Crystal structures and Hirshfeld surface analysis of a series of 4-O-aryl­perfluoro­pyridines

Peloquin, A.J.; Corley, C.A.; Adas, S.K.; Balaich, G.J.; Iacono, S.T.

doi:10.1107/S2056989019009344

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ISSN: 2056-9890

Volume 75| Part 8| August 2019| Pages 1102-1107

https://doi.org/10.1107/S2056989019009344

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Crystal structures and Hirshfeld surface analysis of a series of 4-O-arylperfluoropyridines

Andrew J. Peloquin,^a Cynthia A. Corley,^a Sonya K. Adas,^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 13 June 2019; accepted 28 June 2019; online 4 July 2019)

Five new crystal structures of perfluoropyridine substituted in the 4-position with phenoxy, 4-bromophenoxy, naphthalen-2-yloxy, 6-bromonaphthalen-2-yloxy, and 4,4′-biphenoxy are reported, viz. 2,3,5,6-tetrafluoro-4-phenoxypyridine, C₁₁H₅F₄NO (I), 4-(4-bromophenoxy)-2,3,5,6-tetrafluoropyridine, C₁₁H₄BrF₄NO (II), 2,3,5,6-tetrafluoro-4-[(naphthalen-2-yl)oxy]pyridine, C₁₅H₇F₄NO (III), 4-[(6-bromonaphthalen-2-yl)oxy]-2,3,5,6-tetrafluoropyridine, C₁₅H₆BrF₄NO (IV), and 2,2′-bis[(perfluoropyridin-4-yl)oxy]-1,1′-biphenyl, C₂₂H₈F₈N₂O₂ (V). The dihedral angles between the aromatic ring systems in I–IV are 78.74 (8), 56.35 (8), 74.30 (7), and 64.34 (19)°, respectively. The complete molecule of V is generated by a crystallographic twofold axis: the dihedral angle between the pyridine ring and adjacent phenyl ring is 80.89 (5)° and the equivalent angle between the biphenyl rings is 27.30 (5)°. In each crystal, the packing is driven by C—H⋯F interactions, along with a variety of C—F⋯π, C—H⋯π, C—Br⋯N, C—H⋯N, and C—Br⋯π contacts. Hirshfeld surface analysis was conducted to aid in the visualization of these various influences on the packing.

Keywords: crystal structure; perfluoropyridine.

CCDC references: 1937619; 1937620; 1937621; 1937622; 1937623

1. Chemical context

Pentafluoropyridine, or perfluoropyridine (C₅F₅N) is one of the most important perfluoroheteroaromatic compounds. It is commercially available and its chemistry is well understood. As a result of the presence of five fluorine atoms, in addition to the nitrogen atom of the pyridine ring, these systems are highly electrophilic and undergo substitution reactions readily in a predictable pattern (Baker & Muir, 2010 ; Chambers et al., 1988 ). This chemistry has already been used in the design of several drugs (Bhambra et al., 2016 ) and in peptide modification (Gimenez et al., 2017 ). In an effort to further understand the intermolecular interactions in the solid state of these fluorinated compounds, five new crystal structures of pentafluoropyridine derivatives are herein reported as well as their syntheses.

2. Structural commentary

Compounds I, III, and V each crystallize in orthorhombic space groups, with I and III in P2₁2₁2₁ and V in Pbcn. Compounds II and IV crystallize in the monoclinic space groups P2₁/n and P2₁ respectively (Fig. 1). With the exception of V, which has one half molecule per asymmetric unit, each compound crystallizes with one molecule per asymmetric unit. The dihedral angle between the aryl susbstituent and the pyridine ring ranges between 56.35 (8) and 80.89 (5)°. In V, the rings of the biphenyl system are rotated by 27.30 (5)° from each other.

Figure 1
The molecular structures of (a) I, (b) II, (c) III, (d) IV, and (e) V. Displacement ellipsoids are shown at the 50% probability level.

3. Supramolecular features and Hirshfeld surface analysis

In the crystal structures of each compound, the packing is consolidated by various C—H⋯F and C—F⋯π interactions (Tables 1–5 ). In II, the packing is aided by C—H⋯π and C—Br⋯N interactions, the latter of which lead to the formation of chains in the [10 $[\overline{1}]$ ] direction. Compound III also shows C—H⋯N hydrogen bonding. Further, in IV, C—H⋯π and C—Br⋯π interactions also contribute to the packing. Finally, in I, III, and IV, the packing is aided by halogen bonds of the type C—F⋯F—C or C—F⋯Br—C. In I, the C2—F2⋯F3 distance is 2.8156 (15) Å, with an angle of 119.54 (8)° (symmetry code: 1 − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z). For III, the C2—F2⋯F3 distance is 2.766 (15) Å, with an angle of 146.28 (10)° (symmetry code: 1 − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z). The bromine atom participates in the halogen bonding of IV, with the C11—Br1⋯F2 distance being 3.095 (5) Å and the angle 164.46 (14)° (symmetry code: 2 − x, − $[{1\over 2}]$ + y, 1 − z). All the observed halogen-bonding geometries fall within typically observed values (Cavallo et al., 2016 ).

Table 1
Contact geometry (Å, °) for I

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

X—Y⋯A	X—Y	Y⋯A	X⋯A	X—Y⋯A
C11—H11⋯F1ⁱ	0.95	2.46	3.4049 (19)	170.3
C1—F1⋯Cg1ⁱⁱ	1.3404 (18)	3.6822 (13)	4.8632 (17)	147.20 (9)
Symmetry codes: (i) −x + 2, y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (ii) 2 − x, $[{1\over 2}]$ + x, $[{1\over 2}]$ − z.

Table 2
Contact geometry (Å, °) for II

Cg1 and Cg2 are the centroids of the N1/C1–C4 and C6–C11 rings, respectively.

X—Y⋯A	X—Y	Y⋯A	X⋯A	X—Y⋯A
C10—H10⋯F3ⁱ	0.95	2.39	3.2214 (19)	145.9
C11—H11⋯Cg2ⁱ	0.95	2.90	3.668 (2)	139
C1—F1⋯Cg1ⁱⁱ	1.3395 (19)	3.1531 (14)	4.068 (2)	124.76 (10)
C5—F4⋯Cg1ⁱⁱⁱ	1.3401 (19)	3.1094 (13)	3.6241 (18)	101.55 (9)
C9—Br1⋯N1^iv	1.8952 (17)	3.2639 (16)	5.104 (3)	162.65 (7)
Symmetry codes: (i) −x + $[{3\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{3\over 2}]$ ; (ii) −x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{3\over 2}]$ ; (iii) −x + 1, −y + 1, −z + 2; (iv) $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z.

Table 3
Contact geometry (Å, °) for III

Cg1 and Cg2 are the centroids of the N1/C1–C5 and C6–C15 rings, respectively.

X—Y⋯A	X—Y	Y⋯A	X⋯A	X—Y⋯A
C7—H7⋯F3ⁱ	0.95	2.50	3.4366 (19)	169.6
C15—H15⋯N1ⁱⁱ	0.95	2.59	3.455 (2)	152.1
C1—F1⋯Cg2ⁱⁱⁱ	1.334 (2)	3.2922 (15)	3.5581 (19)	90.28 (10)
C5—F4⋯Cg1^iv	1.343 (2)	3.2790 (14)	4.2804 (18)	130.88 (11)
Symmetry codes: (i) x + 1, y, z; (ii) −x, y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (iii) 1 − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z; (iv) − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z.

Table 4
Contact geometry (Å, °) for IV

Cg1, Cg2, and Cg3 are the centroids of the N1/C1–C5, C6–C15, and C8–C13 rings, respectively.

X—Y⋯A	X—Y	Y⋯A	X⋯A	X—Y⋯A
C15—H15⋯F3ⁱⁱ	0.95	2.43	3.105 (5)	127.5
C9—H9⋯Cg3ⁱ	0.95	2.83	3.519 (5)	130
C11—Br1⋯Cg1ⁱⁱⁱ	1.901 (4)	3.6283 (19)	4.923 (5)	122.74 (13)
C11—Br1⋯Cg2^iv	1.901 (4)	3.735 (2)	5.037 (4)	123.34 (12)
C4—F3⋯Cg1^v	1.344 (6)	3.082 (3)	3.936 (5)	120.3 (3)
Symmetry codes: (i) −x + 1, y + $[{1\over 2}]$ , −z + 1; (ii) x + 1, y, z; (iii) −x + 1, y − $[{1\over 2}]$ , −z + 1; (iv) −x + 2, y − $[{1\over 2}]$ , −z + 1; (v) −x, y − $[{1\over 2}]$ , −z.

Table 5
Contact geometry (Å, °) for V

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

X—Y⋯A	X—Y	Y⋯A	X⋯A	X—Y⋯A
C11—H11⋯F3ⁱ	0.95	2.63	3.2361 (13)	121.8
C11—H11⋯F3ⁱⁱ	0.95	2.60	3.2711 (12)	127.8
C11—H11⋯O1ⁱ	0.95	2.61	3.3446 (13)	134.3
C5—F4⋯Cg1ⁱⁱⁱ	1.3382 (12)	3.4138 (9)	4.3778 (12)	128.77 (6)
Symmetry codes: (i) −x + 1, −y + 1, −z + 1; (ii) x, −y + 1, z − $[{1\over 2}]$ ; (iii) x, 1 − y, $[{1\over 2}]$ + z.

Hirshfeld surface analysis was used to further investigate the intermolecular interactions in the crystal structures. The Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ) was generated by CrystalExplorer17.5 (Turner et al., 2017 ), and was comprised of d_norm surface plots. The plots of the Hirshfeld surface are mapped over d_norm using standard surface resolution with a fixed colour scale of −0.1300 (red) to 1.2500 (blue). The characteristic bright-red spots near F1 and H11 in the Hirshfeld surface of I (Fig. 2a) confirm the previously mentioned C11—H11⋯F1 (symmetry code: −x + 2, y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ) inter-atomic contacts. As expected, the same bright-red spots are observed for the C10—H10⋯F3 (symmetry code: −x + $[{3\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{3\over 2}]$ ) in II (Fig. 2b), C7—H7⋯F3 (symmetry code: x + 1, y, z) in III (Fig. 2c), C15—H15⋯F3 (symmetry code: −x + 1, y + $[{1\over 2}]$ , −z + 1) in IV (Fig. 2d), and both C11—H11⋯F3ⁱ and C11—H11⋯F3ⁱⁱ [symmetry codes: (i) −x + 1, −y + 1, −z + 1; (ii) x, −y + 1, z − $[{1\over 2}]$ ] inter-atomic contacts in V (Fig. 2e). The contributions of the various intermolecular interactions in each of the title compounds are shown in Tables 6–10 . With the exception of IV, the packing is dominated by ⋯H/H⋯F interactions, accounting for as high as 36.9% of the packing forces in I. In IV, the largest contribution is made by C⋯H/H⋯C interactions (19.1%), followed closely by F⋯H/H⋯F (18.8%).

Table 6
Percentage contributions of inter-atomic contacts to the Hirshfeld surface for I

Contact	Percentage contribution
F⋯H/H⋯F	36.9
C⋯H/H⋯C	14.8
F⋯F	12.1
H⋯H	9.6
N⋯H/H⋯N	4.8
F⋯C/C⋯F	4.7
F⋯O/O⋯F	4.2
C⋯C	4.1
N⋯C/C⋯N	3.2
O⋯C/C⋯O	2.2
O⋯N/N⋯O	2.0
F⋯N/N⋯F	1.3
O⋯H/H⋯O	0.1

Table 7
Percentage contributions of inter-atomic contacts to the Hirshfeld surface for II

Contact	Percentage contribution
F⋯H/H⋯F	18.7
F⋯C/C⋯F	11.8
C⋯H/H⋯C	11.7
F⋯F	10.8
Br⋯F/F⋯Br	8.3
Br⋯H/H⋯Br	7.7
H⋯H	6.9
F⋯N/N⋯F	6.1
O⋯H/H⋯O	4.6
Br⋯N/N⋯Br	3.5
C⋯C	3.4
Br⋯C/C⋯Br	2.2
Br⋯O/O⋯Br	1.8
N⋯C/C⋯N	0.9
F⋯O/O⋯F	0.8
O⋯C/C⋯O	0.6
N⋯H/H⋯N	0.2

Table 8
Percentage contributions of inter-atomic contacts to the Hirshfeld surface for III

Contact	Percentage contribution
F⋯H/H⋯F	30.4
C⋯H/H⋯C	22.8
H⋯H	14.0
F⋯C/C⋯F	10.0
F⋯F	6.6
N⋯H/H⋯N	4.2
O⋯C/C⋯O	2.9
F⋯O/O⋯F	2.3
F⋯N/N⋯F	2.0
O⋯H/H⋯O	0.3
O⋯N/N⋯O	1.6
C⋯C	1.5
N⋯C/C⋯N	1.4

Table 9
Percentage contributions of inter-atomic contacts to the Hirshfeld surface for IV

Contact	Percentage contribution
C⋯H/H⋯C	19.1
F⋯H/H⋯F	18.8
F⋯C/C⋯F	9.4
H⋯H	9.1
Br⋯H/H⋯Br	8.7
F⋯F	7.7
Br⋯C/C⋯Br	7.2
F⋯O/O⋯F	4.5
Br⋯F/F⋯Br	3.9
F⋯N/N⋯F	3.7
N⋯H/H⋯N	2.6
C⋯C	1.5
N⋯C/C⋯N	1.1
O⋯N/N⋯O	0.9
Br⋯N/N⋯Br	0.8
O⋯C/C⋯O	0.6
O⋯H/H⋯O	0.3

Table 10
Percentage contributions of inter-atomic contacts to the Hirshfeld surface for V

Contact	Percentage contribution
F⋯H/H⋯F	32.3
F⋯C/C⋯F	19.0
H⋯H	11.6
F⋯F	11.3
N⋯H/H⋯N	7.1
F⋯N/N⋯F	6.3
C⋯H/H⋯C	4.8
O⋯H/H⋯O	4.5
F⋯O/O⋯F	1.8
C⋯C	1.3

Figure 2
Hirshfeld surface of (a) I, (b) II, (c) III, (d) IV, and (e) V mapped with d_norm.

Owing to the presence of nitrogen, oxygen and bromine atoms in the various structures, several other contact types are confirmed by the Hirshfeld surface maps. In II, the C9—Br1⋯N1 (symmetry code: $[{1\over 2}]$ − x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z) halogen bond is clearly visible. The analogous halogen bond is not observed in IV. Only in III does a C—H⋯N interaction significantly contribute to the packing, with the C15—H15⋯N1 (symmetry code: −x, y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ] visible in the d_norm surface plot.

4. Database survey

A search of the November 2019 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 perfluoropyridines bearing a ether-linked substituents in the 4-position returned six results: 2,3,5,6-tetrafluoropyridin-4-ol (UDUXEY; Sen et al., 2009 ); benzophenone O-(2,3,5,6-tetrafluoro-4-pyridyl)oxime (HICBAW; Banks et al., 1995 ); methyl N,O-bis(2,3,5,6-tetrafluoropyridin-4-yl)threoninate (GOFCIP; Webster et al., 2014 ); 2,3,5,6-tetrafluoro-4-(4-nitrophenoxy)pyridine and 4,4′-[(1,1′-binaphthalene)-2,2′diylbis(oxy)]bis(tetrafluoropyridine) (FISJUP and FISJOJ; Brittain & Cobb, 2019 ). In the binaphthalene-derived compound (FISJOJ), analogous to V, the naphthalene ring systems are rotated by 38.91 (5)° from each other.

5. Synthesis and crystallization

2,3,5,6-Tetrafluoro-4-phenoxypyridine (I): To a stirred solution of potassium carbonate (1 M, 147.5 ml), phenol (5.58 g, 59.0 mmol), pentafluoropyridine (6.5 ml, 59 mmol), and DMF (150 ml) were added. The resulting solution was allowed to stir at room temperature for 24 h. Dichloromethane (75 ml) and saturated aqueous ammonium chloride (100 ml) were added and the biphasic solution stirred vigorously for an additional 24 h. The organic layer was separated, washed with water (5 × 200 ml), dried over MgSO₄, and solvent removed via rotary evaporation. The resulting pale-brown solid was dissolved in refluxing EtOH (75 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 (14.3 g, 99%). Colourless needles were obtained from a saturated EtOH solution by cooling to 298 K. ¹H NMR (400 MHz, CDCl₃): 6.92 (d, 2H, J = 8.0 Hz), 7.08 (d, 1H, J = 8.4 Hz), 7.24 (t, 2H, J = 8.0 Hz). ¹⁹F NMR (376 MHz, CDCl₃): −88.9, −154.4.

4-(4-Bromophenoxy)-2,3,5,6-tetrafluoropyridine (II): To a stirred solution of potassium carbonate (1 M, 22.8 ml), 4-bromophenol (1.58 g, 9.11 mmol), pentafluoropyridine (1.00 ml, 9.11 mmol), and DMF (25 ml) were added. The resulting solution was allowed to stir at room temperature for 24 h. Diethyl ether (50 ml) and saturated aqueous ammonium chloride (50 ml) were added and the biphasic solution stirred vigorously for an additional 24 h. The organic layer was separated, washed with water (5 × 100 ml), dried over MgSO₄, and solvent removed via rotary evaporation. The resulting pale brown solid was dissolved in refluxing EtOH (15 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 (2.12 g, 73%). Colourless rectangular prisms were obtained from a saturated EtOH solution by cooling to 298 K. ¹H NMR (400 MHz, CDCl₃): 7.50 (d, 2H, J = 7.5 Hz), 6.96 (d, 2H, J = 7.5 Hz). ¹⁹F NMR (376 MHz, CDCl₃): −87.9, −154.0.

2,3,5,6-Tetrafluoro-4-[(naphthalen-2-yl)oxy]pyridine (III): To a stirred solution of potassium carbonate (1 M, 90 ml), naphthalen-2-ol (4.98 g, 34.5 mmol), pentafluoropyridine (3.8 ml, 34.5 mmol), and DMF (100 ml) were added. The resulting solution was allowed to stir at room temperature for 24 h. Dichloromethane (50 ml) and saturated aqueous ammonium chloride (100 ml) were added and the biphasic solution stirred vigorously for an additional 24 h. The organic layer was separated, washed with water (5 × 200 ml), dried over MgSO₄, and solvent removed via rotary evaporation. The resulting pale brown solid was dissolved in refluxing EtOH (50 ml) and cooled to 298 K for 12 h. Vacuum filtration, washing with cold EtOH (20 ml) and vacuum drying afforded the target compound as a white, crystalline solid (5.90 g, 58%). Colourless rectangular prisms were obtained from a saturated EtOH solution by cooling to 298 K. ¹H NMR (500 MHz, CDCl₃): 7.90-7.86 (m, 2H), 7.76 (d, 1H, J = 8 Hz), 7.54-7.47 (m, 2H), 7.35–7.31 (m, 2H). ¹⁹F NMR (471 MHz, CDCl₃): −88.3, −154.0.

2,3,5,6-Tetrafluoro-4-[(6-bromonaphthalen-2-yl)oxy]pyridine (IV): To a stirred solution of potassium carbonate (1 M, 60 ml), 6-bromo-2-naphthol (5.00 g, 22.4 mmol), pentafluoropyridine (2.45 ml, 22.4 mmol), and DMF (60 ml) were added. The resulting solution was allowed to stir at room temperature for 24 h. Diethyl ether (50 ml) and saturated aqueous ammonium chloride (100 ml) were added and the biphasic solution stirred vigorously for an additional 2 h. The organic layer was separated, washed with water (5 × 200 ml), dried over MgSO₄, and solvent removed via rotary evaporation. The resulting off-white solid was dissolved in refluxing EtOH (40 ml) and cooled to 298 K for 12 h. Vacuum filtration, washing with cold EtOH (20 ml) and vacuum drying afforded the target compound as a white, crystalline solid (6.46 g, 78%). Colourless plates were obtained from a saturated EtOH solution by cooling to 298 K. ¹H NMR (500 MHz, CDCl₃): 8.00 (s, 1H), 7.81–7.75 (m, 1H), 7.63–7.55 (m, 2H), 7.35–7.27 (m, 2H). ¹⁹F NMR (471 MHz, CDCl₃): −87.9, −153.8.

2,2′-Bis[(2,3,5,6-tetrafluoropyridin-4-yl)oxy]-1,1′-biphenyl (V): To a stirred solution of potassium carbonate (1 M, 30 ml), 2,2′-biphenol (1.02 g, 5.37 mmol), pentafluoropyridine (1.2 ml, 11 mmol), and DMF (30 ml) were added. The resulting solution was allowed to stir at room temperature for 24 h. Diethyl ether (50 ml) and saturated aqueous ammonium chloride (100 ml) were added and the biphasic solution stirred vigorously for an additional 2 h. The organic layer was separated, washed with water (5 × 200 ml), dried over MgSO₄, and solvent removed via rotary evaporation. The resulting off-white solid was dissolved in refluxing EtOH (10 ml) and cooled to 298 K for 12 h. Vacuum filtration, washing with cold EtOH (20 ml) and vacuum drying afforded the target compound as a white solid (2.57 g, 97%). Colourless rectangular prisms were obtained from a saturated EtOH solution by cooling to 298 K. ¹H NMR (500 MHz, CDCl₃): 7.45–7.24 (m, 6H), 6.99 (t, 2H, J = 7.5 Hz). ¹⁹F NMR (471 MHz, CDCl₃): −88.9, −155.0.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 11. H atoms were positioned geometrically and refined using a riding model with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C). The absolute structures of I and III were intermediate in the present refinement. Compound IV was refined as an inversion twin.

Table 11
Experimental details

	I	II	III	IV	V
Crystal data
Chemical formula	C₁₁H₅F₄NO	C₁₁H₄BrF₄NO	C₁₅H₇F₄NO	C₁₅H₆BrF₄NO	C₂₂H₈F₈N₂O₂
M_r	243.16	322.06	293.22	372.12	484.30
Crystal system, space group	Orthorhombic, P2₁2₁2₁	Monoclinic, P2₁/n	Orthorhombic, P2₁2₁2₁	Monoclinic, P2₁	Orthorhombic, Pbcn
Temperature (K)	100	100	100	100	100
a, b, c (Å)	5.4199 (5), 10.3293 (9), 17.4076 (15)	13.3530 (5), 5.8584 (2), 14.8863 (6)	5.4703 (5), 9.2548 (9), 24.109 (2)	6.0135 (3), 7.4994 (4), 14.6318 (7)	18.8516 (6), 10.6512 (3), 9.2196 (3)
α, β, γ (°)	90, 90, 90	90, 113.585 (2), 90	90, 90, 90	90, 101.401 (2), 90	90, 90, 90
V (Å³)	974.54 (15)	1067.24 (7)	1220.6 (2)	646.84 (6)	1851.22 (10)
Z	4	4	4	2	4
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα	Mo Kα
μ (mm⁻¹)	0.16	3.89	0.14	3.23	0.17
Crystal size (mm)	0.25 × 0.11 × 0.09	0.15 × 0.10 × 0.09	0.54 × 0.36 × 0.29	0.30 × 0.14 × 0.04	0.33 × 0.27 × 0.26

Data collection
Diffractometer	Bruker SMART APEX CCD	Bruker SMART APEX CCD	Bruker SMART APEX CCD	Bruker SMART APEX CCD	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2017 )	Multi-scan (SADABS; Bruker, 2017)	Multi-scan (SADABS; Bruker, 2017)	Multi-scan (SADABS; Bruker, 2017)	Multi-scan (SADABS; Bruker, 2017)
T_min, T_max	0.93, 0.99	0.21, 0.72	0.83, 0.96	0.63, 0.89	0.87, 0.96
No. of measured, independent and observed [I > 2σ(I)] reflections	13236, 2603, 2520	19174, 3544, 3013	26820, 3296, 3149	12954, 2775, 2566	36854, 2830, 2554
R_int	0.021	0.040	0.025	0.040	0.028
(sin θ/λ)_max (Å⁻¹)	0.684	0.735	0.684	0.641	0.714

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.073, 1.05	0.031, 0.083, 1.06	0.031, 0.078, 1.07	0.031, 0.058, 1.14	0.036, 0.098, 1.06
No. of reflections	2603	3544	3296	2775	2830
No. of parameters	154	163	190	200	154
No. of restraints	0	0	0	1	0
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.15	0.84, −0.77	0.27, −0.15	0.70, −0.47	0.54, −0.24
Absolute structure	Flack x determined using 1019 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )	–	Flack x determined using 1255 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013)	Refined as an inversion twin	–
Absolute structure parameter	−0.20 (13)	–	−0.08 (14)	0.171 (12)	–
Computer programs: APEX3 and SAINT (Bruker, 2017), SHELXT (Sheldrick, 2015a ), SHELXL2016/6 (Sheldrick, 2015b ), Mercury (Macrae et al., 2008 ), Olex2 (Dolomanov et al., 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 1937619; 1937620; 1937621; 1937622; 1937623

Crystal structure: contains datablocks global, I, II, III, IV, V. DOI: https://doi.org/10.1107/S2056989019009344/hb7833sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019009344/hb7833Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989019009344/hb7833IIsup3.hkl

Structure factors: contains datablock III. DOI: https://doi.org/10.1107/S2056989019009344/hb7833IIIsup4.hkl

Structure factors: contains datablock IV. DOI: https://doi.org/10.1107/S2056989019009344/hb7833IVsup5.hkl

Structure factors: contains datablock V. DOI: https://doi.org/10.1107/S2056989019009344/hb7833Vsup6.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989019009344/hb7833Isup7.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989019009344/hb7833IIsup8.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989019009344/hb7833IIIsup9.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989019009344/hb7833IVsup10.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989019009344/hb7833Vsup11.cml

checkCIF report

Computing details top

For all 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: SHELXL2016/6 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2008). Software used to prepare material for publication: Olex2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010) for (I); publCIF (Westrip, 2010) for (II), (III), (IV), (V).

2,3,5,6-Tetrafluoro-4-phenoxypyridine (I) top

Crystal data top

C₁₁H₅F₄NO	D_x = 1.657 Mg m⁻³
M_r = 243.16	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 7895 reflections
a = 5.4199 (5) Å	θ = 2.3–29.5°
b = 10.3293 (9) Å	µ = 0.16 mm⁻¹
c = 17.4076 (15) Å	T = 100 K
V = 974.54 (15) Å³	Needle, colourless
Z = 4	0.25 × 0.11 × 0.09 mm
F(000) = 488

Data collection top

Bruker SMART APEX CCD diffractometer	2603 independent reflections
Radiation source: fine focus sealed tube	2520 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
Detector resolution: 8.3333 pixels mm^-1	θ_max = 29.1°, θ_min = 2.3°
ω Scans scans	h = −7→7
Absorption correction: multi-scan (SADABS; Bruker, 2017)	k = −14→14
T_min = 0.93, T_max = 0.99	l = −23→23
13236 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.028	w = 1/[σ²(F_o²) + (0.0371P)² + 0.2471P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.073	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.26 e Å⁻³
2603 reflections	Δρ_min = −0.15 e Å⁻³
154 parameters	Absolute structure: Flack x determined using 1019 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: −0.20 (13)
Primary atom site location: structure-invariant direct methods

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	1.0458 (2)	0.96948 (10)	0.27358 (6)	0.0304 (2)
F2	0.64334 (19)	0.87849 (9)	0.34737 (5)	0.0247 (2)
F3	0.4522 (2)	0.64159 (11)	0.12257 (6)	0.0339 (3)
F4	0.8628 (2)	0.74537 (11)	0.05818 (6)	0.0354 (3)
O1	0.3304 (2)	0.70337 (11)	0.27133 (6)	0.0220 (2)
N1	0.9535 (3)	0.85667 (14)	0.16598 (8)	0.0232 (3)
C1	0.8951 (3)	0.88735 (15)	0.23682 (9)	0.0214 (3)
C2	0.6915 (3)	0.84050 (14)	0.27546 (8)	0.0185 (3)
C3	0.5371 (3)	0.75320 (15)	0.23844 (9)	0.0182 (3)
C4	0.5954 (3)	0.72270 (15)	0.16263 (9)	0.0223 (3)
C5	0.8047 (3)	0.77713 (16)	0.13038 (9)	0.0240 (3)
C6	0.3557 (3)	0.65167 (14)	0.34628 (8)	0.0179 (3)
C7	0.1718 (3)	0.68151 (16)	0.39875 (9)	0.0212 (3)
H7	0.041504	0.738816	0.385477	0.025*
C8	0.1829 (3)	0.62530 (16)	0.47149 (9)	0.0227 (3)
H8	0.058655	0.644261	0.508309	0.027*
C9	0.3749 (3)	0.54150 (15)	0.49061 (9)	0.0214 (3)
H9	0.380741	0.503169	0.540181	0.026*
C10	0.5583 (3)	0.51402 (15)	0.43697 (9)	0.0210 (3)
H10	0.689859	0.4575	0.450189	0.025*
C11	0.5492 (3)	0.56943 (15)	0.36367 (9)	0.0194 (3)
H11	0.673132	0.550979	0.326676	0.023*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0275 (5)	0.0317 (5)	0.0320 (5)	−0.0123 (4)	−0.0031 (4)	0.0032 (4)
F2	0.0311 (5)	0.0254 (5)	0.0177 (4)	−0.0052 (4)	0.0026 (4)	−0.0038 (4)
F3	0.0478 (7)	0.0312 (5)	0.0228 (5)	−0.0132 (5)	−0.0036 (5)	−0.0051 (4)
F4	0.0497 (7)	0.0354 (6)	0.0210 (5)	0.0030 (5)	0.0127 (5)	−0.0014 (4)
O1	0.0185 (5)	0.0281 (6)	0.0193 (5)	−0.0037 (5)	−0.0018 (4)	0.0049 (4)
N1	0.0218 (6)	0.0234 (6)	0.0242 (6)	0.0035 (5)	0.0047 (5)	0.0067 (5)
C1	0.0201 (7)	0.0196 (7)	0.0245 (7)	−0.0010 (6)	−0.0025 (6)	0.0044 (6)
C2	0.0208 (7)	0.0184 (6)	0.0163 (6)	0.0007 (6)	−0.0006 (5)	0.0013 (5)
C3	0.0178 (6)	0.0177 (6)	0.0191 (6)	0.0008 (5)	−0.0012 (5)	0.0029 (5)
C4	0.0295 (8)	0.0184 (7)	0.0190 (7)	−0.0002 (6)	−0.0018 (6)	0.0005 (5)
C5	0.0316 (8)	0.0222 (7)	0.0182 (7)	0.0061 (7)	0.0058 (6)	0.0029 (6)
C6	0.0178 (6)	0.0185 (6)	0.0175 (6)	−0.0035 (5)	−0.0013 (5)	0.0009 (5)
C7	0.0160 (6)	0.0235 (7)	0.0240 (7)	0.0018 (6)	0.0000 (6)	−0.0006 (6)
C8	0.0199 (7)	0.0270 (7)	0.0214 (7)	−0.0002 (6)	0.0041 (6)	−0.0017 (6)
C9	0.0238 (7)	0.0216 (7)	0.0188 (7)	−0.0013 (6)	0.0010 (6)	0.0019 (5)
C10	0.0199 (7)	0.0186 (7)	0.0245 (7)	0.0013 (6)	0.0005 (6)	0.0022 (6)
C11	0.0183 (6)	0.0186 (7)	0.0212 (7)	−0.0002 (5)	0.0035 (6)	0.0000 (5)

Geometric parameters (Å, º) top

F1—C1	1.3404 (18)	C6—C11	1.383 (2)
F2—C2	1.3375 (17)	C6—C7	1.387 (2)
F3—C4	1.3382 (19)	C7—C8	1.394 (2)
F4—C5	1.3366 (18)	C7—H7	0.9500
O1—C3	1.3594 (18)	C8—C9	1.394 (2)
O1—C6	1.4164 (18)	C8—H8	0.9500
N1—C5	1.307 (2)	C9—C10	1.393 (2)
N1—C1	1.312 (2)	C9—H9	0.9500
C1—C2	1.380 (2)	C10—C11	1.399 (2)
C2—C3	1.389 (2)	C10—H10	0.9500
C3—C4	1.393 (2)	C11—H11	0.9500
C4—C5	1.385 (2)

C3—O1—C6	116.81 (12)	C11—C6—O1	120.43 (13)
C5—N1—C1	116.66 (14)	C7—C6—O1	116.98 (13)
N1—C1—F1	117.05 (14)	C6—C7—C8	118.34 (15)
N1—C1—C2	124.49 (15)	C6—C7—H7	120.8
F1—C1—C2	118.46 (14)	C8—C7—H7	120.8
F2—C2—C1	120.62 (14)	C9—C8—C7	120.50 (15)
F2—C2—C3	120.48 (14)	C9—C8—H8	119.8
C1—C2—C3	118.90 (14)	C7—C8—H8	119.8
O1—C3—C2	123.16 (13)	C10—C9—C8	119.95 (14)
O1—C3—C4	120.02 (14)	C10—C9—H9	120.0
C2—C3—C4	116.73 (14)	C8—C9—H9	120.0
F3—C4—C5	121.20 (15)	C9—C10—C11	120.18 (15)
F3—C4—C3	120.24 (15)	C9—C10—H10	119.9
C5—C4—C3	118.56 (15)	C11—C10—H10	119.9
N1—C5—F4	117.04 (15)	C6—C11—C10	118.52 (14)
N1—C5—C4	124.62 (15)	C6—C11—H11	120.7
F4—C5—C4	118.33 (16)	C10—C11—H11	120.7
C11—C6—C7	122.50 (14)

C5—N1—C1—F1	−179.60 (14)	C1—N1—C5—F4	180.00 (14)
C5—N1—C1—C2	0.7 (2)	C1—N1—C5—C4	−1.1 (2)
N1—C1—C2—F2	−178.92 (14)	F3—C4—C5—N1	−179.80 (15)
F1—C1—C2—F2	1.4 (2)	C3—C4—C5—N1	−0.4 (2)
N1—C1—C2—C3	1.1 (2)	F3—C4—C5—F4	−0.9 (2)
F1—C1—C2—C3	−178.63 (13)	C3—C4—C5—F4	178.56 (14)
C6—O1—C3—C2	−49.3 (2)	C3—O1—C6—C11	−46.61 (19)
C6—O1—C3—C4	134.31 (15)	C3—O1—C6—C7	136.93 (15)
F2—C2—C3—O1	1.0 (2)	C11—C6—C7—C8	−0.5 (2)
C1—C2—C3—O1	−178.94 (14)	O1—C6—C7—C8	175.90 (14)
F2—C2—C3—C4	177.58 (14)	C6—C7—C8—C9	0.1 (2)
C1—C2—C3—C4	−2.4 (2)	C7—C8—C9—C10	0.4 (2)
O1—C3—C4—F3	−1.8 (2)	C8—C9—C10—C11	−0.6 (2)
C2—C3—C4—F3	−178.48 (14)	C7—C6—C11—C10	0.3 (2)
O1—C3—C4—C5	178.73 (14)	O1—C6—C11—C10	−175.95 (14)
C2—C3—C4—C5	2.1 (2)	C9—C10—C11—C6	0.2 (2)

4-(4-Bromophenoxy)-2,3,5,6-tetrafluoropyridine (II) top

Crystal data top

C₁₁H₄BrF₄NO	F(000) = 624
M_r = 322.06	D_x = 2.004 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.3530 (5) Å	Cell parameters from 7652 reflections
b = 5.8584 (2) Å	θ = 2.6–31.9°
c = 14.8863 (6) Å	µ = 3.89 mm⁻¹
β = 113.585 (2)°	T = 100 K
V = 1067.24 (7) Å³	Rectangular prism, colourless
Z = 4	0.15 × 0.10 × 0.09 mm

Data collection top

Bruker SMART APEX CCD diffractometer	3544 independent reflections
Radiation source: fine focus sealed tube	3013 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
Detector resolution: 8.3333 pixels mm^-1	θ_max = 31.5°, θ_min = 1.7°
ω Scans scans	h = −19→19
Absorption correction: multi-scan (SADABS; Bruker, 2017)	k = −8→8
T_min = 0.21, T_max = 0.72	l = −21→21
19174 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)] = 0.031	H-atom parameters constrained
wR(F²) = 0.083	w = 1/[σ²(F_o²) + (0.050P)²] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.002
3544 reflections	Δρ_max = 0.84 e Å⁻³
163 parameters	Δρ_min = −0.77 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
Br1	0.69708 (2)	0.16236 (3)	0.49318 (2)	0.01909 (7)
F1	0.26006 (9)	0.89335 (18)	0.84433 (9)	0.0217 (2)
F2	0.38676 (8)	1.02091 (16)	0.74927 (8)	0.0180 (2)
F3	0.57954 (9)	0.32539 (15)	0.85557 (9)	0.0198 (2)
F4	0.44206 (9)	0.22697 (18)	0.94178 (8)	0.0204 (2)
O1	0.55019 (9)	0.75025 (19)	0.75137 (9)	0.0171 (3)
N1	0.35097 (12)	0.5592 (2)	0.89200 (11)	0.0165 (3)
C1	0.33969 (13)	0.7540 (3)	0.84459 (13)	0.0158 (3)
C2	0.40295 (14)	0.8195 (2)	0.79609 (13)	0.0138 (3)
C3	0.48559 (14)	0.6752 (3)	0.79564 (13)	0.0139 (3)
C4	0.49951 (13)	0.4716 (3)	0.84799 (12)	0.0146 (3)
C5	0.42904 (14)	0.4238 (3)	0.89247 (12)	0.0151 (3)
C6	0.57942 (13)	0.6035 (3)	0.69117 (12)	0.0140 (3)
C7	0.52283 (14)	0.4050 (3)	0.65069 (13)	0.0161 (3)
H7	0.460999	0.360861	0.662945	0.019*
C8	0.55832 (14)	0.2716 (3)	0.59177 (13)	0.0167 (3)
H8	0.522146	0.13251	0.564996	0.02*
C9	0.64660 (14)	0.3426 (3)	0.57230 (13)	0.0147 (3)
C10	0.70034 (14)	0.5462 (3)	0.61029 (13)	0.0162 (3)
H10	0.759498	0.595176	0.594964	0.019*
C11	0.66669 (14)	0.6774 (3)	0.67088 (13)	0.0153 (3)
H11	0.703098	0.816021	0.698056	0.018*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02336 (11)	0.01936 (10)	0.01944 (11)	0.00095 (6)	0.01371 (8)	−0.00288 (6)
F1	0.0176 (5)	0.0205 (5)	0.0311 (7)	0.0047 (4)	0.0139 (5)	−0.0027 (4)
F2	0.0211 (5)	0.0126 (4)	0.0200 (5)	0.0021 (4)	0.0079 (4)	0.0014 (4)
F3	0.0176 (5)	0.0176 (5)	0.0239 (6)	0.0066 (4)	0.0081 (4)	0.0008 (4)
F4	0.0280 (6)	0.0157 (5)	0.0170 (5)	−0.0011 (4)	0.0082 (4)	0.0035 (4)
O1	0.0209 (6)	0.0151 (6)	0.0210 (7)	−0.0036 (5)	0.0145 (5)	−0.0047 (5)
N1	0.0169 (7)	0.0177 (6)	0.0166 (7)	−0.0019 (5)	0.0086 (6)	−0.0027 (5)
C1	0.0138 (7)	0.0155 (7)	0.0182 (9)	0.0004 (6)	0.0065 (6)	−0.0041 (6)
C2	0.0158 (7)	0.0110 (7)	0.0134 (8)	−0.0011 (5)	0.0047 (6)	−0.0020 (5)
C3	0.0136 (7)	0.0155 (7)	0.0137 (8)	−0.0031 (5)	0.0064 (6)	−0.0037 (5)
C4	0.0132 (7)	0.0149 (7)	0.0143 (8)	0.0018 (6)	0.0040 (6)	−0.0020 (5)
C5	0.0196 (8)	0.0136 (7)	0.0107 (8)	−0.0006 (6)	0.0047 (6)	0.0006 (5)
C6	0.0147 (7)	0.0142 (7)	0.0142 (8)	0.0006 (6)	0.0068 (6)	−0.0016 (6)
C7	0.0151 (7)	0.0176 (7)	0.0181 (8)	−0.0044 (6)	0.0094 (6)	−0.0042 (6)
C8	0.0189 (8)	0.0156 (7)	0.0172 (9)	−0.0040 (6)	0.0091 (7)	−0.0045 (6)
C9	0.0153 (7)	0.0167 (7)	0.0132 (8)	0.0016 (6)	0.0068 (6)	−0.0003 (5)
C10	0.0143 (7)	0.0186 (7)	0.0174 (8)	−0.0022 (6)	0.0080 (6)	−0.0009 (6)
C11	0.0151 (7)	0.0166 (7)	0.0155 (8)	−0.0041 (6)	0.0076 (7)	−0.0014 (6)

Geometric parameters (Å, º) top

Br1—C9	1.8952 (17)	C4—C5	1.379 (2)
F1—C1	1.3395 (19)	C6—C11	1.385 (2)
F2—C2	1.3430 (18)	C6—C7	1.386 (2)
F3—C4	1.3386 (18)	C7—C8	1.392 (2)
F4—C5	1.3401 (19)	C7—H7	0.95
O1—C3	1.352 (2)	C8—C9	1.385 (2)
O1—C6	1.4050 (19)	C8—H8	0.95
N1—C5	1.308 (2)	C9—C10	1.390 (2)
N1—C1	1.318 (2)	C10—C11	1.389 (2)
C1—C2	1.368 (2)	C10—H10	0.95
C2—C3	1.392 (2)	C11—H11	0.95
C3—C4	1.396 (2)

C3—O1—C6	120.41 (13)	C11—C6—O1	114.89 (14)
C5—N1—C1	116.63 (15)	C7—C6—O1	123.25 (15)
N1—C1—F1	116.72 (15)	C6—C7—C8	118.76 (16)
N1—C1—C2	124.29 (15)	C6—C7—H7	120.6
F1—C1—C2	118.99 (16)	C8—C7—H7	120.6
F2—C2—C1	121.02 (15)	C9—C8—C7	119.74 (16)
F2—C2—C3	119.63 (15)	C9—C8—H8	120.1
C1—C2—C3	119.34 (15)	C7—C8—H8	120.1
O1—C3—C2	117.79 (14)	C8—C9—C10	121.07 (16)
O1—C3—C4	125.59 (15)	C8—C9—Br1	120.46 (12)
C2—C3—C4	116.43 (15)	C10—C9—Br1	118.47 (13)
F3—C4—C5	120.31 (15)	C11—C10—C9	119.35 (16)
F3—C4—C3	121.15 (15)	C11—C10—H10	120.3
C5—C4—C3	118.54 (15)	C9—C10—H10	120.3
N1—C5—F4	116.96 (15)	C6—C11—C10	119.20 (15)
N1—C5—C4	124.73 (16)	C6—C11—H11	120.4
F4—C5—C4	118.29 (15)	C10—C11—H11	120.4
C11—C6—C7	121.80 (16)

C5—N1—C1—F1	−179.75 (15)	C1—N1—C5—C4	0.5 (3)
C5—N1—C1—C2	0.7 (3)	F3—C4—C5—N1	177.56 (15)
N1—C1—C2—F2	−179.99 (15)	C3—C4—C5—N1	−2.2 (3)
F1—C1—C2—F2	0.5 (2)	F3—C4—C5—F4	−0.9 (2)
N1—C1—C2—C3	−0.2 (3)	C3—C4—C5—F4	179.31 (14)
F1—C1—C2—C3	−179.71 (15)	C3—O1—C6—C11	−163.96 (15)
C6—O1—C3—C2	−137.39 (15)	C3—O1—C6—C7	19.0 (2)
C6—O1—C3—C4	47.9 (2)	C11—C6—C7—C8	3.0 (3)
F2—C2—C3—O1	3.2 (2)	O1—C6—C7—C8	179.83 (16)
C1—C2—C3—O1	−176.63 (15)	C6—C7—C8—C9	−2.0 (3)
F2—C2—C3—C4	178.33 (14)	C7—C8—C9—C10	−0.4 (3)
C1—C2—C3—C4	−1.5 (2)	C7—C8—C9—Br1	179.46 (13)
O1—C3—C4—F3	−2.5 (3)	C8—C9—C10—C11	1.7 (3)
C2—C3—C4—F3	−177.21 (15)	Br1—C9—C10—C11	−178.07 (13)
O1—C3—C4—C5	177.29 (16)	C7—C6—C11—C10	−1.7 (3)
C2—C3—C4—C5	2.5 (2)	O1—C6—C11—C10	−178.70 (15)
C1—N1—C5—F4	179.03 (14)	C9—C10—C11—C6	−0.8 (3)

2,3,5,6-Tetrafluoro-4-[(naphthalen-2-yl)oxy]pyridine (III) top

Crystal data top

C₁₅H₇F₄NO	D_x = 1.596 Mg m⁻³
M_r = 293.22	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 9963 reflections
a = 5.4703 (5) Å	θ = 2.4–29.2°
b = 9.2548 (9) Å	µ = 0.14 mm⁻¹
c = 24.109 (2) Å	T = 100 K
V = 1220.6 (2) Å³	Rectangular prism, colourless
Z = 4	0.54 × 0.36 × 0.29 mm
F(000) = 592

Data collection top

Bruker SMART APEX CCD diffractometer	3296 independent reflections
Radiation source: fine focus sealed tube	3149 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
Detector resolution: 8.3333 pixels mm^-1	θ_max = 29.1°, θ_min = 2.4°
ω Scans scans	h = −7→7
Absorption correction: multi-scan (SADABS; Bruker, 2017)	k = −12→12
T_min = 0.83, T_max = 0.96	l = −32→33
26820 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.031	w = 1/[σ²(F_o²) + (0.0385P)² + 0.2387P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.078	(Δ/σ)_max < 0.001
S = 1.07	Δρ_max = 0.27 e Å⁻³
3296 reflections	Δρ_min = −0.15 e Å⁻³
190 parameters	Absolute structure: Flack x determined using 1255 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: −0.08 (14)
Primary atom site location: structure-invariant direct methods

Special details top

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

	x	y	z	U_iso*/U_eq
F1	0.1901 (3)	0.27940 (14)	0.13034 (5)	0.0479 (3)
F2	0.5809 (2)	0.39295 (12)	0.18393 (4)	0.0389 (3)
F3	0.2850 (2)	0.16943 (11)	0.34729 (4)	0.0312 (2)
F4	−0.0860 (2)	0.06445 (13)	0.28603 (6)	0.0493 (3)
O1	0.6420 (2)	0.34634 (14)	0.29382 (5)	0.0277 (3)
N1	0.0540 (3)	0.17233 (17)	0.20838 (7)	0.0356 (3)
C1	0.2194 (4)	0.25229 (19)	0.18427 (7)	0.0320 (4)
C2	0.4193 (3)	0.31157 (17)	0.21119 (6)	0.0265 (3)
C3	0.4454 (3)	0.28847 (16)	0.26793 (6)	0.0222 (3)
C4	0.2711 (3)	0.20160 (17)	0.29324 (6)	0.0246 (3)
C5	0.0823 (3)	0.14819 (18)	0.26127 (8)	0.0320 (4)
C6	0.6094 (3)	0.40005 (17)	0.34853 (6)	0.0228 (3)
C7	0.7792 (3)	0.36372 (17)	0.38711 (6)	0.0241 (3)
H7	0.908206	0.299232	0.377994	0.029*
C8	0.7619 (3)	0.42322 (17)	0.44129 (6)	0.0226 (3)
C9	0.9344 (3)	0.3885 (2)	0.48337 (7)	0.0285 (3)
H9	1.064542	0.323683	0.475557	0.034*
C10	0.9133 (3)	0.4482 (2)	0.53513 (7)	0.0320 (4)
H10	1.030211	0.425143	0.562892	0.038*
C11	0.7196 (4)	0.5437 (2)	0.54765 (7)	0.0326 (4)
H11	0.707125	0.584129	0.583766	0.039*
C12	0.5492 (4)	0.57864 (19)	0.50802 (7)	0.0294 (3)
H12	0.419415	0.642863	0.516865	0.035*
C13	0.5662 (3)	0.51895 (17)	0.45372 (6)	0.0233 (3)
C14	0.3926 (3)	0.55230 (17)	0.41174 (7)	0.0250 (3)
H14	0.260636	0.615515	0.419906	0.03*
C15	0.4135 (3)	0.49422 (17)	0.35952 (6)	0.0242 (3)
H15	0.298037	0.51716	0.331426	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0678 (8)	0.0484 (7)	0.0276 (5)	0.0196 (6)	−0.0202 (6)	−0.0095 (5)
F2	0.0582 (7)	0.0356 (5)	0.0229 (4)	−0.0087 (5)	0.0076 (5)	0.0027 (4)
F3	0.0379 (6)	0.0285 (5)	0.0271 (5)	−0.0018 (4)	0.0053 (4)	0.0050 (4)
F4	0.0365 (6)	0.0367 (6)	0.0748 (9)	−0.0157 (5)	0.0055 (6)	−0.0067 (6)
O1	0.0237 (5)	0.0394 (6)	0.0199 (5)	−0.0060 (5)	0.0015 (4)	−0.0052 (5)
N1	0.0318 (7)	0.0300 (7)	0.0449 (8)	0.0049 (6)	−0.0128 (7)	−0.0146 (6)
C1	0.0416 (10)	0.0272 (8)	0.0271 (8)	0.0118 (7)	−0.0106 (7)	−0.0084 (6)
C2	0.0358 (8)	0.0221 (7)	0.0216 (7)	0.0024 (7)	−0.0004 (6)	−0.0010 (5)
C3	0.0234 (7)	0.0210 (6)	0.0221 (7)	0.0008 (6)	−0.0015 (6)	−0.0011 (5)
C4	0.0267 (7)	0.0212 (6)	0.0260 (7)	0.0015 (6)	0.0005 (6)	0.0001 (6)
C5	0.0261 (8)	0.0224 (7)	0.0474 (10)	−0.0016 (6)	−0.0013 (7)	−0.0064 (7)
C6	0.0228 (7)	0.0273 (7)	0.0182 (6)	−0.0047 (6)	0.0010 (5)	−0.0003 (6)
C7	0.0192 (6)	0.0293 (7)	0.0237 (6)	−0.0001 (6)	0.0012 (5)	−0.0001 (6)
C8	0.0200 (7)	0.0264 (7)	0.0215 (6)	−0.0026 (6)	−0.0010 (6)	0.0033 (5)
C9	0.0230 (7)	0.0378 (9)	0.0248 (7)	0.0001 (7)	−0.0019 (6)	0.0061 (6)
C10	0.0306 (8)	0.0429 (10)	0.0227 (7)	−0.0051 (8)	−0.0055 (7)	0.0062 (7)
C11	0.0396 (9)	0.0379 (9)	0.0204 (7)	−0.0058 (8)	−0.0011 (7)	−0.0016 (6)
C12	0.0333 (8)	0.0298 (8)	0.0251 (7)	−0.0003 (7)	0.0009 (7)	−0.0028 (6)
C13	0.0246 (7)	0.0231 (7)	0.0222 (7)	−0.0034 (6)	−0.0001 (6)	0.0015 (5)
C14	0.0250 (7)	0.0234 (7)	0.0264 (7)	0.0018 (6)	−0.0010 (6)	0.0003 (6)
C15	0.0237 (7)	0.0259 (7)	0.0231 (7)	−0.0016 (6)	−0.0041 (6)	0.0025 (5)

Geometric parameters (Å, º) top

F1—C1	1.334 (2)	C7—H7	0.95
F2—C2	1.334 (2)	C8—C13	1.421 (2)
F3—C4	1.3389 (18)	C8—C9	1.422 (2)
F4—C5	1.343 (2)	C9—C10	1.369 (2)
O1—C3	1.3538 (19)	C9—H9	0.95
O1—C6	1.4209 (18)	C10—C11	1.413 (3)
N1—C5	1.304 (3)	C10—H10	0.95
N1—C1	1.305 (3)	C11—C12	1.374 (2)
C1—C2	1.385 (3)	C11—H11	0.95
C2—C3	1.392 (2)	C12—C13	1.424 (2)
C3—C4	1.389 (2)	C12—H12	0.95
C4—C5	1.380 (2)	C13—C14	1.421 (2)
C6—C7	1.357 (2)	C14—C15	1.374 (2)
C6—C15	1.407 (2)	C14—H14	0.95
C7—C8	1.421 (2)	C15—H15	0.95

C3—O1—C6	117.82 (12)	C7—C8—C9	121.61 (15)
C5—N1—C1	116.78 (16)	C13—C8—C9	119.34 (14)
N1—C1—F1	117.23 (17)	C10—C9—C8	120.20 (16)
N1—C1—C2	124.26 (16)	C10—C9—H9	119.9
F1—C1—C2	118.50 (18)	C8—C9—H9	119.9
F2—C2—C1	121.05 (15)	C9—C10—C11	120.68 (15)
F2—C2—C3	120.19 (16)	C9—C10—H10	119.7
C1—C2—C3	118.73 (16)	C11—C10—H10	119.7
O1—C3—C4	124.90 (14)	C12—C11—C10	120.51 (15)
O1—C3—C2	118.27 (15)	C12—C11—H11	119.7
C4—C3—C2	116.76 (15)	C10—C11—H11	119.7
F3—C4—C5	120.43 (15)	C11—C12—C13	120.26 (16)
F3—C4—C3	121.15 (14)	C11—C12—H12	119.9
C5—C4—C3	118.42 (15)	C13—C12—H12	119.9
N1—C5—F4	116.90 (17)	C14—C13—C8	119.22 (13)
N1—C5—C4	125.00 (17)	C14—C13—C12	121.77 (15)
F4—C5—C4	118.11 (17)	C8—C13—C12	119.00 (14)
C7—C6—C15	123.10 (14)	C15—C14—C13	120.81 (15)
C7—C6—O1	117.64 (14)	C15—C14—H14	119.6
C15—C6—O1	119.15 (13)	C13—C14—H14	119.6
C6—C7—C8	119.25 (14)	C14—C15—C6	118.57 (14)
C6—C7—H7	120.4	C14—C15—H15	120.7
C8—C7—H7	120.4	C6—C15—H15	120.7
C7—C8—C13	119.05 (13)

C5—N1—C1—F1	−179.02 (15)	C3—O1—C6—C7	134.10 (15)
C5—N1—C1—C2	0.1 (3)	C3—O1—C6—C15	−49.6 (2)
N1—C1—C2—F2	−179.70 (15)	C15—C6—C7—C8	−0.4 (2)
F1—C1—C2—F2	−0.6 (2)	O1—C6—C7—C8	175.80 (13)
N1—C1—C2—C3	−1.6 (3)	C6—C7—C8—C13	0.3 (2)
F1—C1—C2—C3	177.43 (14)	C6—C7—C8—C9	179.80 (15)
C6—O1—C3—C4	−39.6 (2)	C7—C8—C9—C10	179.68 (15)
C6—O1—C3—C2	143.33 (15)	C13—C8—C9—C10	−0.8 (2)
F2—C2—C3—O1	−2.2 (2)	C8—C9—C10—C11	0.6 (3)
C1—C2—C3—O1	179.72 (14)	C9—C10—C11—C12	−0.2 (3)
F2—C2—C3—C4	−179.48 (15)	C10—C11—C12—C13	−0.1 (3)
C1—C2—C3—C4	2.4 (2)	C7—C8—C13—C14	0.2 (2)
O1—C3—C4—F3	0.8 (2)	C9—C8—C13—C14	−179.35 (15)
C2—C3—C4—F3	177.89 (14)	C7—C8—C13—C12	−179.93 (15)
O1—C3—C4—C5	−178.91 (15)	C9—C8—C13—C12	0.5 (2)
C2—C3—C4—C5	−1.8 (2)	C11—C12—C13—C14	179.78 (16)
C1—N1—C5—F4	−179.19 (15)	C11—C12—C13—C8	−0.1 (2)
C1—N1—C5—C4	0.6 (3)	C8—C13—C14—C15	−0.6 (2)
F3—C4—C5—N1	−179.41 (16)	C12—C13—C14—C15	179.57 (16)
C3—C4—C5—N1	0.3 (3)	C13—C14—C15—C6	0.5 (2)
F3—C4—C5—F4	0.4 (2)	C7—C6—C15—C14	0.0 (2)
C3—C4—C5—F4	−179.88 (14)	O1—C6—C15—C14	−176.10 (14)

4-[(6-Bromonaphthalen-2-yl)oxy]-2,3,5,6-tetrafluoropyridine (IV) top

Crystal data top

C₁₅H₆BrF₄NO	F(000) = 364
M_r = 372.12	D_x = 1.911 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 6.0135 (3) Å	Cell parameters from 7392 reflections
b = 7.4994 (4) Å	θ = 3.1–27.4°
c = 14.6318 (7) Å	µ = 3.23 mm⁻¹
β = 101.401 (2)°	T = 100 K
V = 646.84 (6) Å³	Plate, colourless
Z = 2	0.30 × 0.14 × 0.04 mm

Data collection top

Bruker SMART APEX CCD diffractometer	2775 independent reflections
Radiation source: fine focus sealed tube	2566 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
Detector resolution: 8.3333 pixels mm^-1	θ_max = 27.1°, θ_min = 1.4°
ω Scans scans	h = −7→7
Absorption correction: multi-scan (SADABS; Bruker, 2017)	k = −9→9
T_min = 0.63, T_max = 0.89	l = −18→18
12954 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.031	w = 1/[σ²(F_o²) + (0.0174P)² + 0.147P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.058	(Δ/σ)_max = 0.001
S = 1.14	Δρ_max = 0.70 e Å⁻³
2775 reflections	Δρ_min = −0.46 e Å⁻³
200 parameters	Absolute structure: Refined as an inversion twin
1 restraint	Absolute structure parameter: 0.171 (12)
Primary atom site location: structure-invariant direct methods

Special details top

Refinement. Refined as a 2-component inversion twin.

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

	x	y	z	U_iso*/U_eq
Br1	1.11387 (6)	0.12723 (7)	0.65331 (3)	0.02027 (12)
F1	0.1437 (5)	0.8959 (4)	0.1693 (2)	0.0341 (8)
F2	0.4300 (3)	0.6186 (6)	0.20499 (14)	0.0245 (5)
F3	−0.1671 (5)	0.2537 (4)	0.04981 (19)	0.0325 (7)
F4	−0.4284 (4)	0.5505 (4)	0.0217 (2)	0.0430 (9)
O1	0.2637 (6)	0.2724 (4)	0.1423 (2)	0.0258 (8)
N1	−0.1424 (7)	0.7231 (7)	0.0963 (3)	0.0276 (11)
C1	0.0692 (8)	0.7344 (7)	0.1415 (3)	0.0242 (11)
C2	0.2157 (7)	0.5921 (6)	0.1599 (3)	0.0163 (12)
C3	0.1384 (8)	0.4227 (8)	0.1316 (3)	0.0187 (11)
C4	−0.0837 (8)	0.4126 (7)	0.0826 (3)	0.0227 (11)
C5	−0.2127 (9)	0.5642 (8)	0.0680 (4)	0.0277 (15)
C6	0.4160 (7)	0.2377 (6)	0.2262 (3)	0.0196 (10)
C7	0.3753 (7)	0.2843 (6)	0.3113 (3)	0.0186 (10)
H7	0.238946	0.343679	0.31662	0.022*
C8	0.5417 (7)	0.2423 (5)	0.3922 (3)	0.0148 (9)
C9	0.5119 (7)	0.2886 (6)	0.4829 (3)	0.0164 (9)
H9	0.375158	0.344584	0.490712	0.02*
C10	0.6783 (7)	0.2534 (6)	0.5599 (3)	0.0165 (9)
H10	0.657322	0.284878	0.620469	0.02*
C11	0.8803 (7)	0.1702 (5)	0.5475 (3)	0.0157 (11)
C12	0.9146 (6)	0.1211 (10)	0.4619 (2)	0.0165 (7)
H12	1.052023	0.064184	0.45575	0.02*
C13	0.7438 (6)	0.1551 (7)	0.3814 (3)	0.0150 (11)
C14	0.7724 (7)	0.1040 (8)	0.2918 (3)	0.0199 (11)
H14	0.90638	0.042866	0.284841	0.024*
C15	0.6108 (6)	0.1412 (10)	0.2154 (3)	0.0208 (9)
H15	0.628527	0.10273	0.155347	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.01749 (18)	0.0207 (2)	0.0211 (2)	0.0017 (3)	0.00019 (13)	0.0006 (3)
F1	0.047 (2)	0.021 (2)	0.036 (2)	0.0032 (15)	0.0129 (16)	0.0016 (15)
F2	0.0190 (10)	0.0269 (13)	0.0241 (12)	−0.0047 (19)	−0.0044 (9)	−0.003 (2)
F3	0.0324 (15)	0.0414 (19)	0.0232 (15)	−0.0209 (14)	0.0041 (12)	−0.0085 (13)
F4	0.0148 (13)	0.082 (3)	0.0296 (16)	0.0036 (13)	−0.0019 (12)	0.0034 (15)
O1	0.037 (2)	0.0213 (19)	0.0158 (17)	0.0043 (15)	−0.0035 (14)	−0.0020 (14)
N1	0.022 (3)	0.039 (3)	0.022 (3)	0.010 (2)	0.005 (2)	0.007 (2)
C1	0.036 (3)	0.020 (3)	0.019 (3)	0.004 (2)	0.011 (2)	0.001 (2)
C2	0.0181 (19)	0.018 (4)	0.0127 (19)	−0.0040 (19)	0.0015 (15)	0.0025 (18)
C3	0.022 (3)	0.023 (3)	0.011 (2)	−0.001 (2)	0.0038 (19)	0.004 (2)
C4	0.022 (2)	0.035 (3)	0.012 (2)	−0.010 (2)	0.0045 (18)	−0.002 (2)
C5	0.015 (3)	0.051 (4)	0.017 (3)	0.001 (2)	0.001 (2)	0.004 (2)
C6	0.026 (2)	0.014 (2)	0.017 (2)	−0.0022 (19)	−0.0007 (18)	−0.0005 (19)
C7	0.018 (2)	0.016 (2)	0.021 (2)	0.0012 (17)	0.0039 (18)	0.0000 (19)
C8	0.018 (2)	0.008 (2)	0.019 (2)	−0.0034 (16)	0.0052 (17)	−0.0006 (17)
C9	0.016 (2)	0.013 (2)	0.021 (2)	0.0029 (17)	0.0047 (18)	−0.0009 (18)
C10	0.019 (2)	0.014 (2)	0.017 (2)	−0.0024 (18)	0.0045 (18)	−0.0025 (18)
C11	0.0161 (19)	0.009 (3)	0.021 (2)	−0.0012 (15)	0.0009 (16)	0.0038 (16)
C12	0.0174 (17)	0.0099 (18)	0.0233 (19)	0.000 (3)	0.0069 (14)	0.000 (3)
C13	0.0178 (18)	0.009 (3)	0.020 (2)	−0.0012 (17)	0.0077 (15)	0.0013 (19)
C14	0.0220 (19)	0.016 (3)	0.024 (2)	0.000 (2)	0.0118 (16)	−0.004 (2)
C15	0.028 (2)	0.020 (3)	0.0167 (19)	−0.003 (3)	0.0091 (15)	0.001 (3)

Geometric parameters (Å, º) top

Br1—C11	1.901 (4)	C7—C8	1.427 (6)
F1—C1	1.328 (6)	C7—H7	0.95
F2—C2	1.342 (4)	C8—C13	1.416 (6)
F3—C4	1.344 (6)	C8—C9	1.417 (6)
F4—C5	1.344 (6)	C9—C10	1.376 (6)
O1—C3	1.348 (6)	C9—H9	0.95
O1—C6	1.403 (5)	C10—C11	1.408 (6)
N1—C5	1.304 (7)	C10—H10	0.95
N1—C1	1.316 (6)	C11—C12	1.360 (6)
C1—C2	1.376 (6)	C12—C13	1.424 (5)
C2—C3	1.387 (7)	C12—H12	0.95
C3—C4	1.388 (6)	C13—C14	1.408 (6)
C4—C5	1.369 (7)	C14—C15	1.358 (6)
C6—C7	1.361 (6)	C14—H14	0.95
C6—C15	1.412 (7)	C15—H15	0.95

C3—O1—C6	120.7 (4)	C13—C8—C7	119.1 (4)
C5—N1—C1	116.0 (5)	C9—C8—C7	121.7 (4)
N1—C1—F1	116.6 (5)	C10—C9—C8	120.9 (4)
N1—C1—C2	124.5 (5)	C10—C9—H9	119.6
F1—C1—C2	118.9 (4)	C8—C9—H9	119.6
F2—C2—C1	119.8 (4)	C9—C10—C11	119.1 (4)
F2—C2—C3	121.0 (4)	C9—C10—H10	120.5
C1—C2—C3	119.2 (5)	C11—C10—H10	120.5
O1—C3—C2	125.8 (4)	C12—C11—C10	122.0 (4)
O1—C3—C4	118.2 (5)	C12—C11—Br1	118.8 (3)
C2—C3—C4	115.8 (5)	C10—C11—Br1	119.2 (3)
F3—C4—C5	121.4 (4)	C11—C12—C13	119.8 (4)
F3—C4—C3	119.1 (5)	C11—C12—H12	120.1
C5—C4—C3	119.5 (5)	C13—C12—H12	120.1
N1—C5—F4	116.7 (4)	C14—C13—C8	119.7 (4)
N1—C5—C4	124.8 (5)	C14—C13—C12	121.3 (4)
F4—C5—C4	118.4 (5)	C8—C13—C12	119.0 (4)
C7—C6—O1	123.3 (4)	C15—C14—C13	120.8 (4)
C7—C6—C15	122.5 (4)	C15—C14—H14	119.6
O1—C6—C15	114.2 (4)	C13—C14—H14	119.6
C6—C7—C8	118.7 (4)	C14—C15—C6	119.2 (4)
C6—C7—H7	120.7	C14—C15—H15	120.4
C8—C7—H7	120.7	C6—C15—H15	120.4
C13—C8—C9	119.2 (4)

C5—N1—C1—F1	179.0 (5)	C3—O1—C6—C15	−147.8 (5)
C5—N1—C1—C2	0.0 (8)	O1—C6—C7—C8	179.9 (4)
N1—C1—C2—F2	178.6 (4)	C15—C6—C7—C8	3.4 (7)
F1—C1—C2—F2	−0.3 (6)	C6—C7—C8—C13	0.5 (6)
N1—C1—C2—C3	−1.5 (7)	C6—C7—C8—C9	179.3 (4)
F1—C1—C2—C3	179.5 (4)	C13—C8—C9—C10	1.5 (6)
C6—O1—C3—C2	42.9 (7)	C7—C8—C9—C10	−177.3 (4)
C6—O1—C3—C4	−141.8 (4)	C8—C9—C10—C11	0.0 (6)
F2—C2—C3—O1	−2.3 (7)	C9—C10—C11—C12	−1.0 (7)
C1—C2—C3—O1	177.8 (4)	C9—C10—C11—Br1	178.3 (3)
F2—C2—C3—C4	−177.7 (4)	C10—C11—C12—C13	0.6 (8)
C1—C2—C3—C4	2.4 (7)	Br1—C11—C12—C13	−178.8 (4)
O1—C3—C4—F3	1.6 (7)	C9—C8—C13—C14	178.2 (5)
C2—C3—C4—F3	177.4 (4)	C7—C8—C13—C14	−3.0 (7)
O1—C3—C4—C5	−177.8 (4)	C9—C8—C13—C12	−1.9 (7)
C2—C3—C4—C5	−2.0 (7)	C7—C8—C13—C12	176.9 (4)
C1—N1—C5—F4	180.0 (4)	C11—C12—C13—C14	−179.2 (5)
C1—N1—C5—C4	0.5 (9)	C11—C12—C13—C8	0.9 (8)
F3—C4—C5—N1	−178.8 (5)	C8—C13—C14—C15	1.6 (8)
C3—C4—C5—N1	0.6 (9)	C12—C13—C14—C15	−178.3 (6)
F3—C4—C5—F4	1.7 (7)	C13—C14—C15—C6	2.2 (9)
C3—C4—C5—F4	−178.9 (4)	C7—C6—C15—C14	−4.9 (9)
C3—O1—C6—C7	35.4 (6)	O1—C6—C15—C14	178.4 (5)

2,2'-Bis[(2,3,5,6-tetrafluoropyridin-4-yl)oxy]-1,1'-biphenyl (V) top

Crystal data top

C₂₂H₈F₈N₂O₂	D_x = 1.738 Mg m⁻³
M_r = 484.30	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcn	Cell parameters from 9894 reflections
a = 18.8516 (6) Å	θ = 3.1–31.0°
b = 10.6512 (3) Å	µ = 0.17 mm⁻¹
c = 9.2196 (3) Å	T = 100 K
V = 1851.22 (10) Å³	Rectangular prism, colourless
Z = 4	0.33 × 0.27 × 0.26 mm
F(000) = 968

Data collection top

Bruker SMART APEX CCD diffractometer	2830 independent reflections
Radiation source: fine focus sealed tube	2554 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
Detector resolution: 8.3333 pixels mm^-1	θ_max = 30.5°, θ_min = 2.2°
ω Scans scans	h = −26→26
Absorption correction: multi-scan (SADABS; Bruker, 2017)	k = −15→15
T_min = 0.87, T_max = 0.96	l = −13→13
36854 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)] = 0.036	H-atom parameters constrained
wR(F²) = 0.098	w = 1/[σ²(F_o²) + (0.0477P)² + 1.0353P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2830 reflections	Δρ_max = 0.54 e Å⁻³
154 parameters	Δρ_min = −0.24 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	0.23289 (4)	0.82100 (7)	0.58850 (9)	0.02742 (18)
F2	0.36863 (4)	0.80572 (6)	0.50165 (8)	0.02166 (16)
F3	0.39175 (4)	0.45355 (6)	0.81381 (8)	0.02052 (15)
F4	0.25208 (4)	0.47778 (7)	0.87330 (8)	0.02652 (17)
O1	0.45506 (4)	0.60742 (7)	0.62192 (8)	0.01451 (15)
N1	0.24272 (5)	0.64972 (10)	0.73110 (11)	0.0206 (2)
C1	0.27334 (6)	0.72890 (11)	0.64163 (12)	0.0190 (2)
C2	0.34353 (5)	0.72303 (10)	0.59814 (11)	0.01551 (19)
C3	0.38644 (5)	0.62907 (9)	0.65624 (11)	0.01334 (18)
C4	0.35408 (5)	0.54608 (9)	0.75268 (11)	0.01526 (19)
C5	0.28294 (6)	0.56017 (11)	0.78372 (12)	0.0184 (2)
C6	0.49905 (5)	0.70787 (9)	0.57843 (11)	0.01314 (18)
C7	0.51479 (5)	0.80445 (9)	0.67541 (11)	0.01353 (19)
C8	0.56072 (6)	0.89900 (10)	0.62696 (11)	0.0168 (2)
H8	0.571595	0.967538	0.689043	0.02*
C9	0.59065 (6)	0.89380 (10)	0.48901 (12)	0.0184 (2)
H9	0.621893	0.958404	0.457927	0.022*
C10	0.57499 (6)	0.79449 (11)	0.39657 (12)	0.0176 (2)
H10	0.59608	0.790723	0.30309	0.021*
C11	0.52840 (5)	0.70047 (10)	0.44090 (11)	0.01560 (19)
H11	0.516981	0.632684	0.378125	0.019*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0200 (3)	0.0288 (4)	0.0334 (4)	0.0094 (3)	−0.0009 (3)	0.0074 (3)
F2	0.0203 (3)	0.0201 (3)	0.0246 (3)	−0.0002 (2)	0.0006 (3)	0.0094 (3)
F3	0.0197 (3)	0.0198 (3)	0.0220 (3)	0.0033 (2)	0.0021 (2)	0.0073 (3)
F4	0.0211 (3)	0.0304 (4)	0.0280 (4)	−0.0027 (3)	0.0089 (3)	0.0090 (3)
O1	0.0122 (3)	0.0132 (3)	0.0181 (3)	−0.0012 (2)	0.0020 (3)	0.0001 (3)
N1	0.0146 (4)	0.0256 (5)	0.0217 (4)	0.0017 (3)	0.0019 (3)	0.0007 (4)
C1	0.0160 (4)	0.0206 (5)	0.0203 (5)	0.0038 (4)	−0.0018 (4)	0.0006 (4)
C2	0.0156 (4)	0.0152 (4)	0.0157 (4)	−0.0001 (3)	−0.0008 (3)	0.0016 (3)
C3	0.0129 (4)	0.0141 (4)	0.0130 (4)	−0.0007 (3)	0.0000 (3)	−0.0016 (3)
C4	0.0151 (4)	0.0155 (4)	0.0152 (4)	0.0006 (3)	0.0003 (3)	0.0012 (4)
C5	0.0160 (4)	0.0217 (5)	0.0174 (5)	−0.0025 (4)	0.0030 (4)	0.0018 (4)
C6	0.0120 (4)	0.0126 (4)	0.0148 (4)	−0.0011 (3)	0.0001 (3)	0.0010 (3)
C7	0.0141 (4)	0.0135 (4)	0.0130 (4)	0.0008 (3)	−0.0003 (3)	0.0008 (3)
C8	0.0188 (5)	0.0145 (4)	0.0170 (5)	−0.0029 (4)	−0.0011 (4)	0.0002 (3)
C9	0.0185 (5)	0.0173 (5)	0.0196 (5)	−0.0037 (4)	0.0009 (4)	0.0030 (4)
C10	0.0163 (4)	0.0210 (5)	0.0153 (4)	−0.0015 (4)	0.0020 (3)	0.0018 (4)
C11	0.0153 (4)	0.0172 (4)	0.0143 (4)	−0.0008 (3)	0.0001 (3)	−0.0014 (3)

Geometric parameters (Å, º) top

F1—C1	1.3356 (13)	C6—C11	1.3856 (14)
F2—C2	1.3383 (12)	C6—C7	1.3949 (14)
F3—C4	1.3390 (12)	C7—C8	1.4012 (14)
F4—C5	1.3382 (12)	C7—C7ⁱ	1.4842 (19)
O1—C3	1.3517 (12)	C8—C9	1.3925 (15)
O1—C6	1.4118 (12)	C8—H8	0.95
N1—C5	1.3114 (14)	C9—C10	1.3900 (15)
N1—C1	1.3134 (15)	C9—H9	0.95
C1—C2	1.3840 (15)	C10—C11	1.3934 (14)
C2—C3	1.3938 (14)	C10—H10	0.95
C3—C4	1.3942 (14)	C11—H11	0.95
C4—C5	1.3795 (14)

C3—O1—C6	119.96 (8)	C11—C6—O1	116.82 (9)
C5—N1—C1	116.44 (10)	C7—C6—O1	120.12 (9)
N1—C1—F1	116.81 (10)	C6—C7—C8	117.20 (9)
N1—C1—C2	124.97 (10)	C6—C7—C7ⁱ	120.93 (7)
F1—C1—C2	118.22 (10)	C8—C7—C7ⁱ	121.85 (8)
F2—C2—C1	120.06 (9)	C9—C8—C7	120.86 (10)
F2—C2—C3	121.52 (9)	C9—C8—H8	119.6
C1—C2—C3	118.42 (10)	C7—C8—H8	119.6
O1—C3—C2	126.01 (9)	C10—C9—C8	120.28 (10)
O1—C3—C4	117.37 (9)	C10—C9—H9	119.9
C2—C3—C4	116.52 (9)	C8—C9—H9	119.9
F3—C4—C5	120.55 (9)	C9—C10—C11	120.06 (10)
F3—C4—C3	120.20 (9)	C9—C10—H10	120.0
C5—C4—C3	119.25 (10)	C11—C10—H10	120.0
N1—C5—F4	117.00 (9)	C6—C11—C10	118.63 (10)
N1—C5—C4	124.36 (10)	C6—C11—H11	120.7
F4—C5—C4	118.64 (10)	C10—C11—H11	120.7
C11—C6—C7	122.93 (9)

C5—N1—C1—F1	−179.46 (10)	F3—C4—C5—N1	178.43 (10)
C5—N1—C1—C2	1.11 (17)	C3—C4—C5—N1	−1.84 (17)
N1—C1—C2—F2	177.24 (10)	F3—C4—C5—F4	−1.58 (16)
F1—C1—C2—F2	−2.18 (16)	C3—C4—C5—F4	178.15 (9)
N1—C1—C2—C3	−2.24 (17)	C3—O1—C6—C11	−119.50 (10)
F1—C1—C2—C3	178.34 (10)	C3—O1—C6—C7	64.48 (12)
C6—O1—C3—C2	30.14 (14)	C11—C6—C7—C8	2.07 (15)
C6—O1—C3—C4	−153.56 (9)	O1—C6—C7—C8	177.84 (9)
F2—C2—C3—O1	−1.91 (16)	C11—C6—C7—C7ⁱ	−176.48 (10)
C1—C2—C3—O1	177.56 (10)	O1—C6—C7—C7ⁱ	−0.71 (15)
F2—C2—C3—C4	−178.24 (9)	C6—C7—C8—C9	−1.77 (15)
C1—C2—C3—C4	1.24 (15)	C7ⁱ—C7—C8—C9	176.77 (10)
O1—C3—C4—F3	3.69 (14)	C7—C8—C9—C10	0.33 (16)
C2—C3—C4—F3	−179.66 (9)	C8—C9—C10—C11	0.92 (17)
O1—C3—C4—C5	−176.05 (9)	C7—C6—C11—C10	−0.88 (16)
C2—C3—C4—C5	0.61 (15)	O1—C6—C11—C10	−176.78 (9)
C1—N1—C5—F4	−179.01 (10)	C9—C10—C11—C6	−0.66 (16)
C1—N1—C5—C4	0.98 (17)

Symmetry code: (i) −x+1, y, −z+3/2.

Contact geometry (Å ,°) for I top

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

X—Y···A	X—Y	Y···A	X···A	X—Y···A
C11—H11···F1ⁱ	0.95	2.46	3.4049 (19)	170.3
C1—F1···Cg1ⁱⁱ	1.3404 (18)	3.6822 (13)	4.8632 (17)	147.20 (9)

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

Contact geometry (Å, °) for II top

Cg1 and Cg2 are the centroids of the N1/C1–C4 and C6–C11 rings, respectively.

X—Y···A	X—Y	Y···A	X···A	X—Y···A
C10—H10···F3ⁱ	0.95	2.39	3.2214 (19)	145.9
C11—H11···Cg2ⁱ	0.95	2.90	3.668 (2)	139
C1—F1···Cg1ⁱⁱ	1.3395 (19)	3.1531 (14)	4.068 (2)	124.76 (10)
C5—F4···Cg1ⁱⁱⁱ	1.3401 (19)	3.1094 (13)	3.6241 (18)	101.55 (9)
C9—Br1···N1^iv	1.8952 (17)	3.2639 (16)	5.104 (3)	162.65 (7)

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

Contact geometry (Å, °) for III top

Cg1 and Cg2 are the centroids of the N1/C1–C5 and C6–C15 rings respectively.

X—Y···A	X—Y	Y···A	X···A	X—Y···A
C7—H7···F3ⁱ	0.95	2.50	3.4366 (19)	169.6
C15—H15···N1ⁱⁱ	0.95	2.59	3.455 (2)	152.1
C1—F1···Cg2ⁱⁱⁱ	1.334 (2)	3.2922 (15)	3.5581 (19)	90.28 (10)
C5—F4···Cg1^iv	1.343 (2)	3.2790 (14)	4.2804 (18)	130.88 (11)

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

Contact geometry (Å, °) for IV top

Cg1, Cg2, and Cg3 are the centroids of the N1/C1–C5, C6–C15, and C8–C13 rings, respectively.

X—Y···A	X—Y	Y···A	X···A	X—Y···A
C15—H15···F3ⁱⁱ	0.95	2.43	3.105 (5)	127.5
C9—H9···Cg3ⁱ	0.95	2.83	3.519 (5)	130
C11—Br1···Cg1ⁱⁱⁱ	1.901 (4)	3.6283 (19)	4.923 (5)	122.74 (13)
C11—Br1···Cg2^iv	1.901 (4)	3.735 (2)	5.037 (4)	123.34 (12)
C4—F3···Cg1^v	1.344 (6)	3.082 (3)	3.936 (5)	120.3 (3)

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

Contact geometry (Å, °) for V top

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

X—Y···A	X—Y	Y···A	X···A	X—Y···A
C11—H11···F3ⁱ	0.95	2.63	3.2361 (13)	121.8
C11—H11···F3ⁱⁱ	0.95	2.60	3.2711 (12)	127.8
C11—H11···O1ⁱ	0.95	2.61	3.3446 (13)	134.3
C5—F4···Cg1ⁱⁱⁱ	1.3382 (12)	3.4138 (9)	4.3778 (12)	128.77 (6)

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

Percentage contributions of inter-atomic contacts to the Hirshfeld surface for I top

Contact	Percentage contribution
F···H/H···F	36.9
C···H/H···C	14.8
F···F	12.1
H···H	9.6
N···H/H···N	4.8
F···C/C···F	4.7
F···O/O···F	4.2
C···C	4.1
N···C/C···N	3.2
O···C/C···O	2.2
O···N/N···O	2.0
F···N/N···F	1.3
O···H/H···O	0.1

Percentage contributions of inter-atomic contacts to the Hirshfeld surface for II top

Contact	Percentage contribution
F···H/H···F	18.7
F···C/C···F	11.8
C···H/H···C	11.7
F···F	10.8
Br···F/F···Br	8.3
Br···H/H···Br	7.7
H···H	6.9
F···N/N···F	6.1
O···H/H···O	4.6
Br···N/N···Br	3.5
C···C	3.4
Br···C/C···Br	2.2
Br···O/O···Br	1.8
N···C/C···N	0.9
F···O/O···F	0.8
O···C/C···O	0.6
N···H/H···N	0.2

Percentage contributions of inter-atomic contacts to the Hirshfeld surface for III top

Contact	Percentage contribution
F···H/H···F	30.4
C···H/H···C	22.8
H···H	14.0
F···C/C···F	10.0
F···F	6.6
N···H/H···N	4.2
O···C/C···O	2.9
F···O/O···F	2.3
F···N/N···F	2.0
O···H/H···O	0.3
O···N/N···O	1.6
C···C	1.5
N···C/C···N	1.4

Percentage contributions of inter-atomic contacts to the Hirshfeld surface for IV top

Contact	Percentage contribution
C···H/H···C	19.1
F···H/H···F	18.8
F···C/C···F	9.4
H···H	9.1
Br···H/H···Br	8.7
F···F	7.7
Br···C/C···Br	7.2
F···O/O···F	4.5
Br···F/F···Br	3.9
F···N/N···F	3.7
N···H/H···N	2.6
C···C	1.5
N···C/C···N	1.1
O···N/N···O	0.9
Br···N/N···Br	0.8
O···C/C···O	0.6
O···H/H···O	0.3

Percentage contributions of inter-atomic contacts to the Hirshfeld surface for V top

Contact	Percentage contribution
F···H/H···F	32.3
F···C/C···F	19.0
H···H	11.6
F···F	11.3
N···H/H···N	7.1
F···N/N···F	6.3
C···H/H···C	4.8
O···H/H···O	4.5
F···O/O···F	1.8
C···C	1.3

Funding information

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

References

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Volume 75| Part 8| August 2019| Pages 1102-1107

https://doi.org/10.1107/S2056989019009344

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structures and Hirshfeld surface analysis of a series of 4-O-aryl­perfluoro­pyridines

1. Chemical context

2. Structural commentary

3. Supra­molecular features and Hirshfeld surface analysis

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Funding information

References

research communications

Crystal structures and Hirshfeld surface analysis of a series of 4-O-arylperfluoropyridines

3. Supramolecular features and Hirshfeld surface analysis