(1-Pyridinio)perfluoro­phenacyl­ide: a new stable pyridinium ylide in the enol form

The title compound, C₁₃H₆F₅NO, exists in the enol form and adopts the E configuration about the enol double bond. It is the first example of an enol-type pyridinium ylide. The enol structure was unambiguously determined on the basis of the significantly longer C-O bond and shorter C-C bond. Intra­molecular C-H...O and C-H...F hydrogen bonds are responsible for promotion of the enol form and for the stability of this compound.

S1. Comment

Pyridinium ylides are an important family of synthetic intermediates for a variety of organic compounds, such as indolidines (Tsuge et al., 1985; Kanemasa et al., 1989; Zhang et al., 2000; Wu & Chen, 2002; Kakehi, 2005; Xia et al., 2006) and cyclopropanes (Shestopalov et al., 1989; Vo et al., 1997; Kojima et al., 2000; Yamada et al., 2007). Among the various types of pyridinium ylides, pyridinium acylmethylides are often employed for organic synthesis because they can be readily prepared from the corresponding pyridinium salts with a base. These pyridinium ylides are generally unstable and are therefore used in reactions without isolation. However, when an electron-withdrawing group is attached to the C atom next to the pyridinium ring, the stabilization of the ylides increases significantly.

In the course of our research on the reactivity of pyridinium ylides (Yamada et al., 2007), we found that the title compound, (I), is significantly stable without having an electron-withdrawing group on the C atom next to the pyridinium ring. Moreover, the X-ray structure clarifies that the equilibrium in the keto–enol tautomerism is shifted significantly to the enol form.

A view of the molecular structure of (I) is given in Fig. 1. The pyridinium ring is almost coplanar with the enol plane, and the pyridinium and perfluorophenyl rings adopt the E configuration. The N1—C6—C7—O1 and N1—C6—C7—C8 torsion angles are 0.2 (2) and -178.72 (13)°, respectively, suggesting double-bond character for the C6—C7 bond.

Several pyridinium ylides have previously been structurally characterized to date, all of them with an electron-withdrawing group at C6 contributing to the stabilization of the anionic charge. The bond lengths around the anions of these compounds are compared with those of (I) in Table 1. The C6—C7 distances for the reported pyridinium ylides are in the range 1.411–1.443 (5) Å, and the C7—O1 distances occur between 1.211 (3) and 1.242 (s.u.?) Å. The C6—C7 bond length of 1.3648 (19) Å in (I) is the shortest value ever reported for a pyridinium ylide and is also much shorter than the general Csp²—Csp² bond length (Allen et al., 1987). It is, however, very close to that of the Csp²═Csp² bond of a classic enol tautomer (Allen et al., 1987) and is also close to the reported value of 1.360 (13) Å for the C═C double bond in lithium 3,3-dimethyl-1-buten-2-olate [Cambridge Structural Database (CSD, Version 5.28; Allen, 2002) refcode DETRAV (Laube et al., 1985)]. In contrast, the C7—O1 distance of 1.257 (2) Å is the longest value among those reported and is intermediate between a C═O double bond and a C—O single bond. The relatively shorter N1—C6 distance of (I) is also in agreement with the sp² character of atom C6. These observed bond lengths strongly suggest that this pyridinium ylide exists in the enol form. It is important to note that when the perfluorophenyl ring was replaced with a phenyl ring, the ylide became unstable and could not be isolated. Therefore, the perfluorophenyl ring determines the stability of the pyridinium ylide.

The crystal structure of (I) is built up by two intramolecular C—H···O and C—H···F hydrogen bonds and two intermolecular C—H···O and C—H···F hydrogen bonds (Fig. 2 and Table 2) which are the result of the partial negative charges on O and F. The intramolecular C5—H5···O1 hydrogen bond results in the small C1—N1—C6—C7 torsion angle [7.7 (2)°]. The C5···O1 distance is much shorter than those of the other related pyridinium ylides, suggesting a stronger interaction for this hydrogen bond. On the other hand, the -56.04 (19)° torsion angle of C6—C7—C8—C9 is the result of the attractive C6—H6···F1 interaction and electrostatic repulsion between the negatively charged O and F atoms. These hydrogen bonds promote the formation of the enol form.

Molecules of (I) in the crystal structure are linked through two weak C—H···F and C—H···O hydrogen bonds, forming chains running along the a axis (Fig. 2). Atoms C5 and C6 in the molecule at (x, y, z) act as hydrogen-bond donors via atoms H5 and H6 to atoms C5 and F5 in the molecule at (x - 1/2, -y + 1/2, z). There are no other significant intermolecular interactions.

In summary, the significantly longer C—O and shorter C—C bond lengths around the anionic moiety demonstrate that the ylide (I) exists in the enol form. The perfluorophenyl group is responsible for the stability and promotion of the enol tautomer through intramolecular hydrogen bonds.

Related literature

For related literature, see: Allen (2002); Allen et al. (1987); Kakehi (2005); Kanemasa et al. (1989); Kojima et al. (2000); Laube et al. (1985); Shestopalov et al. (1989); Tsuge et al. (1985); Vo et al. (1997); Wu & Chen (2002); Xia et al. (2006); Yamada et al. (2007); Zhang et al. (2000).

S2. Experimental

Triethylamine (75 ml, 0.53 mmol) was added to a solution of 1-(2-oxo-2-(perfluorophenyl)ethyl)pyridinium bromide (129 mg, 0.35 mmol) in CH₂Cl₂ (4 ml). The mixture was stirred at room temperature for 2 h. The product was extracted three times with CH₂Cl₂. The combined organic layer was dried over anhydrous MgSO₄ and evaporated to give (I) (95.5 mg). The recrystallization of (I) from CH₂Cl₂ gave yellow crystals suitable for X-ray crystallographic analysis (yield 96%; decomposition point 377 K). IR (KBr, ν, cm^-1): 1634 (s), 1570 (m), 1484 (m), 1372 (s); ¹H NMR (400 MHz, CDCl₃, δ, p.p.m.): 9.50 (d, J = 6.4 Hz, 2H), 7.58 (t, J = 7.2 Hz, 1H), 7.53 (m, 2H), 6.17 (s, 1H); MS m/z 287 (M⁺, 97%), 285 (100), 120 (48), 65 (51).

S3. Refinement

All H atoms were located in difference Fourier maps and refined isotropically without any restraints.

Computing details

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC & Rigaku, 2006) or SHELXTL?; 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: CrystalStructure (Rigaku/MSC & Rigaku, 2006).

Figures

	Fig. 1. The molecular structure of the title pyridinium ylide, (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. Part of the crystal structure of compound (I), viewed along the b axis. Hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) x - 1/2, -y + 3/2, z; (ii) x + 1/2, -y + 3/2, z.]

(1-Pyridinio)perfluorophenacylide

Crystal data

C13H6F5NO	F(000) = 576.00
Mr = 287.19	Dx = 1.686 Mg m^−3
Monoclinic, P21/a	Cu Kα radiation, λ = 1.54187 Å
Hall symbol: -P 2yab	Cell parameters from 5146 reflections
a = 11.5658 (4) Å	θ = 3.6–68.2°
b = 8.0116 (3) Å	µ = 1.47 mm^−1
c = 12.2308 (4) Å	T = 296 K
β = 93.453 (2)°	Prism, yellow
V = 1131.24 (7) Å^3	0.40 × 0.25 × 0.10 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer	2056 independent reflections
Radiation source: fine-focus sealed tube	1825 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
ω scans	θmax = 68.2°, θmin = 6.6°
Absorption correction: empirical (using intensity measurements) (ABSCOR; Higashi, 1995)	h = −13→13
Tmin = 0.592, Tmax = 0.867	k = −9→9
12696 measured reflections	l = −14→14

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.034	All H-atom parameters refined
wR(F^2) = 0.104	w = 1/[σ^2(Fo^2) + (0.0616P)^2 + 0.1477P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
2056 reflections	Δρmax = 0.18 e Å^−3
207 parameters	Δρmin = −0.16 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0037 (7)

Special details

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 was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
F1	0.24693 (8)	1.06550 (12)	0.85795 (7)	0.0647 (3)
F2	0.28115 (8)	1.03358 (13)	1.07499 (7)	0.0673 (3)
F3	0.44075 (9)	0.81399 (13)	1.16103 (7)	0.0687 (3)
F4	0.57016 (9)	0.63476 (12)	1.02752 (8)	0.0706 (3)
F5	0.53203 (8)	0.65352 (12)	0.81009 (8)	0.0679 (3)
O1	0.46787 (9)	0.90855 (16)	0.65392 (8)	0.0649 (3)
N1	0.23436 (10)	0.86968 (15)	0.54225 (9)	0.0503 (3)
C1	0.30972 (14)	0.9183 (2)	0.46700 (12)	0.0574 (4)
C2	0.27583 (16)	0.9272 (2)	0.35822 (13)	0.0659 (4)
C3	0.16487 (17)	0.8845 (3)	0.32194 (14)	0.0714 (5)
C4	0.08934 (17)	0.8350 (3)	0.39810 (15)	0.0761 (5)
C5	0.12391 (14)	0.8283 (2)	0.50654 (14)	0.0666 (5)
C6	0.26590 (13)	0.8601 (2)	0.65533 (11)	0.0534 (4)
C7	0.37595 (12)	0.87934 (18)	0.70037 (11)	0.0484 (3)
C8	0.38702 (11)	0.85931 (17)	0.82457 (10)	0.0462 (3)
C9	0.32453 (12)	0.95199 (17)	0.89630 (11)	0.0479 (3)
C10	0.34107 (12)	0.93749 (18)	1.00832 (11)	0.0498 (3)
C11	0.42220 (12)	0.82862 (18)	1.05265 (11)	0.0507 (3)
C12	0.48707 (12)	0.73598 (18)	0.98433 (11)	0.0512 (3)
C13	0.46833 (12)	0.75087 (18)	0.87253 (11)	0.0494 (3)
H1	0.3862 (16)	0.946 (2)	0.4967 (14)	0.066 (5)*
H2	0.3308 (17)	0.971 (2)	0.3078 (16)	0.074 (5)*
H3	0.1399 (17)	0.894 (2)	0.2488 (16)	0.077 (5)*
H4	0.011 (2)	0.811 (3)	0.3766 (17)	0.086 (6)*
H5	0.0733 (18)	0.802 (3)	0.5631 (16)	0.081 (6)*
H6	0.2045 (15)	0.834 (2)	0.6978 (14)	0.061 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F1	0.0620 (6)	0.0727 (6)	0.0595 (5)	0.0196 (4)	0.0050 (4)	−0.0034 (4)
F2	0.0627 (6)	0.0868 (7)	0.0540 (5)	0.0017 (4)	0.0159 (4)	−0.0206 (4)
F3	0.0742 (6)	0.0901 (7)	0.0413 (4)	−0.0148 (5)	−0.0010 (4)	0.0012 (4)
F4	0.0621 (6)	0.0771 (6)	0.0707 (6)	0.0094 (4)	−0.0111 (4)	0.0067 (5)
F5	0.0618 (6)	0.0783 (6)	0.0648 (5)	0.0184 (4)	0.0131 (4)	−0.0104 (4)
O1	0.0450 (6)	0.1040 (9)	0.0465 (6)	−0.0079 (5)	0.0107 (4)	−0.0003 (5)
N1	0.0463 (6)	0.0616 (7)	0.0433 (6)	−0.0041 (5)	0.0059 (5)	−0.0004 (5)
C1	0.0505 (8)	0.0753 (10)	0.0471 (8)	−0.0043 (7)	0.0102 (6)	0.0004 (6)
C2	0.0657 (10)	0.0866 (12)	0.0464 (8)	−0.0019 (8)	0.0102 (7)	0.0018 (7)
C3	0.0776 (12)	0.0909 (12)	0.0448 (8)	−0.0046 (9)	−0.0039 (8)	0.0003 (8)
C4	0.0618 (11)	0.1043 (14)	0.0606 (9)	−0.0176 (9)	−0.0095 (8)	0.0038 (9)
C5	0.0513 (9)	0.0927 (12)	0.0560 (9)	−0.0152 (8)	0.0038 (7)	0.0059 (8)
C6	0.0458 (7)	0.0741 (10)	0.0412 (7)	−0.0060 (6)	0.0092 (6)	0.0021 (6)
C7	0.0466 (7)	0.0577 (8)	0.0417 (7)	−0.0008 (6)	0.0090 (5)	−0.0027 (5)
C8	0.0412 (7)	0.0548 (7)	0.0431 (7)	−0.0055 (5)	0.0069 (5)	−0.0038 (5)
C9	0.0414 (7)	0.0534 (7)	0.0494 (7)	−0.0012 (5)	0.0058 (5)	−0.0030 (5)
C10	0.0454 (7)	0.0601 (8)	0.0448 (7)	−0.0093 (6)	0.0114 (5)	−0.0097 (6)
C11	0.0492 (8)	0.0620 (8)	0.0408 (6)	−0.0155 (6)	0.0028 (5)	−0.0004 (6)
C12	0.0440 (7)	0.0556 (8)	0.0534 (8)	−0.0047 (6)	−0.0014 (6)	0.0033 (6)
C13	0.0423 (7)	0.0561 (8)	0.0506 (7)	−0.0011 (5)	0.0081 (5)	−0.0058 (6)

Geometric parameters (Å, º)

F1—C9	1.3423 (16)	C7—C8	1.5252 (18)
F2—C10	1.3438 (17)	C8—C9	1.3856 (19)
F3—C11	1.3352 (15)	C8—C13	1.3845 (18)
F4—C12	1.3413 (16)	C9—C10	1.3768 (18)
F5—C13	1.3424 (17)	C10—C11	1.3689 (19)
O1—C7	1.2572 (17)	C11—C12	1.374 (2)
N1—C1	1.3619 (19)	C12—C13	1.3767 (18)
N1—C5	1.3657 (19)	C1—H1	0.962 (18)
N1—C6	1.4110 (17)	C2—H2	0.98 (2)
C1—C2	1.366 (2)	C3—H3	0.926 (19)
C2—C3	1.376 (2)	C4—H4	0.94 (2)
C3—C4	1.373 (2)	C5—H5	0.96 (2)
C4—C5	1.363 (2)	C6—H6	0.928 (18)
C6—C7	1.3648 (19)
F1···F3^i	2.9442 (14)	C12···C10^ii	3.283 (2)
F1···F4^ii	3.4420 (13)	C13···F2^vi	3.4628 (17)
F1···F4^iii	3.4009 (13)	C13···F2^ii	3.4008 (16)
F1···F5^iii	3.0698 (13)	C13···F4^ix	3.3620 (17)
F1···C3^iv	3.562 (2)	C13···C10^ii	3.5819 (19)
F1···C10^i	3.5768 (17)	F1···H3^iv	3.250 (19)
F1···C11^i	3.1182 (17)	F2···H2^v	2.914 (19)
F2···F4^ii	3.4423 (14)	F2···H3^v	2.98 (2)
F2···F4^iii	2.8178 (13)	F3···H2^v	2.59 (2)
F2···F5^ii	3.5444 (13)	F3···H3^vii	2.991 (19)
F2···C2^v	3.5716 (18)	F3···H4^vii	2.89 (2)
F2···C3^v	3.584 (2)	F4···H3^vii	2.787 (19)
F2···C8^i	3.5200 (16)	F5···H3^x	2.935 (19)
F2···C9^i	3.5924 (17)	F5···H4^x	3.58 (2)
F2···C12^i	3.5367 (16)	F5···H5^viii	3.11 (2)
F2···C12^ii	3.3698 (17)	F5···H6^viii	2.492 (18)
F2···C13^i	3.4628 (17)	O1···H1^xi	2.824 (18)
F2···C13^ii	3.4008 (16)	O1···H2^xi	2.539 (19)
F3···F1^vi	2.9442 (14)	O1···H4^iv	3.26 (2)
F3···O1^ii	3.3004 (14)	O1···H5^viii	2.39 (2)
F3···C2^v	3.291 (2)	O1···H6^viii	3.372 (17)
F3···C3^vii	3.537 (2)	C1···H4^viii	3.22 (2)
F3···C4^vii	3.491 (2)	C1···H5^iv	3.39 (2)
F3···C8^ii	3.2875 (16)	C2···H4^viii	3.32 (2)
F3···C9^ii	3.4067 (17)	C2···H5^iv	3.57 (2)
F4···F1^ii	3.4420 (13)	C2···H6^iv	3.339 (16)
F4···F1^viii	3.4009 (13)	C4···H1^x	3.377 (18)
F4···F2^ii	3.4423 (14)	C4···H1^iii	3.519 (18)
F4···F2^viii	2.8178 (13)	C4···H5^xiv	3.51 (2)
F4···F4^ix	2.7600 (13)	C5···H1^x	3.066 (18)
F4···F5^ix	3.3104 (13)	C5···H1^iii	3.516 (18)
F4···C9^viii	3.5047 (17)	C6···H2^x	3.353 (19)
F4···C10^viii	3.2088 (17)	C7···H5^viii	3.26 (2)
F4···C12^ix	3.0446 (17)	C11···H2^v	3.54 (2)
F4···C13^ix	3.3620 (17)	C13···H3^x	3.421 (19)
F5···F1^viii	3.0698 (13)	H1···O1^xi	2.824 (18)
F5···F2^ii	3.5444 (13)	H1···C4^iv	3.377 (18)
F5···F4^ix	3.3104 (13)	H1···C4^viii	3.519 (18)
F5···C3^x	3.463 (2)	H1···C5^iv	3.066 (18)
F5···C6^viii	3.3953 (17)	H1···C5^viii	3.516 (18)
F5···C9^viii	3.5835 (16)	H1···H1^xi	2.77 (2)
O1···F3^ii	3.3004 (14)	H1···H4^iv	3.48 (2)
O1···C1^xi	3.3448 (19)	H1···H4^viii	2.96 (2)
O1···C2^xi	3.255 (2)	H1···H5^iv	2.99 (2)
O1···C4^iv	3.531 (2)	H1···H5^viii	3.01 (2)
O1···C5^viii	3.240 (2)	H2···F2^xii	2.914 (19)
C1···O1^xi	3.3448 (19)	H2···F3^xii	2.59 (2)
C1···C5^iv	3.385 (2)	H2···O1^xi	2.539 (19)
C2···F2^xii	3.5716 (18)	H2···C6^iv	3.353 (19)
C2···F3^xii	3.291 (2)	H2···C11^xii	3.54 (2)
C2···O1^xi	3.255 (2)	H2···H4^viii	3.16 (2)
C2···C6^iv	3.504 (2)	H2···H5^iv	3.25 (2)
C3···F1^x	3.562 (2)	H2···H6^iv	2.94 (2)
C3···F2^xii	3.584 (2)	H3···F1^x	3.250 (19)
C3···F3^xiii	3.537 (2)	H3···F2^xii	2.98 (2)
C3···F5^iv	3.463 (2)	H3···F3^xiii	2.991 (19)
C4···F3^xiii	3.491 (2)	H3···F4^xiii	2.787 (19)
C4···O1^x	3.531 (2)	H3···F5^iv	2.935 (19)
C5···O1^iii	3.240 (2)	H3···C13^iv	3.421 (19)
C5···C1^x	3.385 (2)	H4···F3^xiii	2.89 (2)
C6···F5^iii	3.3953 (17)	H4···F5^iv	3.58 (2)
C6···C2^x	3.504 (2)	H4···O1^x	3.26 (2)
C8···F2^vi	3.5200 (16)	H4···C1^iii	3.22 (2)
C8···F3^ii	3.2875 (16)	H4···C2^iii	3.32 (2)
C9···F2^vi	3.5924 (17)	H4···H1^x	3.48 (2)
C9···F3^ii	3.4067 (17)	H4···H1^iii	2.96 (2)
C9···F4^iii	3.5047 (17)	H4···H2^iii	3.16 (2)
C9···F5^iii	3.5835 (16)	H4···H5^xiv	3.35 (3)
C9···C11^ii	3.4408 (19)	H5···F5^iii	3.11 (2)
C9···C12^ii	3.5701 (19)	H5···O1^iii	2.39 (2)
C10···F1^vi	3.5768 (17)	H5···C1^x	3.39 (2)
C10···F4^iii	3.2088 (17)	H5···C2^x	3.57 (2)
C10···C11^ii	3.437 (2)	H5···C4^xiv	3.51 (2)
C10···C12^ii	3.283 (2)	H5···C7^iii	3.26 (2)
C10···C13^ii	3.5819 (19)	H5···H1^x	2.99 (2)
C11···F1^vi	3.1182 (17)	H5···H1^iii	3.01 (2)
C11···C9^ii	3.4408 (19)	H5···H2^x	3.25 (2)
C11···C10^ii	3.437 (2)	H5···H4^xiv	3.35 (3)
C11···C11^ii	3.566 (2)	H6···F5^iii	2.492 (18)
C12···F2^vi	3.5367 (16)	H6···O1^iii	3.372 (17)
C12···F2^ii	3.3698 (17)	H6···C2^x	3.339 (16)
C12···F4^ix	3.0446 (17)	H6···H2^x	2.94 (2)
C12···C9^ii	3.5701 (19)
C1—N1—C5	118.53 (12)	F3—C11—C10	120.96 (12)
C1—N1—C6	122.66 (12)	F3—C11—C12	119.70 (12)
C5—N1—C6	118.81 (12)	C10—C11—C12	119.32 (12)
N1—C1—C2	121.02 (14)	F4—C12—C11	119.45 (12)
C1—C2—C3	120.57 (16)	F4—C12—C13	120.65 (12)
C2—C3—C4	118.18 (15)	C11—C12—C13	119.88 (12)
C3—C4—C5	120.66 (17)	F5—C13—C8	120.37 (11)
N1—C5—C4	121.04 (15)	F5—C13—C12	117.11 (12)
N1—C6—C7	124.70 (13)	C8—C13—C12	122.51 (12)
O1—C7—C6	129.20 (12)	N1—C1—H1	115.0 (10)
O1—C7—C8	116.56 (11)	C2—C1—H1	124.0 (10)
C6—C7—C8	114.23 (12)	C1—C2—H2	118.3 (11)
C7—C8—C9	123.96 (11)	C3—C2—H2	121.0 (11)
C7—C8—C13	120.14 (11)	C2—C3—H3	121.4 (12)
C9—C8—C13	115.78 (11)	C4—C3—H3	120.4 (12)
F1—C9—C8	120.34 (11)	C3—C4—H4	120.4 (13)
F1—C9—C10	117.05 (12)	C5—C4—H4	118.8 (13)
C8—C9—C10	122.57 (12)	N1—C5—H5	115.1 (12)
F2—C10—C9	120.64 (12)	C4—C5—H5	123.8 (12)
F2—C10—C11	119.40 (11)	N1—C6—H6	113.5 (10)
C9—C10—C11	119.92 (13)	C7—C6—H6	121.7 (10)
C1—N1—C5—C4	0.1 (2)	C9—C8—C13—F5	178.91 (12)
C5—N1—C1—C2	0.6 (2)	C9—C8—C13—C12	−0.4 (2)
C1—N1—C6—C7	−7.7 (2)	C13—C8—C9—F1	177.32 (12)
C6—N1—C1—C2	−179.52 (15)	C13—C8—C9—C10	−0.4 (2)
C5—N1—C6—C7	172.20 (15)	F1—C9—C10—F2	0.15 (19)
C6—N1—C5—C4	−179.78 (17)	F1—C9—C10—C11	−177.48 (12)
N1—C1—C2—C3	−1.1 (2)	C8—C9—C10—F2	177.89 (12)
C1—C2—C3—C4	0.8 (2)	C8—C9—C10—C11	0.3 (2)
C2—C3—C4—C5	−0.1 (2)	F2—C10—C11—F3	1.5 (2)
C3—C4—C5—N1	−0.4 (3)	F2—C10—C11—C12	−177.06 (12)
N1—C6—C7—O1	0.2 (2)	C9—C10—C11—F3	179.15 (12)
N1—C6—C7—C8	−178.72 (13)	C9—C10—C11—C12	0.6 (2)
O1—C7—C8—C9	124.87 (15)	F3—C11—C12—F4	−1.5 (2)
O1—C7—C8—C13	−50.93 (18)	F3—C11—C12—C13	−179.91 (12)
C6—C7—C8—C9	−56.04 (19)	C10—C11—C12—F4	177.04 (12)
C6—C7—C8—C13	128.16 (14)	C10—C11—C12—C13	−1.3 (2)
C7—C8—C9—F1	1.3 (2)	F4—C12—C13—F5	3.6 (2)
C7—C8—C9—C10	−176.32 (13)	F4—C12—C13—C8	−177.09 (12)
C7—C8—C13—F5	−4.95 (19)	C11—C12—C13—F5	−178.08 (12)
C7—C8—C13—C12	175.72 (13)	C11—C12—C13—C8	1.3 (2)

Symmetry codes: (i) −x+1/2, y+1/2, −z+2; (ii) −x+1, −y+2, −z+2; (iii) x−1/2, −y+3/2, z; (iv) −x+1/2, y+1/2, −z+1; (v) x, y, z+1; (vi) −x+1/2, y−1/2, −z+2; (vii) x+1/2, −y+3/2, z+1; (viii) x+1/2, −y+3/2, z; (ix) −x+1, −y+1, −z+2; (x) −x+1/2, y−1/2, −z+1; (xi) −x+1, −y+2, −z+1; (xii) x, y, z−1; (xiii) x−1/2, −y+3/2, z−1; (xiv) −x, −y+2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···F1	0.94 (2)	2.72 (2)	2.994 (2)	97.7 (11)
C1—H1···O1	0.97 (2)	2.10 (2)	2.842 (2)	131.7 (15)
C5—H5···O1^iii	0.97 (2)	2.39 (2)	3.240 (2)	147.3 (17)
C6—H6···F5^iii	0.94 (2)	2.48 (2)	3.396 (2)	164.9 (14)

Symmetry code: (iii) x−1/2, −y+3/2, z.