3,3′,5,5′-Tetra­methyl-4,4′-bipyrazole–penta­fluoro­phenol (2/3)

In the title compound, 2C₁₀H₁₄N₄·3C₆HF₅O, one of the penta­fluoro­phenol mol­ecules resides on a mirror plane bisecting the O...F axis. The components aggregate by N—H...N, N—H...O and O—H...N hydrogen bonds involving equal disordering of the H atoms into mol­ecular ensembles based on a 2:1 pyrazole–phenol cyclic pattern [O...N = 2.7768 (16) Å and N...N = 2.859 (2) Å], crosslinked into one-dimensional columns via hydrogen bonding between the outer pyrazole groups and additional penta­fluoro­phenol mol­ecules. The latter yields a 1:1 pyrazole–phenol catemer with alternating strong O—H...N [2.5975 (16) Å] and weaker N—H...O [2.8719 (17) Å] hydrogen bonds. This is the first reported mol­ecular adduct of a penta­fluorinated phenol and a nitro­gen base, and suggests the utility of highly acidic phenols and pyrazoles for developing hydrogen-bonded cocrystals.

S1. Comment

N-unsubstituted pyrazoles provide rich and versatile possibilities for engineering of hydrogen-bonded solids (Desiraju, 1989), since the molecular frame combines bond donor (NH) and acceptor (N) sites for self-association (Foces-Foces et al., 2000) or for exploitation of characteristic interactions in multicomponent systems. Thus, the hydrogen-bonding functionalities of pyrazoles and phenols complement each other, and these species commonly cocrystallize forming binary adducts in which the components are rationally integrated by NH···O and OH···N bonding (Boldog et al., 2004). Such incorporation of a strong OH bond-donor unit within the pyrazole catemer is interesting in view of the solid-state tautomerism of pyrazoles [e.g. N—H···N to N···H—N; Aguilar-Parrilla et al., 1992] as a tool for enhancing the strength of partial bonding contributions (Steiner, 2002) and the promotion of the proton dynamics leading to a long-range fast proton transfer. Therefore, it is of interest to explore whether the highly acidic phenols are applicable for the design of molecular adducts with pyrazoles and if the catemeric motif dominates the structure over the formation of different cyclic patterns. In this context we examined 3,3',5,5'-tetramethyl-4,4'-bipyrazole (Me₄bpz), the only pyrazole exhibiting catemer/trimer supramolecular isomerism (Boldog et al., 2003), and pentafluorophenol, where the acidity is comparable to that of carbonic acids (pK_a = 5.50 versus pK_a = 9.95 for phenol).

Compound (I) is the first structurally examined genuine molecular adduct formed by pentafluorophenol and a nitrogen base, unlike the ionic pentafluorophenolate of highly basic 1,8-bis(dimethylamino)naphthalene (Odiaga et al., 1992). The asymmetric unit of (I) includes molecular components lying in general positions and a molecule of pentafluorophenol, with the O2—F8 axis located on a mirror plane (Fig. 1). The primary interaction of the pyrazole and phenol functions occurs by means of NH···N, NH···O and OH···N hydrogen bonding that yields a combination of two distinct supramolecular motifs.

Firstly, two pyrazole and one phenol groups form a rare cyclic pattern, which is related to characteristic pyrazole trimers (Foces-Foces et al., 2000) from the substitution of one pyrazole unit for phenol. A similar hydrogen-bonded cycle incorporating a water molecule was observed for a series of isostructural adducts (Me₄bpz)₃(H₂O)(L) (L is acetone, ethylacetate and tetrahydrofuran) (Boldog et al., 2001). Since two bipyrazole molecules of the (Me₄bpz)₂(C₆F₅OH) cyclic unit are related by a mirror plane [symmetry code: (i) x, -y + 3/2, z], the donor and acceptor sites of the hydrogen bond are not distinguishable and the H atoms are equally disordered over two positions (Fig. 1). Accordingly, both N···O separations are equivalent by symmetry [N4···O2 = 2.7768 (16) Å] and they are intermediate between the values for NH···O (2.92 Å) and OH···N (2.70 Å) bonds in a 1:1 adduct of 3,5-dimethylpyrazole and phenol (Boldog et al., 2004). The C₆F₅OH unit is oriented at 30.69 (5)° to the plane of two pyrazole rings, while the bipyrazole molecule has a twisted conformation with a dihedral angle between the two pyrazole groups of 72.16 (6)° [torsion angle C1—C2—C7—C8 72.8 (2)°].

Secondly, the hydrogen bonding between the outer pyrazole groups and second pentafluorophenol molecule yields the infinite alterating motif –A(BA)_n–, which may be viewed as a typical pyrazole catemer expanded by inclusion of a second component. Successive aggregates of (Me₄bpz)₂(C₆F₅OH) are related by a 2₁ axis [symmetry code: (iii) x + 1/2, -y + 3/2, -z + 1/2] and the phenol linkers provide integration of the units into columns along the x-axis direction (Figs. 2 and 3). There is a clear differentiation in the N···O separations, suggesting two distinct types of hydrogen bonding and ordering of the H atoms. The first indicates a strong interaction [O1H···N1 = 2.5975 (16) Å], while for the bond involving the pyrazole NH donor the N and O atoms are much more distal [N2H···O1ⁱⁱ = 2.8719 (17) Å; symmetry code: (ii) x - 1/2, y, -z + 1/2]. The only precedent for an OH···N interaction of fluorinated phenols is a 2.64 Å intermolecular bond in 4'-(4-hydroxy-2,3,5,6-tetrafluorophenyl)-2,2':6',2''-terpyridine (Constable et al., 2003).

Ordering of the H atoms in the catemer is supported by the internal angles involving the N atoms [C1—N1—N2 = 105.46 (12)° and N1—N2—C3 = 112.50 (12)°], which are most sensitive to the tautomerism of pyrazole (Alkorta et al., 1999). Such differentiation agrees with the C—N—N(H) and C—N(H)—N angles (104.0–106.7° and 111.1–113.0°, respectively) for hydrogen-bonded Me₄bpz structures (Table 2), while convergence of these parameters is a positive sign for the disordering of the H atoms, as occurs for the cyclic pattern in (Me₄bpz)₂(C₆F₅OH).

Several types of weaker interactions are also relevant in the crystal packing. Along the catemer, the pentafluorophenol molecules are situated almost parallel to each other [symmetry code: (iv) x + 1/2, y, -z + 1/2; Fig. 2] and afford a weak slipped π–π stack with an intercentroid distance of 3.588 (2) Å and an interplanar angle of 12.13 (4)°. Interdigitation of the columns (Fig. 3) leads to close contacts between the C6–C8/N3/N4 pyrazole ring and atom F7^v [symmetry code: (v) x + 1/2, y, -z + 3/2], situated almost exactly above the ring centroid [π···F^v = 3.287 (2) Å, with the F···π axis making an angle to the aromatic plane of 85.2°]. Such stacking commonly occurs for N-heterocycles and negatively polarized atoms, and is especially characteristic for the most electron-deficient azines and counter-anions (Schottel et al., 2008). The short C10···F3^vi separations [3.288 (2) Å; symmetry code: (vi) -x + 3/2, -y + 1, z + 1/2] may be attributed to very weak CH···F bonding (H···F3^vi = 2.59 Å and C10H···F3^vi = 129°) (Desiraju & Steiner, 1999).

In conclusion, (I) suggests the utility of pyrazoles and highly acidic fluorinated phenols as complementary components for developing of hydrogen-bonded cocrystals. The efficient hydorgen-bond donor properties of C₆F₅OH allow its integration within either cyclic or infinite supramolecular pyrazole motifs. The (pz)₂(C₆F₅OH) cycle displays disordering of the NH and OH H atoms, while along the two-component catemer the H atoms are ordered and immobile.

Related literature

For related literature, see: Aguilar-Parrilla, Gerd Scherer, Limbach, Foces-Foces, Cano, Smith, Toiron & Elguero (1992); Alkorta et al. (1999); Boldog et al. (2001, 2003, 2004); Constable et al. (2003); Desiraju (1989); Desiraju & Steiner (1999); Foces-Foces, Alkorta & Elguero (2000); Mosby (1957); Odiaga et al. (1992); Schottel et al. (2008); Steiner (2002).

S2. Experimental

Me₄bpz was synthesized according to the method reported by Mosby (1957). Large colorless crystals of the molecular complex 2(Me₄bpz):3(C₆F₅OH) were prepared by slow evaporation of a solution of Me₄bpz (0.190 g, 1 mmol) and pentafluorophenol (0.184 g, 1 mmol) in 5 ml of methanol.

S3. Refinement

Methyl H atoms were treated as riding in geometrically idealized positions, with C—H distances of 0.97 Å and U_iso(H) values of 1.5U_eq(c), with equal idealized disordering of the H atoms bonded to atoms C4, C9 and C10. H atoms bonded to N and O atoms were located in difference maps and then their coordinates were fixed [with U_iso(H) = 1.5U_eq(O,N)], giving O—H distances of 0.90 and 0.92 Å and a range of N—H distances of 0.85–0.90 Å. H atoms bonded to atoms O2, N3 and N4 were included with partial occupancy factors of 0.5, considering a disordering scheme for hydrogen bonding within the cyclic pyrazole/phenol pattern.

Computing details

Data collection: SMART-NT (Bruker, 1998); cell refinement: SAINT-NT (Bruker, 1999); data reduction: SAINT-NT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Version 1.700.00; Farrugia, 1999).

Figures

	Fig. 1. A view of (I), with the atom-labeling scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate hydrogen bonds. Atoms O2, C17, C20 and F8 are located on a mirror plane and therefore the H atoms within the pyrazole/phenol cycle are equally disordered by symmetry. [Symmetry code: (i) -x, -y + 3/2, z.]
	Fig. 2. Interconnection of the [(Me4bpz)2(C6F5OH)] ensembles in (I) by hydrogen bonding involving the outer pyrazole and pentafluorophenol rings with the alternating [(pyrazole)/(phenol)]n catemer. Dashed lines indicate hydrogen bonds. H atoms have been omitted for clarity and N atoms are shaded grey. [Symmetry codes: (i) -x, -y + 3/2, z; (iv) x + 1/2, y, -z + 1/2.]
	Fig. 3. A view of (I) along the direction of the hydrogen-bonded columns, showing the interdigitation of the pentafluorophenyl groups (projection on a bc plane). F atoms have been omitted for clarity.

3,3',5,5'-Tetramethyl-4,4'-bipyrazole–pentafluorophenol (2/3)

Crystal data

2C10H14N4·3C6HF5O	Dx = 1.583 Mg m^−3
Mr = 932.71	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 13762 reflections
a = 6.9565 (7) Å	θ = 2.9–27.1°
b = 41.727 (4) Å	µ = 0.15 mm^−1
c = 13.4827 (15) Å	T = 213 K
V = 3913.6 (7) Å^3	Prism, colourless
Z = 4	0.27 × 0.20 × 0.20 mm
F(000) = 1896

Data collection

Siemens SMART CCD area-detector diffractometer	4321 independent reflections
Radiation source: fine-focus sealed tube	3634 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
ω scans	θmax = 27.1°, θmin = 2.9°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −8→8
Tmin = 0.950, Tmax = 0.980	k = −52→52
13762 measured reflections	l = −11→17

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.106	w = 1/[σ^2(Fo^2) + (0.05P)^2 + 1.4524P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.003
4321 reflections	Δρmax = 0.23 e Å^−3
297 parameters	Δρmin = −0.20 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0075 (5)

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 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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.68836 (18)	0.54889 (2)	0.20901 (8)	0.0415 (3)
H1O	0.6652	0.5603	0.2644	0.062*
O2	0.7368 (3)	0.7500	0.74202 (11)	0.0479 (4)
H2O	0.7389	0.7691	0.7077	0.072*	0.50
F1	0.60871 (17)	0.51829 (2)	0.38835 (7)	0.0497 (3)
F2	0.54018 (18)	0.45460 (2)	0.39266 (8)	0.0576 (3)
F3	0.53489 (19)	0.42018 (2)	0.22198 (9)	0.0642 (3)
F4	0.6130 (2)	0.44968 (3)	0.04682 (9)	0.0668 (3)
F5	0.68483 (18)	0.51374 (3)	0.04262 (7)	0.0564 (3)
F6	0.6845 (2)	0.69375 (3)	0.84399 (9)	0.0699 (4)
F7	0.5884 (2)	0.69377 (3)	1.03717 (8)	0.0681 (3)
F8	0.5383 (3)	0.7500	1.13590 (10)	0.0698 (5)
N1	0.6118 (2)	0.58828 (3)	0.35288 (9)	0.0381 (3)
N2	0.4511 (2)	0.58589 (3)	0.40882 (9)	0.0393 (3)
H2N	0.3682	0.5696	0.3985	0.059*
N3	0.6310 (2)	0.71574 (3)	0.52143 (9)	0.0361 (3)
H3N	0.6271	0.7361	0.5241	0.054*	0.50
N4	0.67858 (19)	0.70069 (3)	0.60702 (9)	0.0360 (3)
H4N	0.7029	0.7130	0.6596	0.054*	0.50
C1	0.6902 (2)	0.61636 (3)	0.37706 (10)	0.0349 (3)
C2	0.5769 (2)	0.63196 (3)	0.44871 (10)	0.0331 (3)
C3	0.4244 (2)	0.61152 (3)	0.46714 (11)	0.0367 (3)
C4	0.2582 (3)	0.61434 (4)	0.53581 (14)	0.0506 (4)
H4A	0.1777	0.5954	0.5299	0.076*	0.50
H4B	0.1838	0.6332	0.5189	0.076*	0.50
H4C	0.3045	0.6162	0.6034	0.076*	0.50
H4D	0.2663	0.6345	0.5716	0.076*	0.50
H4E	0.2602	0.5967	0.5825	0.076*	0.50
H4F	0.1395	0.6137	0.4981	0.076*	0.50
C5	0.8707 (3)	0.62766 (4)	0.32933 (14)	0.0515 (4)
H5A	0.9650	0.6105	0.3300	0.077*
H5B	0.9205	0.6460	0.3655	0.077*
H5C	0.8442	0.6339	0.2613	0.077*
C6	0.6683 (2)	0.66895 (3)	0.59286 (10)	0.0331 (3)
C7	0.6111 (2)	0.66332 (3)	0.49555 (10)	0.0316 (3)
C8	0.5910 (2)	0.69363 (3)	0.45311 (11)	0.0344 (3)
C9	0.5364 (3)	0.70241 (4)	0.34947 (12)	0.0545 (5)
H9A	0.5348	0.7256	0.3428	0.082*	0.50
H9B	0.4098	0.6939	0.3347	0.082*	0.50
H9C	0.6294	0.6934	0.3036	0.082*	0.50
H9D	0.5145	0.6831	0.3112	0.082*	0.50
H9E	0.6395	0.7147	0.3194	0.082*	0.50
H9F	0.4199	0.7152	0.3505	0.082*	0.50
C10	0.7201 (3)	0.64515 (4)	0.67077 (12)	0.0493 (4)
H10A	0.7541	0.6563	0.7314	0.074*	0.50
H10B	0.8286	0.6325	0.6485	0.074*	0.50
H10C	0.6112	0.6312	0.6832	0.074*	0.50
H10D	0.7085	0.6237	0.6440	0.074*	0.50
H10E	0.6340	0.6475	0.7269	0.074*	0.50
H10F	0.8514	0.6488	0.6922	0.074*	0.50
C11	0.6453 (2)	0.49932 (4)	0.12909 (12)	0.0380 (3)
C12	0.6089 (2)	0.46679 (4)	0.13083 (13)	0.0439 (4)
C13	0.5732 (2)	0.45183 (3)	0.21943 (14)	0.0430 (4)
C14	0.5749 (2)	0.46915 (4)	0.30596 (12)	0.0392 (3)
C15	0.6113 (2)	0.50164 (3)	0.30351 (11)	0.0345 (3)
C16	0.6468 (2)	0.51763 (3)	0.21530 (11)	0.0327 (3)
C17	0.6874 (3)	0.7500	0.83805 (15)	0.0401 (5)
C18	0.6626 (3)	0.72189 (4)	0.89067 (12)	0.0432 (4)
C19	0.6133 (3)	0.72169 (4)	0.98965 (12)	0.0434 (4)
C20	0.5883 (4)	0.7500	1.03941 (16)	0.0433 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0617 (7)	0.0250 (5)	0.0377 (5)	−0.0100 (5)	0.0092 (5)	−0.0053 (4)
O2	0.0620 (11)	0.0527 (9)	0.0289 (7)	0.000	0.0033 (7)	0.000
F1	0.0805 (7)	0.0339 (5)	0.0346 (5)	0.0031 (5)	−0.0011 (5)	−0.0022 (4)
F2	0.0764 (8)	0.0371 (5)	0.0592 (6)	0.0010 (5)	−0.0015 (5)	0.0181 (5)
F3	0.0750 (8)	0.0230 (4)	0.0946 (9)	−0.0055 (5)	−0.0080 (7)	−0.0046 (5)
F4	0.0869 (9)	0.0485 (6)	0.0652 (7)	−0.0067 (6)	0.0000 (6)	−0.0311 (5)
F5	0.0793 (8)	0.0510 (6)	0.0389 (5)	−0.0126 (5)	0.0131 (5)	−0.0078 (4)
F6	0.1007 (10)	0.0530 (7)	0.0560 (6)	0.0101 (6)	−0.0023 (6)	−0.0183 (5)
F7	0.0996 (9)	0.0483 (6)	0.0565 (6)	−0.0067 (6)	0.0015 (6)	0.0144 (5)
F8	0.1011 (14)	0.0750 (11)	0.0331 (7)	0.000	0.0164 (8)	0.000
N1	0.0547 (8)	0.0236 (6)	0.0361 (6)	−0.0025 (5)	−0.0006 (6)	−0.0035 (5)
N2	0.0546 (8)	0.0229 (6)	0.0405 (7)	−0.0082 (5)	−0.0001 (6)	−0.0024 (5)
N3	0.0504 (8)	0.0204 (5)	0.0376 (6)	−0.0013 (5)	−0.0008 (6)	−0.0027 (5)
N4	0.0462 (7)	0.0239 (6)	0.0379 (6)	0.0001 (5)	−0.0003 (5)	−0.0014 (5)
C1	0.0500 (9)	0.0222 (6)	0.0325 (7)	−0.0005 (6)	−0.0029 (6)	−0.0027 (5)
C2	0.0472 (8)	0.0215 (6)	0.0307 (7)	−0.0011 (6)	−0.0026 (6)	−0.0001 (5)
C3	0.0511 (9)	0.0231 (6)	0.0360 (7)	−0.0027 (6)	−0.0009 (7)	0.0013 (5)
C4	0.0585 (11)	0.0363 (8)	0.0570 (10)	−0.0063 (8)	0.0117 (8)	−0.0009 (7)
C5	0.0597 (11)	0.0413 (9)	0.0535 (10)	−0.0074 (8)	0.0134 (9)	−0.0126 (8)
C6	0.0418 (8)	0.0239 (6)	0.0337 (7)	0.0004 (6)	0.0021 (6)	−0.0014 (5)
C7	0.0404 (8)	0.0215 (6)	0.0331 (7)	−0.0011 (5)	0.0019 (6)	−0.0013 (5)
C8	0.0462 (8)	0.0241 (7)	0.0329 (7)	−0.0015 (6)	−0.0007 (6)	−0.0011 (5)
C9	0.0931 (15)	0.0324 (8)	0.0380 (8)	−0.0014 (9)	−0.0117 (9)	0.0027 (6)
C10	0.0791 (13)	0.0297 (8)	0.0391 (8)	0.0057 (8)	−0.0070 (8)	0.0020 (6)
C11	0.0402 (8)	0.0352 (8)	0.0388 (8)	−0.0049 (6)	0.0047 (6)	−0.0052 (6)
C12	0.0437 (9)	0.0338 (8)	0.0542 (9)	−0.0024 (7)	−0.0006 (8)	−0.0186 (7)
C13	0.0389 (8)	0.0225 (6)	0.0678 (11)	−0.0003 (6)	−0.0042 (8)	−0.0036 (7)
C14	0.0374 (8)	0.0288 (7)	0.0514 (9)	0.0028 (6)	−0.0014 (7)	0.0073 (6)
C15	0.0391 (8)	0.0261 (7)	0.0384 (8)	0.0039 (6)	−0.0016 (6)	−0.0031 (6)
C16	0.0320 (7)	0.0260 (7)	0.0402 (8)	−0.0020 (5)	0.0020 (6)	−0.0042 (6)
C17	0.0326 (11)	0.0582 (14)	0.0296 (10)	0.000	−0.0037 (9)	0.000
C18	0.0457 (9)	0.0468 (9)	0.0372 (8)	0.0028 (7)	−0.0051 (7)	−0.0081 (7)
C19	0.0494 (10)	0.0429 (9)	0.0380 (8)	−0.0025 (7)	−0.0028 (7)	0.0077 (7)
C20	0.0496 (13)	0.0514 (14)	0.0288 (10)	0.000	0.0017 (9)	0.000

Geometric parameters (Å, º)

O1—C16	1.3385 (17)	C4—H4F	0.9700
O1—H1O	0.9005	C5—H5A	0.9700
O2—C17	1.340 (3)	C5—H5B	0.9700
O2—H2O	0.9230	C5—H5C	0.9700
F1—C15	1.3384 (17)	C6—C7	1.391 (2)
F2—C14	1.3393 (18)	C6—C10	1.490 (2)
F3—C13	1.3476 (17)	C7—C8	1.3954 (19)
F4—C12	1.3391 (18)	C8—C9	1.494 (2)
F5—C11	1.3403 (19)	C9—H9A	0.9700
F6—C18	1.3407 (19)	C9—H9B	0.9700
F7—C19	1.3411 (19)	C9—H9C	0.9700
F8—C20	1.347 (3)	C9—H9D	0.9700
N1—C1	1.3331 (18)	C9—H9E	0.9700
N1—N2	1.353 (2)	C9—H9F	0.9700
N2—C3	1.3405 (19)	C10—H10A	0.9700
N2—H2N	0.9028	C10—H10B	0.9700
N3—C8	1.3328 (18)	C10—H10C	0.9700
N3—N4	1.3548 (18)	C10—H10D	0.9700
N3—H3N	0.8510	C10—H10E	0.9700
N4—C6	1.3398 (18)	C10—H10F	0.9700
N4—H4N	0.8916	C11—C12	1.381 (2)
C1—C2	1.406 (2)	C11—C16	1.391 (2)
C1—C5	1.487 (2)	C12—C13	1.371 (3)
C2—C3	1.384 (2)	C13—C14	1.373 (2)
C2—C7	1.4721 (18)	C14—C15	1.379 (2)
C3—C4	1.486 (2)	C15—C16	1.386 (2)
C4—H4A	0.9700	C17—C18	1.382 (2)
C4—H4B	0.9700	C17—C18^i	1.382 (2)
C4—H4C	0.9700	C18—C19	1.378 (2)
C4—H4D	0.9700	C19—C20	1.369 (2)
C4—H4E	0.9700	C20—C19^i	1.369 (2)
C16—O1—H1O	115.1	C8—C9—H9C	109.5
C17—O2—H2O	119.2	H9A—C9—H9C	109.5
C1—N1—N2	105.46 (12)	H9B—C9—H9C	109.5
C3—N2—N1	112.50 (12)	C8—C9—H9D	109.5
C3—N2—H2N	127.1	C8—C9—H9E	109.5
N1—N2—H2N	119.9	H9D—C9—H9E	109.5
C8—N3—N4	108.61 (11)	C8—C9—H9F	109.5
C8—N3—H3N	135.5	H9D—C9—H9F	109.5
N4—N3—H3N	115.8	H9E—C9—H9F	109.5
C6—N4—N3	108.88 (12)	C6—C10—H10A	109.5
C6—N4—H4N	133.9	C6—C10—H10B	109.5
N3—N4—H4N	117.2	H10A—C10—H10B	109.5
N1—C1—C2	110.23 (14)	C6—C10—H10C	109.5
N1—C1—C5	121.20 (14)	H10A—C10—H10C	109.5
C2—C1—C5	128.57 (13)	H10B—C10—H10C	109.5
C3—C2—C1	105.53 (13)	C6—C10—H10D	109.5
C3—C2—C7	126.47 (14)	C6—C10—H10E	109.5
C1—C2—C7	128.00 (14)	H10D—C10—H10E	109.5
N2—C3—C2	106.29 (14)	C6—C10—H10F	109.5
N2—C3—C4	122.42 (14)	H10D—C10—H10F	109.5
C2—C3—C4	131.29 (14)	H10E—C10—H10F	109.5
C3—C4—H4A	109.5	F5—C11—C12	119.58 (14)
C3—C4—H4B	109.5	F5—C11—C16	118.60 (13)
H4A—C4—H4B	109.5	C12—C11—C16	121.80 (15)
C3—C4—H4C	109.5	F4—C12—C13	119.89 (14)
H4A—C4—H4C	109.5	F4—C12—C11	120.37 (16)
H4B—C4—H4C	109.5	C13—C12—C11	119.72 (15)
C3—C4—H4D	109.5	F3—C13—C12	120.29 (15)
C3—C4—H4E	109.5	F3—C13—C14	119.75 (16)
H4D—C4—H4E	109.5	C12—C13—C14	119.96 (14)
C3—C4—H4F	109.5	F2—C14—C13	120.10 (14)
H4D—C4—H4F	109.5	F2—C14—C15	119.97 (14)
H4E—C4—H4F	109.5	C13—C14—C15	119.92 (15)
C1—C5—H5A	109.5	F1—C15—C14	119.15 (14)
C1—C5—H5B	109.5	F1—C15—C16	119.06 (12)
H5A—C5—H5B	109.5	C14—C15—C16	121.77 (14)
C1—C5—H5C	109.5	O1—C16—C15	124.20 (13)
H5A—C5—H5C	109.5	O1—C16—C11	118.94 (13)
H5B—C5—H5C	109.5	C15—C16—C11	116.82 (13)
N4—C6—C7	108.47 (12)	O2—C17—C18	121.89 (10)
N4—C6—C10	123.07 (13)	O2—C17—C18^i	121.89 (10)
C7—C6—C10	128.42 (13)	C18—C17—C18^i	116.2 (2)
C6—C7—C8	105.20 (12)	F6—C18—C19	118.54 (16)
C6—C7—C2	126.95 (12)	F6—C18—C17	119.22 (15)
C8—C7—C2	127.85 (13)	C19—C18—C17	122.23 (16)
N3—C8—C7	108.84 (13)	F7—C19—C20	119.94 (15)
N3—C8—C9	122.01 (13)	F7—C19—C18	119.99 (15)
C7—C8—C9	129.15 (13)	C20—C19—C18	120.07 (16)
C8—C9—H9A	109.5	F8—C20—C19	120.40 (10)
C8—C9—H9B	109.5	F8—C20—C19^i	120.40 (10)
H9A—C9—H9B	109.5	C19—C20—C19^i	119.2 (2)
C1—N1—N2—C3	0.31 (17)	C16—C11—C12—C13	0.0 (3)
C8—N3—N4—C6	−0.07 (18)	F4—C12—C13—F3	−2.5 (3)
N2—N1—C1—C2	−0.33 (17)	C11—C12—C13—F3	179.10 (15)
N2—N1—C1—C5	−179.38 (14)	F4—C12—C13—C14	177.95 (16)
N1—C1—C2—C3	0.24 (17)	C11—C12—C13—C14	−0.5 (3)
C5—C1—C2—C3	179.21 (16)	F3—C13—C14—F2	0.5 (2)
N1—C1—C2—C7	179.98 (14)	C12—C13—C14—F2	−179.95 (15)
C5—C1—C2—C7	−1.1 (3)	F3—C13—C14—C15	−179.07 (15)
N1—N2—C3—C2	−0.16 (18)	C12—C13—C14—C15	0.5 (3)
N1—N2—C3—C4	−179.62 (15)	F2—C14—C15—F1	−0.9 (2)
C1—C2—C3—N2	−0.05 (17)	C13—C14—C15—F1	178.67 (14)
C7—C2—C3—N2	−179.79 (14)	F2—C14—C15—C16	−179.59 (14)
C1—C2—C3—C4	179.34 (17)	C13—C14—C15—C16	0.0 (2)
C7—C2—C3—C4	−0.4 (3)	F1—C15—C16—O1	3.3 (2)
N3—N4—C6—C7	−0.47 (18)	C14—C15—C16—O1	−177.95 (15)
N3—N4—C6—C10	177.19 (15)	F1—C15—C16—C11	−179.15 (14)
N4—C6—C7—C8	0.80 (17)	C14—C15—C16—C11	−0.4 (2)
C10—C6—C7—C8	−176.70 (17)	F5—C11—C16—O1	−0.3 (2)
N4—C6—C7—C2	−178.44 (15)	C12—C11—C16—O1	178.13 (15)
C10—C6—C7—C2	4.1 (3)	F5—C11—C16—C15	−177.98 (14)
C3—C2—C7—C6	71.6 (2)	C12—C11—C16—C15	0.5 (2)
C1—C2—C7—C6	−108.09 (19)	O2—C17—C18—F6	−1.5 (3)
C3—C2—C7—C8	−107.48 (19)	C18^i—C17—C18—F6	179.96 (12)
C1—C2—C7—C8	72.8 (2)	O2—C17—C18—C19	179.46 (19)
N4—N3—C8—C7	0.59 (18)	C18^i—C17—C18—C19	0.9 (3)
N4—N3—C8—C9	−178.90 (16)	F6—C18—C19—F7	0.0 (3)
C6—C7—C8—N3	−0.85 (18)	C17—C18—C19—F7	179.11 (18)
C2—C7—C8—N3	178.38 (15)	F6—C18—C19—C20	−179.47 (19)
C6—C7—C8—C9	178.59 (19)	C17—C18—C19—C20	−0.4 (3)
C2—C7—C8—C9	−2.2 (3)	F7—C19—C20—F8	−0.1 (3)
F5—C11—C12—F4	0.0 (2)	C18—C19—C20—F8	179.4 (2)
C16—C11—C12—F4	−178.44 (15)	F7—C19—C20—C19^i	−179.66 (14)
F5—C11—C12—C13	178.40 (15)	C18—C19—C20—C19^i	−0.2 (4)

Symmetry code: (i) x, −y+3/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N1	0.90	1.71	2.5975 (16)	168
O2—H2O···N4^i	0.92	1.90	2.7768 (16)	158
N2—H2N···O1^ii	0.90	2.10	2.8719 (17)	143
N3—H3N···N3^i	0.85	2.01	2.859 (2)	176
N4—H4N···O2	0.89	1.92	2.7768 (16)	161

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