4′-[2-(Trifluoro­meth­yl)phen­yl]-2,2′:6′,2′′-terpyridine

Ledwaba, P.; Munro, O.Q.; Stewart, K.

doi:10.1107/S1600536809002384

organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Pages o376-o377

doi:10.1107/S1600536809002384

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4′-[2-(Trifluoromethyl)phenyl]-2,2′:6′,2′′-terpyridine

Peter Ledwaba,^a Orde Q. Munro ^a and Kirsty Stewart ^a ^*

^aSchool of Chemical and Physical Sciences, University of KwaZulu–Natal, Scottsville 3209, South Africa
^*Correspondence e-mail: stewart@ukzn.ac.za

(Received 14 January 2009; accepted 19 January 2009; online 23 January 2009)

The title compound, C₂₂H₁₄F₃N₃, is a versatile tridentate N-donor ligand consisting of a terpyridyl (terpy) molecule substituted in the 4′-position by a phenyl group, itself substituted in an ortho-position by a bulky trifluoromethyl group. The phenyl ring is twisted as a result of steric interactions involving the bulky trifluoromethyl substituent. This is reflected in the dihedral angle between the mean plane through the C atoms of the phenyl ring and the terpyridyl unit being 69.2 (1)°. The crystal structure contains no short van der Waals contacts. However, the terpy units stack in a head-to-tail orientation perpendicular to the c axis. The structure is is loosely stabilized by π–π interactions between the terminal pyridine rings of adjacent molecules along the stack. The perpendicular distance between the mean planes through the terpy moieties of adjacent molecules is 3.4 (1) Å.

Related literature

For related structures, see: Bessel et al. (1992 ); Brandt et al. (1954 ); Dwyer & Mellor (1964 ); Field et al. (2002 ); Gillard (1983 ); Lindoy & Livingstone (1967 ); Morgan & Burstall (1932 , 1934 , 1938 ); Serpone et al. (1983 ); Storrier et al. (1997 ). For background, see Constable et al. (1990 , 1992 ); Hunter & Sanders (1990 ); Kröhnke (1976 ); Thummel & Jahng (1985 ).

Experimental

Crystal data

C₂₂H₁₄F₃N₃
M_r = 377.36
Triclinic, $[P \overline 1]$
a = 7.767 (5) Å
b = 10.923 (3) Å
c = 11.748 (3) Å
α = 75.64 (2)°
β = 74.03 (4)°
γ = 72.93 (4)°
V = 900.8 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 (2) K
0.60 × 0.30 × 0.30 mm

Data collection

Oxford Diffraction Xcalibur2 CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2003 $[Oxford Diffraction (2003). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.930, T_max = 0.969
3953 measured reflections
3155 independent reflections
2840 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.148
S = 1.06
3155 reflections
254 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2003 $[Oxford Diffraction (2003). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2003 $[Oxford Diffraction (2003). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809002384/hg2469sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809002384/hg2469Isup2.hkl

checkCIF report

Comment top

The tridentate coordinating ligand 2,2':6',2''-terpyridine (terpy) was first isolated by Morgan & Burstall (1932, 1934, 1938) as one of the numerous products from the reaction of pyridine with iron(III) chloride.

Since the 1930s, numerous groups have examined terpy, prompted by the use of related ligands 2,2'-bipyridine (bipy) and 1,10-phenanthroline (phen), in photochemical and photophysical processes (Brandt et al., 1954; Dwyer & Mellor, 1964; Gillard, 1983; Lindoy & Livingstone, 1967; Serpone et al., 1983).

Reported here is the crystal structure of the tridentate terpyridyl ligand substituted in the 4'-position by a phenyl group, itself substituted in an ortho-position by a bulky trifluoromethyl group. Ortho-substitution of the 4'-phenyl ring was chosen since steric interactions between the bulky group and the 3'(5')-proton on the central pyridine ring are expected to force the 4'-substituent to rotate around the interannular bond i.e. the ligand will become non-planar.

In the crystal structure of 4'-(2'''-trifluoromethylphenyl)-2, 2':6',2''-terpyridine, the three pyridyl rings of the terpyridyl moiety are essentially co-planar as is preferred for maximum conjugative interaction (Thummel & Jahng, 1985). This is reflected by torsion angles between the two outer rings and the central ring of -6.5 (2)° and 9.9 (2)° for N1—C1—C6—C7 and C9—C10—C11—N3 respectively.

The terminal pyridine rings adopt a trans–trans conformation about the interannular bonds C1—C6 and C10—C11. Several derivatized terpy ligands have been found to adopt this trans–trans geometry by X-ray crystal analysis (Constable et al., 1990) which is more energetically favourable when compared to other conformations as a result of the minimal nitrogen lone pair repulsions (Thummel & Jahng, 1985).

The interannular bond distances C1—C6 and C10—C11 are 1.493 (2) Å and 1.484 (2) Å respectively; these distances are comparable with the averaged values of 1.49 (1) Å and 1.49 (1) Å measured for the terpy (Bessel et al., 1992) and 4'-(Ph)-terpy (Constable et al., 1990) ligands respectively.

As previously postulated, the o-tolyl moiety is twisted about the interannular bond C8—C16, as reflected in a dihedral angle between the mean plane through the carbon atoms of the 4'-substituted and the terpyridyl moiety of 69.2 (1)°. This angle may be compared with those adopted by terpyridyl ligands containing similar substituents in the 4'-position of the terpy moiety in molecules such as the free 4'-phenyl-terpyridine (10.9°) (Constable et al., 1990), 6,6''-dibromo-4'-phenyl-terpyridine (35.1°) (Constable et al, 1992) and 4'-(4-anilino)-terpyridine (27.2°) (Storrier et al., 1997). The larger angle witnessed in the title compound is consistent with the bulky nature of the trifluoro group and the fact that it substitutes the ortho-position of the phenyl moiety. Clearly, substitution of a trifluoro group in the ortho-position of the 4'-phenyl group causes a larger rotation about the interannular bond because of steric interactions between the CF₃ group and a hydrogen atom of the central pyridine ring that is also ortho with respect to the interannular bond.

There are no short van der Waals contacts less than the sum of the van der Waals radii in this system. However it is worth noting, that the terpy units stack in a head to tail orientation perpendicular to the [c]-axis, presumably as a result of minimizing steric interactions between the bulky trifluoromethyl substituents on adjacent molecules. However it is clear that this arrangement is not entirely successful and that poor packing does result from the presence of these bulky substituents reflected in the large solvent accessible void of 31 Å³. This packing orientation allows for π–π interactions between the terminal pyridine rings of adjacent molecules along the stack. The perpendicular distance between the mean planes through the terpy moieties of adjacent molecules is 3.4 (1)Å which is short enough to support π–π interactions being well within the upper distance limit of 3.8 Å for π–π interactions between organic molecules (Hunter & Sanders, 1990).

The stucture of the title compound is shown in Fig. 1. Fig. 2 shows a view perpendicular to the mean plane through the atoms comprising the terpyridyl (terpy) moiety of two adjacent terpy units in the crystals of the 4'-(2'''-trifluoromethylphenyl)-2, 2':6', 2''-terpyridine ligand. Note that the successive molecules are related by a centre of inversion.

Related literature top

For related literature, see: Bessel et al. (1992); Brandt et al. (1954); Constable et al. (1990, 1992); Dwyer & Mellor (1964); Field et al. (2002); Gillard (1983); Hunter & Sanders (1990); Kröhnke (1976); Lindoy & Livingstone (1967); Morgan & Burstall (1932, 1934, 1938); Serpone et al. (1983); Storrier et al. (1997); Thummel & Jahng (1985). [From the Section Editors: It would be much more useful to readers if the "Related literature" section had some kind of simple sub-division, so that, instead of just "For related literature, see···" it said, for example, "For general background, see···. For related structures, see···." etc. Please revise this section as indicated.]

Experimental top

4'-(2'''-trifluoromethylphenyl)-2,2':6',2''-terpyridine was synthesized by the method of Kröhnke (Field et al., 2002; Kröhnke, 1976).

N-{1-(2'-pyridyl)-1-oxo-2-ethyl}pyridinium iodide (0.68 g, 2.2 mmol) and ammonium acetate (10 g, excess) were added to a suspension of 2-R-{3-(2-pyridyl)-3-oxopropenyl}benzene (2.0 mmol) in absolute ethanol (8 ml) and the mixture heated at reflux for 40 min. An off-white solid precipitated on cooling. This was collected by filtration, washed with 50% aqueous ethanol and dried in vacuo. Recrystallization from ethanol afforded colourless crystals of the desired ligands.

Yield: (0.41 g, 54%). m.p. (148 °C). Anal. (Calcd. For C₂₂H₁₄F₃N₃: C 70.0; H 3.7; N 11.1. Found: C 69.9; H 3.9; N 11.0%). MS(EI) m/z: 377, M⁺). ¹H NMR (CDCl₃): [δ 8.72 (m, 2H, H_6,6''); 8.70 (m, 2H, H_3,3''); 8.54 (s, 2H, H_3',5'); 7.84 (m, 2H, H_4,4''); 7.54 (m, 4H, C₆H₄); 7.35 (m, 2 H, H_5,5'')]. UV/vis (CH₃CN): λ_max/nm (ε/M^-1cm^-1): [303 (sh, 1.3 × 10⁴); 277 (2.9 × 10⁴); 239 (3.4 × 10⁴); 208 (3.6 × 10⁴)].

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis RED (Oxford Diffraction, 2003); data reduction: CrysAlis RED (Oxford Diffraction, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. Molecular structure of 4'-(2'''-trifluoromethylphenyl)-2,2':6',2''-terpyridine, showing 50% probability displacement ellipsoids and atomic numbering.
	Fig. 2. A view perpendicular to the mean plane through the atoms comprising the terpyridyl (terpy) moiety of two adjacent terpy units in the crystals of the 4'-(2'''-trifluoromethylphenyl)-2, 2':6', 2''-terpyridine ligand. Note that the successive molecules are related by a centre of inversion.

4'-[2-(Trifluoromethyl)phenyl]-2,2':6',2''-terpyridine top

Crystal data top

C₂₂H₁₄F₃N₃	Z = 2
M_r = 377.36	F(000) = 388
Triclinic, P1	D_x = 1.391 Mg m⁻³
Hall symbol: -P 1	Melting point: 421.15 K
a = 7.767 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.923 (3) Å	Cell parameters from 3155 reflections
c = 11.748 (3) Å	θ = 2.4–25°
α = 75.64 (2)°	µ = 0.11 mm⁻¹
β = 74.03 (4)°	T = 293 K
γ = 72.93 (4)°	Square planar, colourless
V = 900.8 (7) Å³	0.60 × 0.30 × 0.30 mm

Data collection top

Oxford Diffraction Xcalibur2 CCD diffractometer	3155 independent reflections
Radiation source: Enhance (Mo)X-Ray Source	2840 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 8.4190 pixels mm^-1	θ_max = 25.0°, θ_min = 2.4°
ω/2θ scans	h = −4→9
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2003)	k = −12→12
T_min = 0.930, T_max = 0.969	l = −13→13
3953 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.148	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0902P)² + 0.255P] where P = (F_o² + 2F_c²)/3
3155 reflections	(Δ/σ)_max < 0.001
254 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₂₂H₁₄F₃N₃	γ = 72.93 (4)°
M_r = 377.36	V = 900.8 (7) Å³
Triclinic, P1	Z = 2
a = 7.767 (5) Å	Mo Kα radiation
b = 10.923 (3) Å	µ = 0.11 mm⁻¹
c = 11.748 (3) Å	T = 293 K
α = 75.64 (2)°	0.60 × 0.30 × 0.30 mm
β = 74.03 (4)°

Data collection top

Oxford Diffraction Xcalibur2 CCD diffractometer	3155 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2003)	2840 reflections with I > 2σ(I)
T_min = 0.930, T_max = 0.969	R_int = 0.032
3953 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.148	H-atom parameters constrained
S = 1.06	Δρ_max = 0.43 e Å⁻³
3155 reflections	Δρ_min = −0.32 e Å⁻³
254 parameters

Special details top

Experimental. CrysAlis RED, Oxford Diffraction Ltd., Version 170. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
F1	0.5317 (2)	0.91636 (13)	0.35582 (14)	0.0845 (5)
F2	0.71339 (15)	0.74840 (14)	0.42847 (12)	0.0725 (4)
F3	0.4702 (2)	0.83636 (18)	0.54344 (13)	0.0926 (6)
N1	1.1281 (2)	0.32563 (14)	0.24320 (14)	0.0467 (4)
N2	1.02318 (17)	0.64584 (13)	0.06447 (11)	0.0340 (3)
N3	0.79020 (19)	0.97634 (14)	−0.03608 (13)	0.0426 (4)
C1	1.1511 (2)	0.42440 (15)	0.15132 (14)	0.0357 (4)
C2	1.3124 (2)	0.41901 (18)	0.06241 (16)	0.0429 (4)
H2	1.3249	0.4894	−0.0002	0.0564 (15)*
C3	1.4538 (2)	0.30759 (19)	0.06833 (18)	0.0511 (5)
H3	1.5638	0.3026	0.0106	0.0564 (15)*
C4	1.4302 (3)	0.20463 (19)	0.1601 (2)	0.0536 (5)
H4	1.5217	0.1275	0.1648	0.0564 (15)*
C5	1.2666 (3)	0.21853 (19)	0.2456 (2)	0.0549 (5)
H5	1.2518	0.1491	0.3088	0.0564 (15)*
C6	0.9941 (2)	0.54241 (15)	0.14861 (13)	0.0333 (3)
C7	0.8263 (2)	0.54237 (16)	0.23130 (14)	0.0363 (4)
H7	0.8088	0.4674	0.2867	0.0564 (15)*
C8	0.6857 (2)	0.65547 (16)	0.22996 (13)	0.0341 (4)
C9	0.7156 (2)	0.76331 (15)	0.14389 (14)	0.0345 (4)
H9	0.6248	0.8409	0.1413	0.0564 (15)*
C10	0.8849 (2)	0.75402 (15)	0.06062 (13)	0.0328 (4)
C11	0.9179 (2)	0.86326 (15)	−0.04004 (14)	0.0334 (4)
C12	1.0712 (2)	0.84656 (17)	−0.13472 (15)	0.0410 (4)
H12	1.1568	0.7666	−0.1354	0.0564 (15)*
C13	1.0949 (2)	0.94940 (19)	−0.22719 (16)	0.0476 (4)
H13	1.1972	0.9404	−0.2909	0.0564 (15)*
C14	0.9649 (3)	1.06607 (18)	−0.22414 (17)	0.0495 (4)
H14	0.9767	1.1375	−0.2856	0.0564 (15)*
C15	0.8167 (3)	1.07390 (18)	−0.12736 (17)	0.0492 (4)
H15	0.7290	1.1529	−0.1257	0.0564 (15)*
C16	0.5028 (2)	0.65338 (15)	0.31581 (13)	0.0341 (4)
C17	0.4308 (2)	0.72287 (15)	0.41048 (14)	0.0351 (4)
C18	0.2588 (2)	0.71521 (17)	0.48555 (15)	0.0414 (4)
H18	0.2120	0.7612	0.5488	0.0564 (15)*
C19	0.1581 (2)	0.64052 (19)	0.46690 (16)	0.0473 (4)
H19	0.0426	0.6373	0.5163	0.0564 (15)*
C20	0.2281 (3)	0.5707 (2)	0.37529 (17)	0.0526 (5)
H20	0.1606	0.5192	0.3631	0.0564 (15)*
C21	0.3993 (2)	0.57662 (19)	0.30069 (16)	0.0459 (4)
H21	0.4459	0.5282	0.2392	0.0564 (15)*
C22	0.5349 (2)	0.80526 (19)	0.43493 (16)	0.0481 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.1039 (11)	0.0570 (8)	0.1051 (11)	−0.0432 (8)	−0.0206 (9)	−0.0113 (7)
F2	0.0405 (6)	0.1046 (10)	0.0925 (10)	−0.0248 (6)	−0.0147 (6)	−0.0448 (8)
F3	0.0829 (10)	0.1468 (14)	0.0763 (9)	−0.0633 (10)	0.0233 (7)	−0.0738 (10)
N1	0.0386 (8)	0.0444 (8)	0.0533 (9)	−0.0056 (6)	−0.0115 (6)	−0.0057 (7)
N2	0.0272 (6)	0.0400 (7)	0.0361 (7)	−0.0077 (5)	−0.0057 (5)	−0.0112 (6)
N3	0.0359 (7)	0.0409 (8)	0.0466 (8)	−0.0062 (6)	−0.0045 (6)	−0.0089 (6)
C1	0.0325 (8)	0.0396 (9)	0.0391 (8)	−0.0072 (6)	−0.0108 (6)	−0.0128 (7)
C2	0.0349 (8)	0.0485 (10)	0.0443 (9)	−0.0048 (7)	−0.0064 (7)	−0.0154 (7)
C3	0.0331 (9)	0.0588 (11)	0.0607 (11)	−0.0009 (8)	−0.0070 (8)	−0.0257 (9)
C4	0.0388 (9)	0.0459 (10)	0.0775 (13)	0.0035 (8)	−0.0220 (9)	−0.0197 (9)
C5	0.0469 (10)	0.0452 (10)	0.0688 (13)	−0.0050 (8)	−0.0202 (9)	−0.0027 (9)
C6	0.0296 (8)	0.0401 (8)	0.0333 (8)	−0.0085 (6)	−0.0074 (6)	−0.0113 (6)
C7	0.0326 (8)	0.0414 (9)	0.0351 (8)	−0.0102 (6)	−0.0063 (6)	−0.0071 (6)
C8	0.0277 (7)	0.0436 (9)	0.0335 (8)	−0.0112 (6)	−0.0034 (6)	−0.0121 (6)
C9	0.0268 (7)	0.0377 (8)	0.0393 (8)	−0.0069 (6)	−0.0043 (6)	−0.0120 (6)
C10	0.0268 (7)	0.0396 (8)	0.0353 (8)	−0.0099 (6)	−0.0053 (6)	−0.0119 (6)
C11	0.0267 (7)	0.0396 (8)	0.0372 (8)	−0.0093 (6)	−0.0081 (6)	−0.0105 (6)
C12	0.0301 (8)	0.0476 (9)	0.0420 (9)	−0.0079 (7)	−0.0043 (6)	−0.0081 (7)
C13	0.0384 (9)	0.0601 (11)	0.0399 (9)	−0.0157 (8)	−0.0014 (7)	−0.0046 (8)
C14	0.0521 (10)	0.0501 (10)	0.0454 (10)	−0.0181 (8)	−0.0133 (8)	0.0029 (8)
C15	0.0485 (10)	0.0401 (9)	0.0533 (10)	−0.0060 (8)	−0.0103 (8)	−0.0053 (8)
C16	0.0275 (7)	0.0402 (8)	0.0340 (8)	−0.0107 (6)	−0.0053 (6)	−0.0043 (6)
C17	0.0270 (7)	0.0403 (8)	0.0362 (8)	−0.0086 (6)	−0.0045 (6)	−0.0058 (6)
C18	0.0302 (8)	0.0497 (9)	0.0382 (8)	−0.0086 (7)	−0.0001 (6)	−0.0070 (7)
C19	0.0303 (8)	0.0657 (11)	0.0426 (9)	−0.0209 (8)	−0.0033 (7)	0.0019 (8)
C20	0.0468 (10)	0.0716 (13)	0.0498 (10)	−0.0368 (9)	−0.0091 (8)	−0.0042 (9)
C21	0.0462 (9)	0.0571 (11)	0.0415 (9)	−0.0253 (8)	−0.0032 (7)	−0.0132 (8)
C22	0.0403 (9)	0.0588 (11)	0.0489 (10)	−0.0186 (8)	0.0036 (7)	−0.0235 (9)

Geometric parameters (Å, º) top

F1—C22	1.331 (2)	C9—C10	1.400 (2)
F2—C22	1.332 (2)	C9—H9	0.9300
F3—C22	1.325 (2)	C10—C11	1.484 (2)
N1—C5	1.337 (2)	C11—C12	1.390 (2)
N1—C1	1.338 (2)	C12—C13	1.372 (2)
N2—C6	1.333 (2)	C12—H12	0.9300
N2—C10	1.344 (2)	C13—C14	1.376 (3)
N3—C15	1.330 (2)	C13—H13	0.9300
N3—C11	1.340 (2)	C14—C15	1.377 (3)
C1—C2	1.389 (2)	C14—H14	0.9300
C1—C6	1.493 (2)	C15—H15	0.9300
C2—C3	1.381 (3)	C16—C21	1.388 (2)
C2—H2	0.9300	C16—C17	1.398 (2)
C3—C4	1.368 (3)	C17—C18	1.397 (2)
C3—H3	0.9300	C17—C22	1.493 (2)
C4—C5	1.381 (3)	C18—C19	1.372 (3)
C4—H4	0.9300	C18—H18	0.9300
C5—H5	0.9300	C19—C20	1.370 (3)
C6—C7	1.395 (2)	C19—H19	0.9300
C7—C8	1.388 (2)	C20—C21	1.387 (3)
C7—H7	0.9300	C20—H20	0.9300
C8—C9	1.380 (2)	C21—H21	0.9300
C8—C16	1.501 (2)

C5—N1—C1	117.21 (16)	C13—C12—C11	119.27 (16)
C6—N2—C10	118.17 (13)	C13—C12—H12	120.4
C15—N3—C11	116.89 (15)	C11—C12—H12	120.4
N1—C1—C2	122.33 (15)	C12—C13—C14	118.93 (16)
N1—C1—C6	116.64 (15)	C12—C13—H13	120.5
C2—C1—C6	121.03 (15)	C14—C13—H13	120.5
C3—C2—C1	119.02 (17)	C13—C14—C15	118.00 (16)
C3—C2—H2	120.5	C13—C14—H14	121.0
C1—C2—H2	120.5	C15—C14—H14	121.0
C4—C3—C2	119.23 (17)	N3—C15—C14	124.54 (17)
C4—C3—H3	120.4	N3—C15—H15	117.7
C2—C3—H3	120.4	C14—C15—H15	117.7
C3—C4—C5	118.07 (17)	C21—C16—C17	117.94 (14)
C3—C4—H4	121.0	C21—C16—C8	117.85 (14)
C5—C4—H4	121.0	C17—C16—C8	124.21 (14)
N1—C5—C4	124.10 (19)	C18—C17—C16	120.11 (15)
N1—C5—H5	118.0	C18—C17—C22	118.44 (15)
C4—C5—H5	118.0	C16—C17—C22	121.44 (14)
N2—C6—C7	122.53 (15)	C19—C18—C17	120.60 (16)
N2—C6—C1	116.83 (14)	C19—C18—H18	119.7
C7—C6—C1	120.63 (15)	C17—C18—H18	119.7
C8—C7—C6	119.27 (15)	C20—C19—C18	119.89 (15)
C8—C7—H7	120.4	C20—C19—H19	120.1
C6—C7—H7	120.4	C18—C19—H19	120.1
C9—C8—C7	118.43 (14)	C19—C20—C21	120.07 (16)
C9—C8—C16	122.38 (14)	C19—C20—H20	120.0
C7—C8—C16	119.04 (15)	C21—C20—H20	120.0
C8—C9—C10	118.93 (14)	C20—C21—C16	121.37 (17)
C8—C9—H9	120.5	C20—C21—H21	119.3
C10—C9—H9	120.5	C16—C21—H21	119.3
N2—C10—C9	122.57 (15)	F3—C22—F2	105.78 (17)
N2—C10—C11	116.41 (13)	F3—C22—F1	107.02 (17)
C9—C10—C11	120.99 (14)	F2—C22—F1	104.80 (16)
N3—C11—C12	122.37 (15)	F3—C22—C17	112.81 (14)
N3—C11—C10	116.52 (14)	F2—C22—C17	113.43 (15)
C12—C11—C10	121.08 (14)	F1—C22—C17	112.38 (16)

C5—N1—C1—C2	−1.2 (2)	C9—C10—C11—C12	−168.23 (14)
C5—N1—C1—C6	178.95 (15)	N3—C11—C12—C13	0.7 (2)
N1—C1—C2—C3	0.4 (2)	C10—C11—C12—C13	178.79 (15)
C6—C1—C2—C3	−179.75 (14)	C11—C12—C13—C14	−0.7 (3)
C1—C2—C3—C4	1.2 (3)	C12—C13—C14—C15	0.3 (3)
C2—C3—C4—C5	−2.0 (3)	C11—N3—C15—C14	0.0 (3)
C1—N1—C5—C4	0.4 (3)	C13—C14—C15—N3	0.1 (3)
C3—C4—C5—N1	1.2 (3)	C9—C8—C16—C21	109.60 (18)
C10—N2—C6—C7	0.5 (2)	C7—C8—C16—C21	−65.9 (2)
C10—N2—C6—C1	−179.33 (12)	C9—C8—C16—C17	−70.9 (2)
N1—C1—C6—N2	173.37 (13)	C7—C8—C16—C17	113.59 (18)
C2—C1—C6—N2	−6.5 (2)	C21—C16—C17—C18	−0.8 (2)
N1—C1—C6—C7	−6.5 (2)	C8—C16—C17—C18	179.76 (14)
C2—C1—C6—C7	173.69 (14)	C21—C16—C17—C22	178.55 (16)
N2—C6—C7—C8	−2.7 (2)	C8—C16—C17—C22	−0.9 (2)
C1—C6—C7—C8	177.13 (13)	C16—C17—C18—C19	−0.5 (2)
C6—C7—C8—C9	1.9 (2)	C22—C17—C18—C19	−179.83 (16)
C6—C7—C8—C16	177.55 (13)	C17—C18—C19—C20	1.3 (3)
C7—C8—C9—C10	0.9 (2)	C18—C19—C20—C21	−0.7 (3)
C16—C8—C9—C10	−174.63 (13)	C19—C20—C21—C16	−0.6 (3)
C6—N2—C10—C9	2.5 (2)	C17—C16—C21—C20	1.3 (3)
C6—N2—C10—C11	−175.44 (12)	C8—C16—C21—C20	−179.21 (17)
C8—C9—C10—N2	−3.2 (2)	C18—C17—C22—F3	15.5 (2)
C8—C9—C10—C11	174.63 (13)	C16—C17—C22—F3	−163.81 (17)
C15—N3—C11—C12	−0.4 (2)	C18—C17—C22—F2	135.79 (17)
C15—N3—C11—C10	−178.53 (14)	C16—C17—C22—F2	−43.6 (2)
N2—C10—C11—N3	−172.12 (13)	C18—C17—C22—F1	−105.57 (18)
C9—C10—C11—N3	9.9 (2)	C16—C17—C22—F1	75.1 (2)
N2—C10—C11—C12	9.7 (2)

Experimental details

Crystal data
Chemical formula	C₂₂H₁₄F₃N₃
M_r	377.36
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.767 (5), 10.923 (3), 11.748 (3)
α, β, γ (°)	75.64 (2), 74.03 (4), 72.93 (4)
V (Å³)	900.8 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.60 × 0.30 × 0.30

Data collection
Diffractometer	Oxford Diffraction Xcalibur2 CCD diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2003)
T_min, T_max	0.930, 0.969
No. of measured, independent and observed [I > 2σ(I)] reflections	3953, 3155, 2840
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.148, 1.06
No. of reflections	3155
No. of parameters	254
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.32

Computer programs: CrysAlis CCD (Oxford Diffraction, 2003), CrysAlis RED (Oxford Diffraction, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Acknowledgements

The authors acknowledge financial support from the South African National Research Foundation and the Department of Labour. We also extend our appreciation to Professor John Field for helpful discussions and guidance.

References

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