On substituted pyrazole derivatives. I. 3-Methyl-4-[(Z)-2-(4-methyl­phenyl)hydrazin-1-yl­idene]-1-(3-nitro­phenyl)-1H-pyrazol-5(4H)-one and 3-methyl-4-[(Z)-2-(4-methyl­phenyl)hydrazin-1-yl­idene]-1-[4-(tri­fluoro­methyl)phenyl]-1H-pyrazol-5(4H)-one

The title substituted pyrazole derivatives, C₁₇H₁₅N₅O₃ and C₁₈H₁₅F₃N₄O, share most of their mol­ecular features, in particular the hydrazinylidene (-HN-N=) rather than the diazene (-N=N-) tautomeric form, and differ only in the substituents (NO₂ and CF₃) on one of the outer phenyl rings. The mol­ecular units are basically planar, with the rotation of the phenyl rings being hindered by the presence of two intra­molecular hydrogen bonds having the keto O atom as acceptor. In both structures, the packing is governed by weak C-H...O, C-H...[pi] and [pi]-[pi] inter­actions. The subtle way in which minor structural differences lead to rather different supra­molecular structures is analysed.

S1. Introduction

Substituted pyrazoles have been the target of extensive research in a diversity of areas, e.g. biology, chemistry, pharmacology and medicine. From the biological side, the inter­est promoted by this type of compound has led to an important class of bioactive molecules in the pharmaceutical industry that includes such blockbuster drugs as Celebrex (Penning et al., 1997) and Viagra (Terrett et al., 1996). Pyrazole heterocycles are also of pharmacological inter­est as anti-anxiety, anti­pyretic, analgesic, anti-inflamatory, anti­parasitic and anti­microbial drugs (Elguero et al., 2002), and some related derivatives have been described as potent PDE4B inhibitors (Card et al., 2005).

From the chemical side, pyrazole derivatives have been used as ligands for obtaining transition metal complexes, since the heterocycle may coordinate to the metal directly via one or both vicinal N atoms (Rojas et al., 2004).

Considering the synthetic route, we have been able to obtain two 4-hydrazinyl­idene-substituted 1H-pyrazol-5-ones [see a and b in Scheme 1 (top) (Bustos et al., 2009), where a is in principle a more rigid structure than b]. The hydrazinyl­idene group in a may generate diazenyl/hydrazinyl­idene tautomers, in both of which the keto O atom acts as an acceptor. In these tautomeric forms, a and a' (Scheme 1, bottom), the hydrazinyl­idene group adopts either a hydrazinyl­idene (–HN—N═) or diazenyl (–N═N–) form. Only one inter­nal double bond is present in the pyrazole ring in the first form (a), while two formal and conjugated double bonds are formed in the second form (a'). In this case, the a' molecule gains stability because the pyrazole ring becomes an aromatic system, so that the stability of both species, viz. a and a', is markedly dependent on the strength of the resonance-assisted hydrogen bond (RAHB).

The present report, the first of an intended series of related papers describing the structures obtained, grouped according to their a(a') or b character, presents two new pyrazole compounds (denoted class a in our nomenclature above), viz. 3-methyl-4-[(Z)-2-(4-methyl­phenyl)­hydrazin-1-yl­idene]-1-(3-nitro­phenyl)-1H-pyrazol-5(4H)-one, (I), with two independent molecules in the asymetric unit, and 3-methyl-4-[(Z)-2-(4-methyl­phenyl)­hydrazin-1-yl­idene]-1-[4-(tri­fluoro­methyl)­phenyl]-1H-pyrazol-5(4H)-one, (II) (Scheme 2).

S2. Experimental

S2.1. Synthesis and crystallization

Chemicals Reagents (ethyl aceto­acetate, sodium nitrite, sodium acetate, sodium hydroxide, 4-methyl­aniline, 4-nitro­phenyhydrazine, 4-(tri­fluoro­phenyl)­hydrazine and glacial acetic acid) and solvents (ethanol, tetra­hydro­furan, chloro­form and chloro­form-d) were procured from common commercial sources (Merck Chemical and Sigma–Aldrich) and used without further purification.

Preparation of the precursor Ethyl (Z)-3-oxo-2-(2-p-tolyl­hydrazinyl­idene)butano­ate was prepared according to the method recommended in the literature (Yao, 1964; Bertolasi et al., 1999; Bustos et al., 2009) and was recrystallized from ethanol.

Preparation of (I) and (II) These compounds were prepared by mixing pure ethyl (Z)-3-oxo-2-(2-p-tolyl­hydrazinyl­idene)butano­ate (2.48 g, 10 mmol), aryl­hydrazine (10 mmol) {(3-nitro­phenyl)­hydrazine (1.85 g, 97%) for (I) and [4-(tri­fluoro­methyl)­phenyl]­hydrazine (1.68 g, 96%) for (II)}, glacial acetic acid (5 ml) and ethanol (30 ml). The mixture was stirred and heated under reflux near the boiling point, and a yellow–orange solid precipitate was obtained after 36 h. The reaction mixture was cooled at 263 K for 2 h and the solid which formed was filtered off by suction at room temperature, washed with an abundant qu­antity of water (500 ml) and dried in a vacuum oven at 313 K for 12 h. Single crystals suitable for diffraction studies were obtained by recrystallization of each compound from an ethanol–tetra­hydro­furan (1:1 v/v) mixture.

Analysis of (I) and (II) For (I): yield 75.3% crude. Elemental analysis, calculated (%) for C₁₇H₁₅N₅O₃: C 60.53, H 4.48, N 20.76; found: C 60.72, H 4.63, N 20.77. For (II): yield 61.4% crude. Elemental analysis, calculated (%) for C₁₈H₁₅F₃N₄O: C 60.00, H 4.20, N 15.55; found : C 60.38, H 4.42, N 16.02.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were originally found in difference maps, but they were treated differently in the refinement. N-bound H atoms were refined with restrained N—H distances [0.85 (1) Å] and free U_iso values. C-bound H atoms were repositioned in their expected positions and allowed to ride (methyl C—H = 0.96 Å and aromatic C—H = 0.93 Å) and the methyl? groups were allowed to rotate around their C—C bond. Riding H atoms were assigned a U_iso(H) value of xU_eq(C), where x is 1.2 for aromatic and 1.5 for methyl H atoms.

S3. Results and discussion

In both (I) and (II) (Scheme 2), the nucleus is a type a pyrazole (see Scheme 1, bottom).

In (I), the outer substituents in the benzene rings are a 4-methyl group on one side and a 3-nitro group on the other. The compound crystallizes in the monoclinic space group P2₁/c with two molecules in the asymmetric unit (Z' = 2), viz. molecule (IA) (Fig. 1a) and molecule (IB) (Fig. 1b). The two units have only slight differences, as disclosed by the small mean unweighted deviation in their least-squares superposition, 0.18 (2) Å. PLATON (Spek, 2009) did not detect any obvious pseudosymmetry in the structure.

The overall molecular structure of (II) differs from that of (I) only in the presence of a 4-tri­fluoro­methyl substituent on benzene ring 2 (see Figs. 1 and 2 for ring codes), but it has a very different crystal structure.

Both structures are very similar with respect to bond distances and angles, which do not deviate from the expected values and therefore will not be discussed in depth. However, we would like to stress for future reference the single–double bond sequence in the pyrazole rings (Table 2), clearly consistent with type a rather than type b nuclei, which will be the subject of a future contribution.

Molecules (I) and (II) are basically flat, but with slight individual deviations from coplanarity of lateral rings 2 and 3 with respect to the central pyrazole (ring 1). Thus, in molecule (IA), the dihedral angles between the planes of rings 1A/2A and 1A/3A are 5.25 (11) and 2.17 (11)°, respectively, while in the molecule (IB) they are a little larger, viz. 6.26 (11) and 10.14 (11)°. A similar situation is found with the out-of-plane rotation of the nitro group with respect to ring 2, which is 1.92 (11)° in molecule (IA) but 14.08 (12)° in molecule (IB). The corresponding angles for (II) [1/2 = 8.47 (17)° and 1/3 = 11.62 (18)°] show it to be slightly more out-of-plane.

Even if noticeable, these angles can be considered small if the (in principle) free rotation of the lateral rings involved is considered. Thus, it is tempting to ascribe this coplanarity to the presence of keto atom O1 at C7, which tends to make two intra­molecular hydrogen bonds, rendering the coplanar arrangement more favourable and thus facilitating the hindering of any eventual rotation of the benzene ring around the N1—C1 bond.

However, a search of the Cambridge Structural Database (CSD, Version 5.34; Allen, 2002) suggests that this limitation can be easily overcome; there are many reported structures which have the same keto environment, but where the benzene and pyrazole rings are far from being coplanar [e.g. 27.60 (2)° (CSD refcode JEBMEI; Connor et al., 1990) and 23.44 (3)° (CSD refcode YICBIV; Skoweranda et al., 1994)]. This suggests that the role of the weak C—H···O hydrogen bond in providing for coplanarity will be relevant only in the absence of other stronger contacts, as is the case in the molecules of (I) and (II).

Perhaps the most inter­esting aspect in the comparison of these two structures lies in the effect which the inter­play of the weak inter­molecular inter­actions present (see hydrogen-bonding details in Table 3 and π–π inter­actions in Table 4) has on the supra­molecular disposition.

In both structures, there are intra­molecular hydrogen bonds for which the keto O atom is an acceptor [O1A and O1B in (I) (Fig. 1), and O1 in (II) (Fig. 2)] and these contribute to the general planarity of the molecules. The hydrazinyl­idene N—H group is involved in these contacts, a fact which probably inhibits further N—H inter­molecular involvement.

The rest of the hydrogen-bonding inter­actions are of the C—H···O type, and give rise to very different substructures.

In the case of (I), the three remaining hydrogen bonds (entries 5, 6 and 7 in Table 3) are parallel to the molecular planes and define two types of independent coplanar slab, parallel to [201] and running along [010] (Fig. 3, left). These slabs are composed of either type (IA) or type (IB) molecules only. In the case of slab A, two different inter­actions are operative, having C3A—H3A and C11A—H11A groups as donors, while only the C3B—H3B group is operative in slab B, the remaining contact being too long for any real significance. In all cases, the H-atom acceptors are nitro O atoms. A striking feature is the planar disposition of this juxtaposition of slabs into a common [201] substructure, even in the absence of any `in-plane' hydrogen-bonding inter­action directly connecting the slabs. The planarity of these substructures (mean deviation from the least-squares plane = 0.214 Å) can be seen in Fig. 3 (right), which shows them side-on.

In (II), the replacement of an active nitro group by an almost inert tri­fluoro­methyl group changes the type of hydrogen-bonded substructure generated. There is only one `in-plane' inter­molecular C—H···O hydrogen bond, also having the fully engaged keto O1 atom as acceptor, which joins pairs of inversion-related molecules and gives rise to weakly bound dimeric units. These dimers act as elemental packing elements in the structure (Fig. 4a). As already noticed in (I), the dimers assemble into planar substructures, this time parallel to [211] (Fig. 4b), with a mean deviation from the least-squares plane of 0.121 Å. Currently, we cannot find any obvious explanation for this particular orientational preference, since it seems that there are no direct inter­actions between units, at least of the usual type herein discussed.

The reasons behind the two drastically different hydrogen-bonding schemes, viz. the presence/absence of active hydrogen-bonding acceptors, are not applicable to π–π bonding, as it derives from two very similar type a nuclei (see Scheme 1). And, in fact, the resulting inter­actions are very alike, as Fig. 5 and Table 4 suggest. However, the way in which they complement the above hydrogen-bonded structures gives rise to different supra­molecular organizations.

In (I), π–π bonds connect molecules in a (IA)···(IA), (IB)···(IB) and (IA)···(IB) fashion, `mixing' them as shown in Fig. 5(a). These stacking inter­actions define columns embedded in the [001] plane, but running in different directions according to their z coordinate, viz. [110] for z ~0 or [110] for z ~0.5 (see Figs. S1a and S1b in Supporting information). This `criss-cross' disposition of π-bonded columns provides an (indirect) linkage between the coplanar hydrogen-bonded slabs, resulting in a fully integrated three-dimensional structure.

In the case of (II), the supra­molecular structure results from the stacking of hydrogen-bonded dimers along [100], generating columnar arrays (see Figs. S2a and S2b in Supporting information). Neighbouring one-dimensional substructures further inter­penetrate along the b axis to form broad two-dimensional structures parallel to [001] (see Fig. S2c in Supporting information).

Summarizing, (I) and (II) are examples of very similar molecular units giving rise to similar weak inter­molecular inter­actions, but their minor molecular differences lead in a subtle way to extremely different supra­molecular organization.

Related literature

For related literature, see: Allen (2002); Bertolasi et al. (1999); Bustos et al. (2009); Card (2005); Connor et al. (1990); Elguero et al. (2002); Penning (1997); Rojas et al. (2004); Skoweranda et al. (1994); Spek (2009); Terrett et al. (1996); Yao (1964).

Computing details

For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. The structures of the two independent molecules in (I), (a) molecule (IA) and (b) molecule (IB), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level. The intramolecular hydrogen bonds accepted by the keto group are shown as dashed lines. Purple labels indicate ring numbering.
	Fig. 2. The structure of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level. The intramolecular hydrogen bonds accepted by the keto group are shown as dashed lines. Purple labels indicate ring numbering.
	Fig. 3. Packing views of (I), showing (left) the coplanar [201] slabs running along [010], composed of type A or type B molecules. Note the absence of in-plane connections between the slabs. (Right) The same view as on the left but rotated along the vertical axis, disclosing the planarity of the whole group. Dashed lines indicate hydrogen bonds. [Symmetry codes: (i) -x + 1, y + 1/2, -z - 1/2; (ii) -x, y + 1/2, -z + 3/2; (iii) -x + 1, y - 1/2, -z - 1/2.]
	Fig. 4. Packing views of (II), showing (a) the coplanar dimeric units, defining a two-dimensional array. Note the absence of in-plane connections between the dimers. (b) The same view as in (a) but rotated along the vertical axis, disclosing the planarity of the assembly of dimers. Dashed lines indicate hydrogen bonds. [Symmetry code: (i) -x + 1, -y + 2, -z.]
	Fig. 5. (a) π–π interaction scheme for (I). [Symmetry codes: (iv) x, -y + 3/2, z - 1/2; (v) -x + 1, -y + 1, -z + 1; (vi) -x, y - 1/2, z - 1/2; (vii) -x, -y + 1, -z; (viii) x - 1, y, z - 1.] (b) π–π interaction scheme for (II). [Symmetry codes: (iii) -x + 1, -y + 1, -z; (iv) -x, -y + 1, -z; (v) x - 1, y, z - 1; (vi) x + 1, y, z + 1; (vii) -x + 2, -y + 1, -z + 2.] Inversion centres are represented as heavy red dots and π–π bonds as double-dashed lines.

(I) 3-Methyl-4-[(Z)-2-(4-methylphenyl)hydrazin-1-ylidene]-1-(3-nitrophenyl)-1H-pyrazol-5(4H)-one

Crystal data

C17H15N5O3	F(000) = 1408
Mr = 337.34	Dx = 1.378 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4994 reflections
a = 16.474 (4) Å	θ = 3.6–25.9°
b = 13.189 (3) Å	µ = 0.10 mm^−1
c = 15.113 (4) Å	T = 295 K
β = 98.031 (4)°	Plate, orange
V = 3251.6 (14) Å^3	0.29 × 0.26 × 0.05 mm
Z = 8

Data collection

Bruker SMART CCD area-detector diffractometer	7170 independent reflections
Radiation source: fine-focus sealed tube	3760 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.059
CCD rotation images, thin slices scans	θmax = 27.8°, θmin = 2.0°
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2002)	h = −21→21
Tmin = 0.96, Tmax = 1.00	k = −17→17
26277 measured reflections	l = −18→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0388P)^2 + 0.8504P] where P = (Fo^2 + 2Fc^2)/3
7170 reflections	(Δ/σ)max < 0.001
463 parameters	Δρmax = 0.16 e Å^−3
2 restraints	Δρmin = −0.14 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq
O1A	0.42527 (9)	0.45000 (10)	0.41784 (10)	0.0668 (4)
N1A	0.38232 (10)	0.28933 (12)	0.45847 (11)	0.0533 (4)
N2A	0.33754 (11)	0.24900 (13)	0.52406 (11)	0.0578 (5)
N3A	0.33459 (10)	0.50859 (13)	0.57314 (11)	0.0554 (4)
N4A	0.36403 (11)	0.58773 (13)	0.53622 (12)	0.0567 (5)
C1A	0.40897 (12)	0.22173 (14)	0.39565 (13)	0.0495 (5)
C2A	0.39797 (13)	0.11809 (15)	0.40490 (15)	0.0643 (6)
H2A	0.3727	0.0936	0.4519	0.077*
C3A	0.42422 (14)	0.05125 (16)	0.34476 (16)	0.0694 (7)
H3A	0.4161	−0.0179	0.3516	0.083*
C4A	0.46235 (12)	0.08529 (16)	0.27458 (15)	0.0598 (6)
H4A	0.4809	0.0405	0.2343	0.072*
C5A	0.47171 (12)	0.18848 (15)	0.26686 (13)	0.0519 (5)
C6A	0.44594 (12)	0.25808 (14)	0.32526 (13)	0.0498 (5)
H6A	0.4532	0.3273	0.3175	0.060*
C7A	0.39004 (12)	0.39327 (15)	0.46468 (14)	0.0526 (5)
C8A	0.34703 (12)	0.41884 (15)	0.54005 (13)	0.0510 (5)
C9A	0.31696 (12)	0.32522 (16)	0.57087 (13)	0.0539 (5)
C10A	0.35176 (12)	0.68640 (15)	0.56808 (13)	0.0510 (5)
C11A	0.38235 (12)	0.76820 (16)	0.52691 (13)	0.0560 (5)
H11A	0.4106	0.7580	0.4785	0.067*
C12A	0.37141 (13)	0.86508 (16)	0.55692 (14)	0.0604 (6)
H12A	0.3927	0.9192	0.5281	0.072*
C13A	0.32965 (13)	0.88463 (16)	0.62874 (14)	0.0604 (6)
C14A	0.29904 (14)	0.80134 (18)	0.66827 (15)	0.0703 (7)
H14A	0.2702	0.8117	0.7162	0.084*
C15A	0.30936 (14)	0.70281 (17)	0.63967 (14)	0.0648 (6)
H15A	0.2881	0.6485	0.6682	0.078*
C16A	0.26713 (14)	0.31186 (18)	0.64507 (14)	0.0699 (6)
H16A	0.2552	0.2412	0.6516	0.105*
H16B	0.2168	0.3489	0.6318	0.105*
H16C	0.2973	0.3368	0.6997	0.105*
C17A	0.31926 (16)	0.99106 (17)	0.66177 (18)	0.0851 (8)
H17A	0.2620	1.0076	0.6552	0.128*
H17B	0.3470	1.0377	0.6275	0.128*
H17C	0.3422	0.9956	0.7236	0.128*
N5A	0.51212 (12)	0.22635 (16)	0.19257 (13)	0.0681 (5)
O2A	0.51939 (13)	0.31712 (13)	0.18322 (12)	0.0977 (6)
O3A	0.53616 (14)	0.16372 (14)	0.14291 (13)	0.1096 (7)
O1B	0.08098 (9)	0.74119 (10)	0.08544 (11)	0.0706 (4)
N1B	0.11792 (10)	0.57896 (12)	0.03954 (12)	0.0557 (4)
N2B	0.15893 (10)	0.53873 (13)	−0.02901 (12)	0.0594 (5)
N3B	0.16947 (10)	0.80061 (13)	−0.07034 (11)	0.0573 (5)
N4B	0.14117 (11)	0.87854 (13)	−0.03034 (13)	0.0584 (5)
C1B	0.08266 (12)	0.51111 (14)	0.09513 (13)	0.0511 (5)
C2B	0.08585 (13)	0.40752 (15)	0.08008 (15)	0.0623 (6)
H2B	0.1125	0.3830	0.0341	0.075*
C3B	0.04954 (14)	0.34054 (16)	0.13314 (15)	0.0654 (6)
H3B	0.0518	0.2714	0.1218	0.078*
C4B	0.01026 (13)	0.37380 (16)	0.20217 (14)	0.0595 (6)
H4B	−0.0142	0.3287	0.2376	0.071*
C5B	0.00878 (12)	0.47643 (16)	0.21644 (13)	0.0528 (5)
C6B	0.04438 (12)	0.54672 (15)	0.16544 (14)	0.0549 (5)
H6B	0.0427	0.6157	0.1779	0.066*
C7B	0.11414 (13)	0.68380 (15)	0.03686 (15)	0.0553 (5)
C8B	0.15707 (12)	0.70982 (15)	−0.03837 (14)	0.0528 (5)
C9B	0.18177 (12)	0.61597 (16)	−0.07387 (14)	0.0562 (5)
C10B	0.14967 (12)	0.97824 (14)	−0.06165 (13)	0.0488 (5)
C11B	0.10728 (13)	1.05447 (15)	−0.02580 (14)	0.0576 (6)
H11B	0.0747	1.0397	0.0181	0.069*
C12B	0.11329 (13)	1.15302 (15)	−0.05537 (14)	0.0569 (5)
H12B	0.0837	1.2037	−0.0315	0.068*
C13B	0.16187 (12)	1.17821 (14)	−0.11909 (13)	0.0490 (5)
C14B	0.20397 (13)	1.10016 (15)	−0.15412 (13)	0.0551 (5)
H14B	0.2371	1.1151	−0.1974	0.066*
C15B	0.19816 (13)	1.00098 (14)	−0.12665 (14)	0.0547 (5)
H15B	0.2266	0.9499	−0.1516	0.066*
C16B	0.22705 (14)	0.60244 (18)	−0.15191 (15)	0.0736 (7)
H16D	0.2342	0.5314	−0.1624	0.110*
H16E	0.2797	0.6345	−0.1397	0.110*
H16F	0.1964	0.6327	−0.2039	0.110*
C17B	0.16895 (14)	1.28664 (15)	−0.14967 (15)	0.0690 (6)
H17D	0.1320	1.3287	−0.1222	0.103*
H17E	0.1552	1.2900	−0.2135	0.103*
H17F	0.2241	1.3100	−0.1328	0.103*
H4BN	0.1160 (13)	0.8659 (19)	0.0141 (12)	0.097 (10)*
H4AN	0.3938 (12)	0.5793 (18)	0.4950 (12)	0.087 (9)*
N5B	−0.03253 (12)	0.51500 (16)	0.28996 (13)	0.0670 (5)
O2B	−0.02081 (11)	0.60306 (13)	0.31440 (11)	0.0874 (5)
O3B	−0.07716 (12)	0.45663 (15)	0.32422 (12)	0.0953 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1A	0.0868 (11)	0.0460 (9)	0.0738 (10)	−0.0084 (8)	0.0333 (9)	−0.0026 (7)
N1A	0.0650 (11)	0.0429 (10)	0.0553 (10)	−0.0008 (8)	0.0205 (9)	0.0017 (8)
N2A	0.0647 (12)	0.0555 (11)	0.0559 (11)	−0.0004 (9)	0.0178 (9)	0.0083 (9)
N3A	0.0574 (11)	0.0541 (11)	0.0550 (11)	−0.0005 (9)	0.0094 (9)	−0.0017 (9)
N4A	0.0636 (12)	0.0516 (11)	0.0585 (12)	0.0001 (9)	0.0212 (10)	−0.0085 (9)
C1A	0.0499 (12)	0.0398 (11)	0.0596 (13)	0.0004 (9)	0.0105 (10)	0.0020 (10)
C2A	0.0780 (16)	0.0422 (13)	0.0796 (16)	0.0013 (11)	0.0345 (13)	0.0064 (11)
C3A	0.0770 (16)	0.0398 (12)	0.0976 (19)	−0.0042 (11)	0.0332 (14)	0.0007 (12)
C4A	0.0606 (14)	0.0490 (13)	0.0728 (15)	0.0006 (10)	0.0203 (12)	−0.0088 (11)
C5A	0.0582 (13)	0.0448 (13)	0.0537 (13)	−0.0031 (9)	0.0115 (10)	0.0011 (10)
C6A	0.0606 (13)	0.0376 (11)	0.0508 (12)	−0.0020 (9)	0.0067 (10)	0.0010 (9)
C7A	0.0590 (13)	0.0430 (12)	0.0572 (13)	0.0001 (10)	0.0127 (11)	0.0022 (10)
C8A	0.0593 (13)	0.0462 (13)	0.0481 (12)	0.0066 (10)	0.0094 (10)	−0.0019 (10)
C9A	0.0572 (13)	0.0560 (13)	0.0487 (12)	0.0033 (10)	0.0079 (10)	0.0018 (10)
C10A	0.0547 (13)	0.0512 (13)	0.0479 (12)	0.0040 (10)	0.0097 (10)	−0.0085 (10)
C11A	0.0609 (14)	0.0602 (14)	0.0496 (13)	0.0032 (11)	0.0169 (11)	−0.0042 (11)
C12A	0.0700 (15)	0.0530 (14)	0.0584 (14)	0.0047 (11)	0.0099 (12)	0.0011 (11)
C13A	0.0661 (15)	0.0561 (14)	0.0589 (14)	0.0069 (11)	0.0090 (12)	−0.0096 (11)
C14A	0.0799 (17)	0.0702 (16)	0.0661 (15)	0.0020 (13)	0.0291 (13)	−0.0141 (13)
C15A	0.0782 (16)	0.0572 (14)	0.0631 (14)	−0.0018 (12)	0.0241 (12)	−0.0068 (11)
C16A	0.0737 (16)	0.0816 (17)	0.0579 (14)	−0.0031 (13)	0.0211 (12)	0.0038 (12)
C17A	0.098 (2)	0.0629 (16)	0.098 (2)	0.0100 (14)	0.0229 (16)	−0.0249 (14)
N5A	0.0852 (14)	0.0613 (13)	0.0621 (13)	−0.0045 (11)	0.0257 (11)	−0.0006 (11)
O2A	0.1528 (18)	0.0595 (11)	0.0921 (13)	−0.0133 (11)	0.0568 (12)	0.0068 (10)
O3A	0.175 (2)	0.0775 (13)	0.0941 (14)	−0.0001 (12)	0.0806 (14)	−0.0112 (11)
O1B	0.0815 (11)	0.0437 (9)	0.0933 (12)	0.0064 (8)	0.0354 (9)	−0.0007 (8)
N1B	0.0600 (11)	0.0402 (10)	0.0695 (12)	0.0026 (8)	0.0185 (9)	−0.0009 (9)
N2B	0.0644 (12)	0.0496 (11)	0.0652 (12)	0.0023 (9)	0.0127 (10)	−0.0032 (9)
N3B	0.0560 (11)	0.0477 (11)	0.0671 (12)	0.0028 (9)	0.0051 (9)	−0.0003 (9)
N4B	0.0651 (12)	0.0471 (11)	0.0647 (12)	−0.0005 (9)	0.0153 (10)	0.0060 (10)
C1B	0.0524 (13)	0.0421 (12)	0.0582 (13)	0.0017 (9)	0.0052 (10)	0.0016 (10)
C2B	0.0775 (16)	0.0425 (12)	0.0681 (15)	0.0040 (11)	0.0140 (12)	−0.0043 (11)
C3B	0.0851 (17)	0.0397 (12)	0.0720 (15)	−0.0036 (11)	0.0137 (13)	0.0001 (11)
C4B	0.0666 (15)	0.0495 (14)	0.0616 (14)	−0.0030 (11)	0.0060 (12)	0.0053 (11)
C5B	0.0537 (13)	0.0510 (13)	0.0527 (13)	0.0069 (10)	0.0040 (10)	0.0015 (10)
C6B	0.0620 (14)	0.0405 (12)	0.0612 (14)	0.0063 (10)	0.0056 (11)	−0.0003 (10)
C7B	0.0519 (13)	0.0406 (12)	0.0734 (15)	0.0020 (10)	0.0084 (11)	0.0021 (11)
C8B	0.0518 (13)	0.0418 (12)	0.0646 (14)	−0.0003 (10)	0.0072 (11)	0.0030 (10)
C9B	0.0541 (13)	0.0491 (13)	0.0647 (14)	0.0001 (10)	0.0054 (11)	0.0004 (11)
C10B	0.0530 (12)	0.0413 (11)	0.0517 (12)	−0.0030 (9)	0.0064 (10)	0.0026 (10)
C11B	0.0643 (14)	0.0535 (14)	0.0590 (14)	−0.0047 (11)	0.0222 (11)	0.0017 (11)
C12B	0.0625 (14)	0.0490 (13)	0.0624 (14)	0.0034 (10)	0.0197 (11)	−0.0063 (10)
C13B	0.0537 (13)	0.0442 (12)	0.0497 (12)	−0.0001 (9)	0.0094 (10)	0.0009 (9)
C14B	0.0652 (14)	0.0532 (13)	0.0507 (12)	0.0010 (11)	0.0208 (11)	0.0027 (10)
C15B	0.0645 (14)	0.0431 (12)	0.0586 (13)	0.0068 (10)	0.0159 (11)	−0.0009 (10)
C16B	0.0830 (17)	0.0678 (15)	0.0741 (16)	0.0021 (13)	0.0255 (14)	−0.0039 (12)
C17B	0.0856 (17)	0.0512 (13)	0.0722 (16)	0.0039 (12)	0.0187 (13)	0.0046 (11)
N5B	0.0803 (14)	0.0590 (13)	0.0618 (12)	0.0074 (11)	0.0104 (11)	0.0026 (11)
O2B	0.1230 (15)	0.0570 (11)	0.0868 (12)	0.0136 (10)	0.0306 (11)	−0.0055 (9)
O3B	0.1183 (15)	0.0946 (14)	0.0796 (12)	−0.0180 (12)	0.0375 (11)	−0.0044 (10)

Geometric parameters (Å, º)

O1A—C7A	1.230 (2)	O1B—C7B	1.234 (2)
N1A—C7A	1.379 (2)	N1B—C7B	1.384 (2)
N1A—C1A	1.416 (2)	N1B—C1B	1.407 (2)
N1A—N2A	1.419 (2)	N1B—N2B	1.417 (2)
N2A—C9A	1.301 (2)	N2B—C9B	1.308 (2)
N3A—N4A	1.308 (2)	N3B—N4B	1.311 (2)
N3A—C8A	1.312 (2)	N3B—C8B	1.318 (2)
N4A—C10A	1.412 (2)	N4B—C10B	1.411 (2)
N4A—H4AN	0.851 (9)	N4B—H4BN	0.854 (10)
C1A—C6A	1.383 (3)	C1B—C2B	1.387 (3)
C1A—C2A	1.388 (3)	C1B—C6B	1.391 (3)
C2A—C3A	1.378 (3)	C2B—C3B	1.384 (3)
C2A—H2A	0.9300	C2B—H2B	0.9300
C3A—C4A	1.381 (3)	C3B—C4B	1.374 (3)
C3A—H3A	0.9300	C3B—H3B	0.9300
C4A—C5A	1.377 (3)	C4B—C5B	1.371 (3)
C4A—H4A	0.9300	C4B—H4B	0.9300
C5A—C6A	1.381 (3)	C5B—C6B	1.387 (3)
C5A—N5A	1.470 (3)	C5B—N5B	1.472 (3)
C6A—H6A	0.9300	C6B—H6B	0.9300
C7A—C8A	1.462 (3)	C7B—C8B	1.461 (3)
C8A—C9A	1.432 (3)	C8B—C9B	1.431 (3)
C9A—C16A	1.490 (3)	C9B—C16B	1.492 (3)
C10A—C11A	1.376 (3)	C10B—C11B	1.378 (3)
C10A—C15A	1.384 (3)	C10B—C15B	1.383 (3)
C11A—C12A	1.376 (3)	C11B—C12B	1.382 (3)
C11A—H11A	0.9300	C11B—H11B	0.9300
C12A—C13A	1.388 (3)	C12B—C13B	1.376 (3)
C12A—H12A	0.9300	C12B—H12B	0.9300
C13A—C14A	1.379 (3)	C13B—C14B	1.387 (3)
C13A—C17A	1.508 (3)	C13B—C17B	1.512 (3)
C14A—C15A	1.387 (3)	C14B—C15B	1.380 (3)
C14A—H14A	0.9300	C14B—H14B	0.9300
C15A—H15A	0.9300	C15B—H15B	0.9300
C16A—H16A	0.9600	C16B—H16D	0.9600
C16A—H16B	0.9600	C16B—H16E	0.9600
C16A—H16C	0.9600	C16B—H16F	0.9600
C17A—H17A	0.9600	C17B—H17D	0.9600
C17A—H17B	0.9600	C17B—H17E	0.9600
C17A—H17C	0.9600	C17B—H17F	0.9600
N5A—O2A	1.213 (2)	N5B—O2B	1.226 (2)
N5A—O3A	1.219 (2)	N5B—O3B	1.228 (2)
C7A—N1A—C1A	129.60 (17)	C7B—N1B—C1B	129.18 (18)
C7A—N1A—N2A	112.16 (16)	C7B—N1B—N2B	112.14 (17)
C1A—N1A—N2A	118.18 (16)	C1B—N1B—N2B	118.51 (16)
C9A—N2A—N1A	106.89 (16)	C9B—N2B—N1B	106.77 (16)
N4A—N3A—C8A	118.04 (17)	N4B—N3B—C8B	117.39 (18)
N3A—N4A—C10A	120.71 (18)	N3B—N4B—C10B	121.18 (19)
N3A—N4A—H4AN	119.6 (16)	N3B—N4B—H4BN	116.9 (17)
C10A—N4A—H4AN	119.6 (16)	C10B—N4B—H4BN	121.9 (17)
C6A—C1A—C2A	119.76 (19)	C2B—C1B—C6B	119.30 (19)
C6A—C1A—N1A	120.55 (17)	C2B—C1B—N1B	120.00 (19)
C2A—C1A—N1A	119.69 (18)	C6B—C1B—N1B	120.70 (18)
C3A—C2A—C1A	120.4 (2)	C3B—C2B—C1B	120.3 (2)
C3A—C2A—H2A	119.8	C3B—C2B—H2B	119.9
C1A—C2A—H2A	119.8	C1B—C2B—H2B	119.9
C2A—C3A—C4A	121.1 (2)	C4B—C3B—C2B	121.6 (2)
C2A—C3A—H3A	119.4	C4B—C3B—H3B	119.2
C4A—C3A—H3A	119.4	C2B—C3B—H3B	119.2
C5A—C4A—C3A	117.06 (19)	C5B—C4B—C3B	117.1 (2)
C5A—C4A—H4A	121.5	C5B—C4B—H4B	121.5
C3A—C4A—H4A	121.5	C3B—C4B—H4B	121.5
C4A—C5A—C6A	123.71 (19)	C4B—C5B—C6B	123.6 (2)
C4A—C5A—N5A	117.94 (19)	C4B—C5B—N5B	118.7 (2)
C6A—C5A—N5A	118.34 (18)	C6B—C5B—N5B	117.67 (19)
C5A—C6A—C1A	117.96 (18)	C5B—C6B—C1B	118.10 (18)
C5A—C6A—H6A	121.0	C5B—C6B—H6B	121.0
C1A—C6A—H6A	121.0	C1B—C6B—H6B	121.0
O1A—C7A—N1A	127.75 (19)	O1B—C7B—N1B	128.1 (2)
O1A—C7A—C8A	128.83 (18)	O1B—C7B—C8B	128.42 (19)
N1A—C7A—C8A	103.43 (17)	N1B—C7B—C8B	103.45 (18)
N3A—C8A—C9A	125.04 (19)	N3B—C8B—C9B	125.6 (2)
N3A—C8A—C7A	128.56 (19)	N3B—C8B—C7B	127.98 (19)
C9A—C8A—C7A	106.37 (17)	C9B—C8B—C7B	106.41 (17)
N2A—C9A—C8A	111.16 (18)	N2B—C9B—C8B	111.23 (19)
N2A—C9A—C16A	122.05 (19)	N2B—C9B—C16B	121.91 (19)
C8A—C9A—C16A	126.78 (19)	C8B—C9B—C16B	126.86 (19)
C11A—C10A—C15A	119.18 (19)	C11B—C10B—C15B	119.73 (18)
C11A—C10A—N4A	119.32 (18)	C11B—C10B—N4B	117.95 (19)
C15A—C10A—N4A	121.50 (19)	C15B—C10B—N4B	122.31 (19)
C10A—C11A—C12A	120.39 (19)	C10B—C11B—C12B	119.73 (19)
C10A—C11A—H11A	119.8	C10B—C11B—H11B	120.1
C12A—C11A—H11A	119.8	C12B—C11B—H11B	120.1
C11A—C12A—C13A	122.2 (2)	C13B—C12B—C11B	121.88 (19)
C11A—C12A—H12A	118.9	C13B—C12B—H12B	119.1
C13A—C12A—H12A	118.9	C11B—C12B—H12B	119.1
C14A—C13A—C12A	116.2 (2)	C12B—C13B—C14B	117.31 (18)
C14A—C13A—C17A	122.2 (2)	C12B—C13B—C17B	121.29 (18)
C12A—C13A—C17A	121.6 (2)	C14B—C13B—C17B	121.40 (19)
C13A—C14A—C15A	122.9 (2)	C15B—C14B—C13B	121.96 (19)
C13A—C14A—H14A	118.6	C15B—C14B—H14B	119.0
C15A—C14A—H14A	118.6	C13B—C14B—H14B	119.0
C10A—C15A—C14A	119.1 (2)	C14B—C15B—C10B	119.38 (19)
C10A—C15A—H15A	120.4	C14B—C15B—H15B	120.3
C14A—C15A—H15A	120.4	C10B—C15B—H15B	120.3
C9A—C16A—H16A	109.5	C9B—C16B—H16D	109.5
C9A—C16A—H16B	109.5	C9B—C16B—H16E	109.5
H16A—C16A—H16B	109.5	H16D—C16B—H16E	109.5
C9A—C16A—H16C	109.5	C9B—C16B—H16F	109.5
H16A—C16A—H16C	109.5	H16D—C16B—H16F	109.5
H16B—C16A—H16C	109.5	H16E—C16B—H16F	109.5
C13A—C17A—H17A	109.5	C13B—C17B—H17D	109.5
C13A—C17A—H17B	109.5	C13B—C17B—H17E	109.5
H17A—C17A—H17B	109.5	H17D—C17B—H17E	109.5
C13A—C17A—H17C	109.5	C13B—C17B—H17F	109.5
H17A—C17A—H17C	109.5	H17D—C17B—H17F	109.5
H17B—C17A—H17C	109.5	H17E—C17B—H17F	109.5
O2A—N5A—O3A	123.4 (2)	O2B—N5B—O3B	123.0 (2)
O2A—N5A—C5A	119.12 (19)	O2B—N5B—C5B	119.0 (2)
O3A—N5A—C5A	117.43 (19)	O3B—N5B—C5B	118.0 (2)

(II) 3-Methyl-4-[(Z)-2-(4-methylphenyl)hydrazin-1-ylidene]-1-[4-(trifluoromethyl)phenyl]-1H-pyrazol-5(4H)-one

Crystal data

C18H15F3N4O	V = 834.03 (7) Å^3
Mr = 360.34	Z = 2
Triclinic, P1	F(000) = 372
Hall symbol: -P 1	Dx = 1.435 Mg m^−3
a = 8.4570 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.8227 (5) Å	µ = 0.12 mm^−1
c = 11.2448 (6) Å	T = 296 K
α = 103.327 (2)°	Plate, orange
β = 107.761 (2)°	0.22 × 0.18 × 0.08 mm
γ = 100.242 (2)°

Data collection

Bruker SMART CCD area-detector diffractometer	2917 independent reflections
Radiation source: fine-focus sealed tube	2222 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
CCD rotation images, thin slices scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2002)	h = −10→10
Tmin = 0.97, Tmax = 1.00	k = −11→11
16333 measured reflections	l = −13→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.207	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.1261P)^2 + 0.3997P] where P = (Fo^2 + 2Fc^2)/3
2917 reflections	(Δ/σ)max = 0.007
240 parameters	Δρmax = 0.55 e Å^−3
1 restraint	Δρmin = −0.30 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq
O1	0.3518 (3)	0.6894 (2)	0.00641 (19)	0.0556 (5)
N1	0.4005 (3)	0.5869 (2)	−0.1853 (2)	0.0458 (6)
N2	0.3731 (3)	0.4449 (2)	−0.2666 (2)	0.0511 (6)
N3	0.2059 (3)	0.3698 (3)	−0.0328 (2)	0.0492 (6)
N4	0.1946 (3)	0.4539 (3)	0.0707 (2)	0.0523 (6)
H4N	0.233 (4)	0.5469 (12)	0.092 (3)	0.063*
C1	0.4782 (3)	0.7050 (3)	−0.2181 (2)	0.0429 (6)
C2	0.5045 (3)	0.6795 (3)	−0.3362 (3)	0.0476 (6)
H2	0.4707	0.5856	−0.3930	0.057*
C3	0.5811 (4)	0.7942 (3)	−0.3688 (3)	0.0492 (7)
H3	0.5988	0.7774	−0.4479	0.059*
C4	0.6318 (3)	0.9344 (3)	−0.2842 (2)	0.0456 (6)
C5	0.6055 (4)	0.9586 (3)	−0.1671 (3)	0.0538 (7)
H5	0.6390	1.0527	−0.1106	0.065*
C6	0.5299 (4)	0.8446 (3)	−0.1326 (3)	0.0528 (7)
H6	0.5138	0.8615	−0.0528	0.063*
C7	0.3445 (3)	0.5859 (3)	−0.0823 (2)	0.0444 (6)
C8	0.2762 (3)	0.4323 (3)	−0.1029 (3)	0.0452 (6)
C9	0.3012 (3)	0.3554 (3)	−0.2172 (3)	0.0493 (7)
C10	0.1237 (3)	0.3921 (3)	0.1514 (3)	0.0488 (7)
C11	0.1401 (5)	0.4799 (3)	0.2704 (4)	0.0704 (9)
H11	0.1934	0.5788	0.2961	0.085*
C12	0.0767 (5)	0.4207 (3)	0.3522 (4)	0.0712 (10)
H12	0.0917	0.4805	0.4343	0.085*
C13	−0.0080 (4)	0.2757 (3)	0.3160 (3)	0.0536 (7)
C14	−0.0247 (4)	0.1901 (3)	0.1946 (3)	0.0570 (7)
H14	−0.0820	0.0920	0.1673	0.068*
C15	0.0414 (4)	0.2462 (3)	0.1121 (3)	0.0556 (7)
H15	0.0304	0.1862	0.0313	0.067*
C16	0.2599 (4)	0.1957 (3)	−0.2743 (3)	0.0661 (8)
H16A	0.2997	0.1737	−0.3460	0.099*
H16B	0.1374	0.1550	−0.3053	0.099*
H16C	0.3156	0.1550	−0.2084	0.099*
C17	−0.0748 (5)	0.2135 (4)	0.4072 (4)	0.0688 (9)
H17A	−0.1984	0.1828	0.3709	0.103*
H17B	−0.0376	0.2862	0.4907	0.103*
H17C	−0.0309	0.1318	0.4183	0.103*
C18	0.7145 (4)	1.0587 (3)	−0.3176 (3)	0.0551 (7)
F1	0.7554 (4)	1.0219 (3)	−0.4216 (3)	0.1302 (12)
F2	0.8554 (3)	1.1427 (3)	−0.2247 (2)	0.1249 (11)
F3	0.6175 (3)	1.1469 (3)	−0.3422 (3)	0.1257 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0706 (13)	0.0522 (11)	0.0567 (11)	0.0203 (10)	0.0386 (10)	0.0158 (9)
N1	0.0526 (13)	0.0420 (12)	0.0483 (12)	0.0122 (9)	0.0263 (10)	0.0134 (9)
N2	0.0591 (14)	0.0450 (13)	0.0505 (12)	0.0107 (11)	0.0252 (11)	0.0121 (10)
N3	0.0446 (12)	0.0549 (13)	0.0525 (13)	0.0151 (10)	0.0203 (10)	0.0191 (11)
N4	0.0565 (14)	0.0472 (13)	0.0632 (15)	0.0146 (11)	0.0318 (12)	0.0208 (12)
C1	0.0432 (14)	0.0450 (14)	0.0460 (14)	0.0149 (11)	0.0216 (11)	0.0142 (11)
C2	0.0568 (16)	0.0442 (14)	0.0451 (14)	0.0133 (12)	0.0253 (12)	0.0103 (11)
C3	0.0573 (16)	0.0526 (15)	0.0429 (14)	0.0138 (13)	0.0265 (12)	0.0138 (12)
C4	0.0441 (14)	0.0496 (15)	0.0488 (15)	0.0130 (11)	0.0217 (12)	0.0181 (12)
C5	0.0636 (18)	0.0455 (15)	0.0564 (16)	0.0133 (13)	0.0321 (14)	0.0100 (12)
C6	0.0700 (18)	0.0467 (15)	0.0497 (15)	0.0123 (13)	0.0376 (14)	0.0107 (12)
C7	0.0437 (14)	0.0517 (15)	0.0456 (14)	0.0176 (11)	0.0228 (11)	0.0164 (12)
C8	0.0398 (13)	0.0496 (14)	0.0509 (14)	0.0113 (11)	0.0188 (11)	0.0212 (12)
C9	0.0494 (15)	0.0493 (15)	0.0499 (15)	0.0104 (12)	0.0198 (12)	0.0156 (12)
C10	0.0457 (14)	0.0483 (15)	0.0651 (17)	0.0160 (12)	0.0283 (13)	0.0270 (13)
C11	0.096 (2)	0.0456 (16)	0.092 (2)	0.0182 (16)	0.065 (2)	0.0217 (16)
C12	0.099 (3)	0.0498 (17)	0.087 (2)	0.0225 (17)	0.066 (2)	0.0180 (16)
C13	0.0598 (17)	0.0520 (16)	0.0695 (18)	0.0232 (13)	0.0394 (15)	0.0282 (14)
C14	0.0568 (17)	0.0526 (16)	0.0646 (18)	0.0078 (13)	0.0260 (14)	0.0233 (14)
C15	0.0609 (17)	0.0565 (17)	0.0488 (15)	0.0108 (14)	0.0226 (13)	0.0151 (13)
C16	0.078 (2)	0.0467 (16)	0.071 (2)	0.0067 (15)	0.0336 (17)	0.0125 (14)
C17	0.086 (2)	0.0658 (19)	0.082 (2)	0.0257 (17)	0.0544 (19)	0.0365 (17)
C18	0.0555 (17)	0.0543 (16)	0.0561 (16)	0.0083 (13)	0.0230 (14)	0.0187 (13)
F1	0.214 (3)	0.0797 (15)	0.118 (2)	−0.0092 (17)	0.124 (2)	0.0189 (14)
F2	0.1007 (18)	0.127 (2)	0.0948 (16)	−0.0522 (15)	0.0009 (13)	0.0479 (15)
F3	0.1095 (19)	0.1066 (19)	0.216 (3)	0.0434 (16)	0.078 (2)	0.113 (2)

Geometric parameters (Å, º)

O1—C7	1.227 (3)	C9—C16	1.482 (4)
N1—C7	1.379 (3)	C10—C11	1.366 (4)
N1—C1	1.410 (3)	C10—C15	1.378 (4)
N1—N2	1.415 (3)	C11—C12	1.381 (4)
N2—C9	1.301 (3)	C11—H11	0.9300
N3—N4	1.304 (3)	C12—C13	1.379 (4)
N3—C8	1.316 (3)	C12—H12	0.9300
N4—C10	1.417 (4)	C13—C14	1.379 (4)
N4—H4N	0.861 (10)	C13—C17	1.505 (4)
C1—C6	1.385 (4)	C14—C15	1.385 (4)
C1—C2	1.386 (4)	C14—H14	0.9300
C2—C3	1.378 (4)	C15—H15	0.9300
C2—H2	0.9300	C16—H16A	0.9600
C3—C4	1.387 (4)	C16—H16B	0.9600
C3—H3	0.9300	C16—H16C	0.9600
C4—C5	1.376 (4)	C17—H17A	0.9600
C4—C18	1.479 (4)	C17—H17B	0.9600
C5—C6	1.382 (4)	C17—H17C	0.9600
C5—H5	0.9300	C18—F2	1.298 (4)
C6—H6	0.9300	C18—F1	1.309 (4)
C7—C8	1.454 (4)	C18—F3	1.313 (4)
C8—C9	1.430 (4)
C7—N1—C1	129.9 (2)	C11—C10—N4	118.6 (3)
C7—N1—N2	112.1 (2)	C15—C10—N4	121.1 (3)
C1—N1—N2	118.1 (2)	C10—C11—C12	119.4 (3)
C9—N2—N1	106.9 (2)	C10—C11—H11	120.3
N4—N3—C8	117.5 (2)	C12—C11—H11	120.3
N3—N4—C10	119.8 (2)	C13—C12—C11	122.0 (3)
N3—N4—H4N	121 (2)	C13—C12—H12	119.0
C10—N4—H4N	119 (2)	C11—C12—H12	119.0
C6—C1—C2	120.3 (2)	C12—C13—C14	117.2 (3)
C6—C1—N1	120.4 (2)	C12—C13—C17	121.0 (3)
C2—C1—N1	119.2 (2)	C14—C13—C17	121.7 (3)
C3—C2—C1	119.6 (2)	C13—C14—C15	121.9 (3)
C3—C2—H2	120.2	C13—C14—H14	119.1
C1—C2—H2	120.2	C15—C14—H14	119.1
C2—C3—C4	120.4 (2)	C10—C15—C14	119.2 (3)
C2—C3—H3	119.8	C10—C15—H15	120.4
C4—C3—H3	119.8	C14—C15—H15	120.4
C5—C4—C3	119.5 (3)	C9—C16—H16A	109.5
C5—C4—C18	119.4 (3)	C9—C16—H16B	109.5
C3—C4—C18	121.1 (2)	H16A—C16—H16B	109.5
C4—C5—C6	120.8 (3)	C9—C16—H16C	109.5
C4—C5—H5	119.6	H16A—C16—H16C	109.5
C6—C5—H5	119.6	H16B—C16—H16C	109.5
C5—C6—C1	119.3 (2)	C13—C17—H17A	109.5
C5—C6—H6	120.3	C13—C17—H17B	109.5
C1—C6—H6	120.3	H17A—C17—H17B	109.5
O1—C7—N1	128.6 (2)	C13—C17—H17C	109.5
O1—C7—C8	128.0 (2)	H17A—C17—H17C	109.5
N1—C7—C8	103.4 (2)	H17B—C17—H17C	109.5
N3—C8—C9	124.4 (2)	F2—C18—F1	105.6 (3)
N3—C8—C7	129.0 (2)	F2—C18—F3	103.9 (3)
C9—C8—C7	106.6 (2)	F1—C18—F3	104.6 (3)
N2—C9—C8	110.9 (2)	F2—C18—C4	113.9 (2)
N2—C9—C16	122.1 (3)	F1—C18—C4	114.3 (3)
C8—C9—C16	127.0 (3)	F3—C18—C4	113.5 (2)
C11—C10—C15	120.3 (3)