3	14.27 (15)
F3—C4—C5—N1	178.64 (10)	C6—N2—C13—C12	−1.96 (12)
C3—C4—C5—N1	−1.70 (17)	O1—N2—C13—C12	−165.88 (8)
F3—C4—C5—F4	−0.44 (16)	C7—C12—C13—O3	177.99 (11)
C3—C4—C5—F4	179.22 (10)	C11—C12—C13—O3	64.81 (15)
C13—N2—C6—O2	−175.80 (10)	C7—C12—C13—N2	−1.85 (10)
O1—N2—C6—O2	−12.23 (15)	C11—C12—C13—N2	−115.02 (9)
C13—N2—C6—C7	5.00 (12)	C9—C8—C14—C11	−48.57 (9)
O1—N2—C6—C7	168.57 (8)	C7—C8—C14—C11	60.61 (9)
O2—C6—C7—C12	175.23 (11)	C10—C11—C14—C8	49.16 (9)
N2—C6—C7—C12	−5.64 (10)	C12—C11—C14—C8	−58.86 (9)
O2—C6—C7—C8	−71.24 (14)

Contact geometry (Å, °) for I top

Cg1 and Cg2 are the centroids of the N1/C1–C5 and N3/C15–C19 rings, respectively.

Y—X···A	Y—X	X···A	Y···A	Y—X···A
C7—H7···O1ⁱ	1.00	2.58	3.347 (2)	133
C9—H9···F4ⁱⁱ	0.95	2.49	3.348(20	150
C12—H12···F2ⁱⁱⁱ	1.00	2.30	3.1903 (18)	147
C21—H21···F7ⁱⁱⁱ	1.00	2.55	3.3855 (17)	141
C21—H21..O3^iv	1.00	2.51	3.2764 (18)	133
C26—H26···O4^v	1.00	2.51	3.3299 (18)	139
C6—O1···Cg1ⁱ	1.2075 (17)	3.0462 (14)	4.022 (16)	135.86 (10)
C13—O2···Cg2^vi	1.2028 (16)	3.1839 (14)	4.0238 (17)	126.98 (9)
C27—O4···Cg2ⁱⁱ	1.2102 (16)	3.2978 (14)	4.0644 (16)	121.58 (9)

Symmetry codes: (i) 1 - x, 1 - y, 2 - z; (ii) -x, 1 - y, 2 - z; (iii) 1 + x, y, z; (iv) 2 - x, 1 - y, 1 - z; (v) 2 - x, 2 - y, 1 - z; (iv) x, y, z.

Contact geometry (Å, °) for II top

Cg1 is the centroid of the N1/C1–C5 ring.

Y—X···A	Y—X	X···A	Y···A	Y—X···A
C7—H7···O2ⁱ	1.00	2.58	3.347 (2)	133
C9—H9···O3ⁱⁱ	0.95	2.49	3.348(20	150
C14—H14B···F4ⁱⁱⁱ	1.00	2.30	3.1903 (18)	147
C5—F4···Cg1^iv	1.3234 (13)	3.1543 (18)	3.892 (2)	114.36 (7)
C13—O3···Cg1^v	1.2060 (14)	3.3224 (19)	4.231 (2)	132.8 (8)

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

Percentage contribution of inter-atomic contacts to the Hirshfeld surfaces for I and II top

Contact	Percentage contribution to I	Percentage contribution to II
F···H/H···F	36.5	39.2
H···H	20.2	14.1
O···H/H···O	13.0	14.0
O···C/C···O	6.2	6.2
N···H/H···N	5.3	0.1
F···F	5.1	2.1
F···C/C···F	3.6	4.9
F···N/N···F	2.4	4.4
O···N/N···O	0.6	4.1
C···H/H···C	3.8	3.2
F···O/O···F	2.4	2.7
O···O	1.2	2.7
N···C/C···N	0.0	2.4

Funding information

Funding for this research was provided by: Air Force Office of Scientific Reseach.

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