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The title compound, C17H11F5N4O, is described and compared with two closely related analogues in the literature. There are two independent mol­ecules in the asymmetric unit, linked by N—H...O hydrogen bonds and π–π inter­actions into dimeric entities, presenting a noticeable noncrystallographic C2 symmetry. These dimers are in turn linked by a medium-strength type-I C—F...F—C inter­action into elongated tetra­mers. Much weaker C—H...F contacts link the tetra­mers into broad two-dimensional substructures parallel to (101).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113024943/fn3154sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113024943/fn3154Isup2.hkl
Contains datablock I

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113024943/fn3154Isup3.cml
Supplementary material

CCDC reference: 969477

Introduction top

Substituted pyrazoles have been the subject of numerous reports concerning their biological activity and potential pharmacological properties. In fact, these compounds are an important class of bioactive targets in the pharmaceutical industry that includes blockbuster drugs such as Viagra (Terrett et al., 1996), Celebrex (Penning et al., 1997) etc. In addition, pyrazoles are attractive from a pharmacological point of view as analgesic, anti­parasitic, anti-anxiety, anti­microbial, anti­pyretic and anti-inflammatory drugs (Elguero et al., 2002), and some related derivatives have been found to be potent PDE4B inhibitors (Card et al., 2005). Pyrazole compounds are also of inter­est in coordination chemistry: since the heterocyclic nuclei may coordinate directly via one or both vicinal N atoms, they have been used as quite effective ligands for obtaining transition metal complexes (Rojas et al., 2004).

In the last few years, we have reported the synthesis and molecular structure of two closely related compounds with a common pyrazole-centred core (hereinafter `B') flanked on both sides by a phenyl and a diazenyl-penta­fluoro­phenyl group, viz. 3,5-di­methyl-1-(4-nitro­phenyl)-4-[(E)-(2,3,4,5,6-penta­fluoro­phenyl)­diazenyl]-1H-pyrazole, (II) (Bustos, Sánchez, Schott et al., 2007) and 3,5-di­methyl-1-(4-nitro­phenyl)-4-[(E)-(2,3,4,5,6-penta­fluoro­phenyl)­diazenyl]-1H-pyrazole, (III) (Alvarez Thon et al., 2013).

Surprisingly, a search of the Cambridge Structural Database (CSD, Version?; Allen, 2002) confirmed these to be the only structures based on such a core which have been reported so far, so we decided to continue investigating the structural possibilities of this family. As a result, we present here the structure of a new member of the group, the title compound (Z)-3-methyl-4-[2-(4-methyl­phenyl)­hydrazinyl­idene]-1-(perfluoro­phenyl)-1H-pyrazol-5(4H)-one, (I), and compare it with the previously reported analogues.

Experimental top

Synthesis and crystallization top

Ethyl (Z)-3-oxo-2-(2-p-tolyl­hydrazinilydene)butano­ate was prepared according to the method recommended in the literature (Yao, 1964; Bertolasi et al., 1999; Bustos, Sánchez, Martínez et al., 2007; Bustos et al., 2009) and recrystallized from ethanol. Solvents (EtOH, CHCl3, CDCl3 and glacial acetic acid) were provided by Merck and perfluoro­phenyl­hydrazine by Aldrich.

Ethyl (Z)-3-oxo-2-(2-p-tolyl­hydrazinilydene)butano­ate (2.48 g, 10 mmol), perfluoro­phenyl­hydrazine (2.04 g, 10 mmol, 97%), glacial acetic acid (5 ml) and ethanol (30 ml) were added to a round-bottomed flask. The mixture was stirred and heated at reflux near the boiling point, and a yellow–orange solid precipitate was formed after 36 h. The reaction mixture was cooled at 263 K for 2 h, and the product was then 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 of (I) suitable for diffraction studies were obtained by recrystallization from an ethanol–water (1:1 v/v) mixture (yield 70.6%; m.p. 395–396 K). Analysis, calculated (%) for C17H11F5N4O: C 53.41, H 2.90, N 14.66; found (%): C 53.26, H 2.88, N 14.88.

Refinement top

H atoms were originally found in a difference Fourier map, but were treated differently. N-bound H atoms were refined with a restrained N—H distance of 0.85 (1) Å, while C-bound H atoms were repositioned in their expected positions and thereinafter allowed to ride, with C—H = 0.96 (methyl) or 0.93 Å (aromatic). Methyl groups were allowed to rotate around their C—C bond. For all H atoms, Uiso(H) = 1.5Ueq(H). [Rephrasing OK?]

Results and discussion top

The title compound, (I), crystallizes with two independent molecules in the asymmetric unit [hereinafter (Ia) and (Ib); Fig 1], linked by a diversity of noncovalent inter­actions into a strongly bound dimer which should be considered the elemental building block of the crystal structure.

The two independent units are extremely similar regarding inter­atomic distances and angles. This similarity can be best assessed in graphical terms through the superposition of the two independent molecules, shown in Fig. 2(a). It is apparent that the only significant difference is found in the C8/N3/N4/C12/C13/C17 region, a fact confirmed by a brief review of some relevant torsion angles, given in the order (Ia)/(Ib): C8—N3—N4—C12 = -178.65 (14)/-173.28 (14)°, N3—N4—C12—C17 = 166.92 (16)/160.32 (16)° and N3—N4—C12—C13 = -13.1 (3)/-18.6 (2)°.

These molecular similarities have, in fact, a deeper significance. A PLATON run (Spek, 2009) using the quaternion algorithm proposed by Mackay (1984) disclosed a striking noncrystallographic twofold pseudorotation relating the two independent units, with a mean r.m.s. atom misfit of 0.14 Å. When pseudosymmetry-related bond lengths and angles are compared, r.m.s. misfits are also extremely low, viz. 0.0063 Å and 0.570°, respectively.

A quick comparison of (I) with its two predecessors, (II) and (III), can be seen in Scheme 1. It is apparent that the main differences appear in the imidazole group and its neighbourhood, through the replacement of one methyl substituent in (II) and (III) with an oxo group in (I), and the protonation of atom N3, with the consequent reorganization of the electron distribution. This `reshuffling' is clearly revealed in some relevant bond distances (Table 2) and in the supra­molecular organization (see below).

Pushing comparisons a bit further, Fig 2(b) shows a comparative overlap of all four molecular units, viz. (Ia), (Ib), (II) and (III), where only the pyrazole rings were used for fitting purposes. It can be seen that the penta­fluoro­phenyl rings present a marked preferred orientation, viz. (Ia), (Ib) and (II) versus (III), while on the phenyl side the preferences are evenly split, the N3—N4 bond being cis to the C6F5 group in (Ia) and (Ib) but trans in (II) and (III).

Similarly, the appearance of the N—H group in (I) renders the supra­molecular organization quite different from those in (II) and (III). Fig. 1 shows the way in which the dimers are built up; the main link is the central R42(4) loop (for nomenclature, see Bernstein et al., 1995) involving all four N—H···O hydrogen bonds presented in Table 3, complemented by the two lateral quasi-symmetrical Cg···Cg inter­actions presented in Table 4. These well connected dimers are in turn joined into a tetra­meric unit by a short F···F contact [F2a···F2ai = 2.7955 (18) Å and C2a—F2a···.F2ai = 138.24 (11)°; symmetry code: (i) -x + 1, -y + 1, -z + 1; Fig. 3). This inter­action could be considered medium strength: a search of the CSD disclosed about 21500 F···F contacts in the range 2.40–2.95Å, and the present one lies in the 40th lower percentile. At this stage it is inter­esting to comment on the characteristics of C—F···F—C inter­actions which, according to their geometric disposition, have historically been divided into type-I and type-II (see Scheme 2); the case analysed herein, developed around an inversion centre, corresponds to the first type. Even if only type-II contacts had been originally ascribed a stabilizing effect, further studies began disclosing a stabilizing character in many type-I cases, in particular those already found in structures (II) and (III). For further details on the subject, see Baker et al. (2012, and references therein).

The inter­actions described so far are all the middle-strength noncovalent ones in the structure. There is a weaker C—Hmethyl···F contact (Table 3, fifth entry, and Fig 4a, labelled A) feebly connecting tetra­mers into broad two-dimensional structures parallel to (101). From Fig. 4(b) it can be seen that the substructure could also be topologically described as made up of two parallel thin planes (with a rather weak inter­nal connection, A bonds) linked by the stronger F···F inter­action (labelled B).

The rather unattractive supra­molecular organization of (I) compared with the much richer ones of (II) and (III) allows a brief comment about the role of the oxo group in the structure. Its presence allows for the pairing of neighbouring molecules into strongly linked dimers. But, at the same time, the very closeness of these structures somehow `shields' the C—F groups from effective inter­molecular inter­actions, to the extent that only one C—F···F—C bond appears in the structure. On the other hand, its role is relevant in that it is the sole linkage in the formation of the tetra­mer, thus providing a further example that type-I C—F···F—C inter­actions should be given due consideration as effective synthons in supra­molecular organization.

Related literature top

For related literature, see: Allen (2002); Alvarez Thon, Bustos, Diaz-Marín, Garland & Baggio (2013); Baker et al. (2012); Bernstein et al. (1995); Bertolasi et al. (1999); Bustos et al. (2009); Bustos, Sánchez, Martínez, Ugarte, Schott, Carey, Garland & Espinoza (2007); Bustos, Sánchez, Schott, Alvarez-Thon & Fuentealba (2007); Card (2005); Elguero et al. (2002); Mackay (1984); Penning et al. (1997); Rojas et al. (2004); Spek (2009); Terrett et al. (1996); Yao (1964).

Computing details top

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 top
[Figure 1] Fig. 1. The dimeric unit in (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Different line types have been used to differentiate the two independent molecules, (Ia) and (Ib). Dashed lines represent noncovalent interactions.
[Figure 2] Fig. 2. (a) A least-squares fit of (Ia) (solid lines) and (Ib) (dashed lines). (b) A least-squares fit of (Ia), (Ib), (II) and (III). In both cases, only imidazole groups have been included in the fit.
[Figure 3] Fig. 3. A schematic view of the tetrameric unit in (I) generated by F···F interactions, shown as the central bond in double-dashed lines. The remaining dashed lines are as in Fig. 1.
[Figure 4] Fig. 4. Packing views of (I), (a) projected down [101], showing the two-dimensional structure generated by the C—H···F bond (A) and (b) viewed down [010], showing the `double-sheet' character of the two-dimensional structure, linked by F···F interactions (B). Dashd lines indicate intermolecular interactions. [Added text OK?]
(Z)-3-Methyl-4-[2-(4-methylphenyl)hydrazinylidene]-1-(pentafluorophenyl)-1H-pyrazol-5(4H)-one top
Crystal data top
C17H11F5N4OF(000) = 1552
Mr = 382.30Dx = 1.480 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 999 reflections
a = 11.6678 (12) Åθ = 2.2–26.3°
b = 16.6283 (17) ŵ = 0.13 mm1
c = 17.8362 (18) ÅT = 297 K
β = 97.368 (2)°Polyhedron, orange
V = 3431.9 (6) Å30.32 × 0.22 × 0.22 mm
Z = 8
Data collection top
Bruker SMART CCD area-detector
diffractometer
7711 independent reflections
Radiation source: fine-focus sealed tube4062 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
CCD rotation images, thin slices scansθmax = 28.0°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS in SAINT-NT; Bruker, 2002)
h = 1415
Tmin = 0.96, Tmax = 0.98k = 2121
28507 measured reflectionsl = 2323
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.123H atoms treated by a mixture of independent and constrained refinement
S = 0.92 w = 1/[σ2(Fo2) + (0.0667P)2]
where P = (Fo2 + 2Fc2)/3
7711 reflections(Δ/σ)max < 0.001
495 parametersΔρmax = 0.18 e Å3
2 restraintsΔρmin = 0.12 e Å3
Crystal data top
C17H11F5N4OV = 3431.9 (6) Å3
Mr = 382.30Z = 8
Monoclinic, P21/nMo Kα radiation
a = 11.6678 (12) ŵ = 0.13 mm1
b = 16.6283 (17) ÅT = 297 K
c = 17.8362 (18) Å0.32 × 0.22 × 0.22 mm
β = 97.368 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
7711 independent reflections
Absorption correction: multi-scan
(SADABS in SAINT-NT; Bruker, 2002)
4062 reflections with I > 2σ(I)
Tmin = 0.96, Tmax = 0.98Rint = 0.032
28507 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0422 restraints
wR(F2) = 0.123H atoms treated by a mixture of independent and constrained refinement
S = 0.92Δρmax = 0.18 e Å3
7711 reflectionsΔρmin = 0.12 e Å3
495 parameters
Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
F1A0.50190 (10)0.43994 (7)0.35505 (6)0.0917 (3)
F2A0.43557 (10)0.42890 (8)0.49344 (6)0.1065 (4)
F3A0.29988 (11)0.30759 (10)0.52667 (7)0.1289 (5)
F4A0.22606 (12)0.19672 (9)0.42029 (9)0.1425 (6)
F5A0.29140 (11)0.20694 (7)0.28119 (8)0.1140 (4)
O10A0.34010 (10)0.44646 (7)0.19669 (6)0.0741 (3)
N1A0.43248 (13)0.32949 (9)0.24210 (7)0.0716 (4)
N2A0.49379 (14)0.26536 (10)0.21374 (8)0.0848 (5)
N3A0.42135 (12)0.38300 (9)0.05095 (7)0.0666 (4)
N4A0.35879 (13)0.44722 (9)0.03982 (8)0.0656 (4)
H4A0.3228 (13)0.4657 (10)0.0755 (8)0.081 (6)*
C1A0.43441 (15)0.37910 (11)0.37010 (9)0.0666 (4)
C2A0.40150 (16)0.37404 (13)0.44071 (10)0.0753 (5)
C3A0.33317 (18)0.31226 (16)0.45762 (12)0.0858 (6)
C4A0.29621 (17)0.25670 (14)0.40428 (15)0.0903 (6)
C5A0.32922 (16)0.26167 (12)0.33346 (12)0.0770 (5)
C6A0.39927 (15)0.32322 (11)0.31471 (9)0.0644 (4)
C7A0.39526 (14)0.38548 (11)0.18767 (9)0.0623 (4)
C8A0.43722 (14)0.35375 (11)0.12069 (9)0.0648 (4)
C9A0.49699 (17)0.28104 (12)0.14296 (10)0.0782 (5)
C11A0.5564 (2)0.22680 (15)0.09328 (12)0.1145 (8)
H11A0.56950.17530.11720.172*
H11B0.62910.25000.08510.172*
H11C0.50880.22020.04560.172*
C12A0.33487 (14)0.48203 (10)0.03302 (9)0.0609 (4)
C13A0.39452 (14)0.45960 (10)0.09166 (9)0.0656 (4)
H13A0.45240.42090.08430.079*
C14A0.36682 (16)0.49568 (12)0.16176 (10)0.0752 (5)
H14A0.40690.48080.20140.090*
C15A0.28118 (17)0.55320 (12)0.17412 (10)0.0772 (5)
C16A0.22477 (17)0.57414 (13)0.11347 (11)0.0863 (6)
H16A0.16750.61330.12020.104*
C17A0.25025 (17)0.53920 (12)0.04378 (10)0.0783 (5)
H17A0.21030.55430.00410.094*
C18A0.2504 (2)0.59211 (17)0.25086 (11)0.1185 (9)
H18A0.17070.60800.25690.178*
H18B0.26290.55440.28970.178*
H18C0.29820.63860.25460.178*
F1B0.03496 (9)0.39618 (7)0.06906 (6)0.0978 (4)
F2B0.03163 (12)0.41981 (8)0.20683 (7)0.1132 (4)
F3B0.22147 (12)0.34489 (8)0.24379 (6)0.1158 (5)
F4B0.34820 (11)0.24954 (8)0.14265 (8)0.1182 (5)
F5B0.28452 (10)0.22800 (7)0.00459 (6)0.0970 (4)
O10B0.11880 (11)0.43062 (7)0.08770 (6)0.0720 (3)
N1B0.09168 (13)0.30130 (8)0.03918 (8)0.0702 (4)
N2B0.06695 (14)0.22392 (8)0.06571 (9)0.0775 (4)
N3B0.07544 (11)0.34048 (9)0.23068 (7)0.0622 (4)
N4B0.10288 (12)0.41561 (9)0.24342 (8)0.0643 (4)
H4B0.1231 (15)0.4463 (9)0.2088 (8)0.088 (6)*
C1B0.05981 (15)0.35999 (10)0.08648 (10)0.0667 (5)
C2B0.09267 (18)0.37214 (11)0.15683 (10)0.0740 (5)
C3B0.18872 (19)0.33346 (13)0.17572 (10)0.0780 (5)
C4B0.25151 (17)0.28452 (12)0.12438 (12)0.0770 (5)
C5B0.21860 (16)0.27375 (10)0.05463 (10)0.0669 (5)
C6B0.12209 (15)0.31098 (10)0.03395 (9)0.0606 (4)
C7B0.09704 (14)0.35906 (10)0.09474 (9)0.0603 (4)
C8B0.07152 (14)0.31423 (10)0.16034 (9)0.0610 (4)
C9B0.05312 (15)0.23266 (11)0.13663 (10)0.0703 (5)
C11B0.0229 (2)0.16308 (12)0.18273 (11)0.0996 (7)
H11D0.05160.17190.19870.149*
H11E0.07990.15760.22630.149*
H11F0.02100.11490.15290.149*
C12B0.12071 (14)0.44568 (10)0.31785 (8)0.0587 (4)
C13B0.08005 (15)0.40606 (11)0.37647 (9)0.0683 (5)
H13B0.03590.35970.36760.082*
C14B0.10574 (16)0.43617 (12)0.44911 (10)0.0742 (5)
H14B0.07790.40930.48880.089*
C15B0.17119 (16)0.50456 (11)0.46458 (9)0.0713 (5)
C16B0.20706 (17)0.54460 (11)0.40370 (10)0.0775 (5)
H16B0.24880.59210.41200.093*
C17B0.18243 (16)0.51569 (11)0.33139 (10)0.0740 (5)
H17B0.20760.54360.29140.089*
C18B0.20426 (19)0.53287 (14)0.54477 (10)0.0977 (7)
H18D0.15570.57710.55500.147*
H18E0.28350.54990.55140.147*
H18F0.19460.48960.57900.147*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
F1A0.0950 (8)0.0923 (8)0.0886 (8)0.0115 (6)0.0143 (6)0.0005 (6)
F2A0.1169 (10)0.1293 (10)0.0709 (7)0.0263 (8)0.0031 (6)0.0205 (7)
F3A0.1122 (10)0.1948 (15)0.0880 (8)0.0334 (9)0.0454 (7)0.0444 (9)
F4A0.1151 (11)0.1317 (11)0.1870 (16)0.0175 (9)0.0438 (10)0.0514 (11)
F5A0.1069 (10)0.0924 (9)0.1375 (11)0.0086 (7)0.0047 (8)0.0170 (8)
O10A0.0823 (8)0.0743 (8)0.0665 (7)0.0193 (7)0.0126 (6)0.0027 (6)
N1A0.0828 (10)0.0756 (10)0.0563 (9)0.0258 (8)0.0089 (7)0.0020 (7)
N2A0.0987 (12)0.0899 (11)0.0646 (10)0.0375 (9)0.0065 (8)0.0012 (8)
N3A0.0618 (9)0.0734 (10)0.0634 (9)0.0017 (8)0.0038 (7)0.0055 (7)
N4A0.0685 (9)0.0728 (10)0.0569 (9)0.0020 (8)0.0133 (7)0.0051 (8)
C1A0.0639 (11)0.0766 (12)0.0601 (11)0.0077 (9)0.0107 (8)0.0083 (9)
C2A0.0716 (12)0.0924 (14)0.0605 (12)0.0183 (11)0.0034 (9)0.0010 (11)
C3A0.0735 (13)0.1160 (18)0.0711 (14)0.0230 (13)0.0220 (11)0.0245 (13)
C4A0.0692 (13)0.0902 (15)0.1136 (19)0.0026 (12)0.0197 (13)0.0332 (14)
C5A0.0687 (12)0.0763 (13)0.0839 (14)0.0047 (10)0.0017 (10)0.0039 (11)
C6A0.0642 (11)0.0728 (12)0.0556 (10)0.0148 (9)0.0056 (8)0.0058 (9)
C7A0.0625 (10)0.0691 (11)0.0540 (10)0.0085 (9)0.0029 (8)0.0003 (9)
C8A0.0630 (10)0.0778 (12)0.0529 (10)0.0055 (9)0.0043 (8)0.0026 (9)
C9A0.0807 (13)0.0910 (14)0.0615 (11)0.0263 (11)0.0035 (9)0.0060 (10)
C11A0.130 (2)0.133 (2)0.0817 (14)0.0615 (16)0.0169 (13)0.0128 (13)
C12A0.0658 (11)0.0677 (11)0.0486 (9)0.0101 (9)0.0058 (8)0.0010 (8)
C13A0.0646 (10)0.0672 (11)0.0649 (11)0.0094 (8)0.0078 (8)0.0053 (9)
C14A0.0803 (13)0.0889 (14)0.0588 (11)0.0198 (11)0.0179 (9)0.0071 (9)
C15A0.0766 (12)0.0909 (14)0.0633 (11)0.0113 (11)0.0056 (9)0.0105 (10)
C16A0.0830 (13)0.0980 (15)0.0780 (13)0.0120 (11)0.0106 (11)0.0181 (11)
C17A0.0844 (13)0.0882 (14)0.0645 (11)0.0094 (11)0.0174 (9)0.0043 (10)
C18A0.1191 (19)0.162 (2)0.0724 (14)0.0046 (17)0.0057 (12)0.0375 (14)
F1B0.0835 (8)0.0933 (8)0.1162 (9)0.0196 (6)0.0115 (6)0.0046 (7)
F2B0.1358 (11)0.1061 (9)0.0878 (8)0.0048 (8)0.0235 (7)0.0239 (7)
F3B0.1462 (11)0.1374 (11)0.0686 (7)0.0499 (9)0.0320 (7)0.0197 (7)
F4B0.0968 (9)0.1225 (10)0.1423 (11)0.0043 (8)0.0426 (8)0.0431 (9)
F5B0.0954 (8)0.0803 (8)0.1086 (9)0.0133 (6)0.0129 (7)0.0021 (7)
O10B0.0943 (9)0.0585 (7)0.0640 (7)0.0063 (6)0.0136 (6)0.0061 (6)
N1B0.0915 (11)0.0600 (9)0.0595 (9)0.0147 (8)0.0117 (8)0.0068 (7)
N2B0.1015 (12)0.0608 (9)0.0697 (10)0.0201 (8)0.0098 (8)0.0058 (7)
N3B0.0604 (8)0.0651 (9)0.0612 (9)0.0028 (7)0.0080 (6)0.0027 (7)
N4B0.0776 (10)0.0624 (10)0.0544 (9)0.0025 (7)0.0142 (7)0.0013 (7)
C1B0.0667 (12)0.0605 (11)0.0707 (12)0.0012 (9)0.0011 (9)0.0109 (9)
C2B0.0876 (14)0.0690 (12)0.0605 (11)0.0129 (10)0.0093 (10)0.0025 (9)
C3B0.0971 (15)0.0845 (14)0.0537 (11)0.0281 (12)0.0147 (11)0.0173 (10)
C4B0.0729 (13)0.0727 (12)0.0871 (14)0.0069 (10)0.0160 (11)0.0254 (11)
C5B0.0729 (12)0.0586 (11)0.0663 (11)0.0042 (9)0.0020 (9)0.0115 (9)
C6B0.0683 (11)0.0575 (10)0.0553 (10)0.0079 (9)0.0046 (8)0.0114 (8)
C7B0.0629 (10)0.0589 (11)0.0582 (10)0.0043 (8)0.0040 (8)0.0064 (8)
C8B0.0627 (10)0.0635 (11)0.0566 (10)0.0056 (8)0.0063 (8)0.0041 (8)
C9B0.0792 (12)0.0669 (12)0.0641 (11)0.0154 (9)0.0064 (9)0.0027 (9)
C11B0.1329 (19)0.0775 (14)0.0895 (14)0.0324 (13)0.0180 (13)0.0025 (11)
C12B0.0633 (10)0.0630 (10)0.0503 (9)0.0068 (8)0.0092 (7)0.0012 (8)
C13B0.0705 (11)0.0732 (12)0.0625 (11)0.0021 (9)0.0139 (8)0.0002 (9)
C14B0.0845 (13)0.0840 (13)0.0557 (11)0.0059 (11)0.0154 (9)0.0068 (9)
C15B0.0791 (12)0.0753 (12)0.0590 (11)0.0165 (10)0.0071 (9)0.0087 (9)
C16B0.0955 (14)0.0694 (12)0.0688 (12)0.0054 (10)0.0151 (10)0.0133 (10)
C17B0.0979 (14)0.0649 (11)0.0620 (11)0.0057 (10)0.0213 (9)0.0021 (9)
C18B0.1170 (17)0.1100 (17)0.0640 (12)0.0154 (14)0.0040 (11)0.0182 (11)
Geometric parameters (Å, º) top
F1A—C1A1.330 (2)F1B—C1B1.3302 (19)
F2A—C2A1.334 (2)F2B—C2B1.330 (2)
F3A—C3A1.340 (2)F3B—C3B1.332 (2)
F4A—C4A1.344 (2)F4B—C4B1.346 (2)
F5A—C5A1.337 (2)F5B—C5B1.3382 (19)
O10A—C7A1.2228 (19)O10B—C7B1.2265 (18)
N1A—C7A1.375 (2)N1B—C7B1.376 (2)
N1A—C6A1.403 (2)N1B—C6B1.404 (2)
N1A—N2A1.4134 (19)N1B—N2B1.4133 (18)
N2A—C9A1.294 (2)N2B—C9B1.304 (2)
N3A—N4A1.2945 (19)N3B—N4B1.3024 (18)
N3A—C8A1.326 (2)N3B—C8B1.3235 (19)
N4A—C12A1.417 (2)N4B—C12B1.409 (2)
N4A—H4A0.863 (9)N4B—H4B0.858 (9)
C1A—C2A1.365 (2)C1B—C2B1.373 (2)
C1A—C6A1.380 (2)C1B—C6B1.377 (2)
C2A—C3A1.358 (3)C2B—C3B1.371 (3)
C3A—C4A1.356 (3)C3B—C4B1.366 (3)
C4A—C5A1.370 (3)C4B—C5B1.360 (3)
C5A—C6A1.378 (3)C5B—C6B1.376 (2)
C7A—C8A1.447 (2)C7B—C8B1.450 (2)
C8A—C9A1.426 (2)C8B—C9B1.429 (2)
C9A—C11A1.496 (3)C9B—C11B1.488 (2)
C11A—H11A0.9600C11B—H11D0.9600
C11A—H11B0.9600C11B—H11E0.9600
C11A—H11C0.9600C11B—H11F0.9600
C12A—C17A1.366 (2)C12B—C13B1.371 (2)
C12A—C13A1.380 (2)C12B—C17B1.374 (2)
C13A—C14A1.387 (2)C13B—C14B1.386 (2)
C13A—H13A0.9300C13B—H13B0.9300
C14A—C15A1.380 (3)C14B—C15B1.378 (3)
C14A—H14A0.9300C14B—H14B0.9300
C15A—C16A1.381 (3)C15B—C16B1.384 (2)
C15A—C18A1.515 (2)C15B—C18B1.508 (2)
C16A—C17A1.370 (2)C16B—C17B1.372 (2)
C16A—H16A0.9300C16B—H16B0.9300
C17A—H17A0.9300C17B—H17B0.9300
C18A—H18A0.9600C18B—H18D0.9600
C18A—H18B0.9600C18B—H18E0.9600
C18A—H18C0.9600C18B—H18F0.9600
C7A—N1A—C6A127.08 (14)C7B—N1B—C6B126.54 (14)
C7A—N1A—N2A112.76 (13)C7B—N1B—N2B112.76 (13)
C6A—N1A—N2A119.13 (13)C6B—N1B—N2B120.14 (13)
C9A—N2A—N1A106.04 (14)C9B—N2B—N1B106.23 (14)
N4A—N3A—C8A117.04 (14)N4B—N3B—C8B117.36 (14)
N3A—N4A—C12A121.24 (14)N3B—N4B—C12B120.55 (14)
N3A—N4A—H4A119.9 (12)N3B—N4B—H4B122.0 (13)
C12A—N4A—H4A118.3 (12)C12B—N4B—H4B116.5 (13)
F1A—C1A—C2A118.48 (17)F1B—C1B—C2B119.00 (17)
F1A—C1A—C6A119.79 (15)F1B—C1B—C6B119.40 (16)
C2A—C1A—C6A121.74 (18)C2B—C1B—C6B121.60 (17)
F2A—C2A—C3A119.42 (18)F2B—C2B—C3B119.95 (18)
F2A—C2A—C1A120.97 (19)F2B—C2B—C1B120.82 (19)
C3A—C2A—C1A119.61 (19)C3B—C2B—C1B119.23 (17)
F3A—C3A—C4A120.1 (2)F3B—C3B—C4B120.3 (2)
F3A—C3A—C2A119.7 (2)F3B—C3B—C2B119.7 (2)
C4A—C3A—C2A120.17 (19)C4B—C3B—C2B119.99 (18)
F4A—C4A—C3A120.3 (2)F4B—C4B—C5B120.5 (2)
F4A—C4A—C5A119.5 (2)F4B—C4B—C3B119.3 (2)
C3A—C4A—C5A120.3 (2)C5B—C4B—C3B120.11 (18)
F5A—C5A—C4A119.7 (2)F5B—C5B—C4B118.64 (18)
F5A—C5A—C6A119.32 (18)F5B—C5B—C6B119.81 (16)
C4A—C5A—C6A121.0 (2)C4B—C5B—C6B121.50 (18)
C5A—C6A—C1A117.24 (17)C5B—C6B—C1B117.56 (16)
C5A—C6A—N1A121.47 (17)C5B—C6B—N1B120.68 (16)
C1A—C6A—N1A121.28 (16)C1B—C6B—N1B121.72 (16)
O10A—C7A—N1A126.35 (15)O10B—C7B—N1B126.48 (15)
O10A—C7A—C8A130.57 (15)O10B—C7B—C8B130.38 (15)
N1A—C7A—C8A103.09 (14)N1B—C7B—C8B103.13 (14)
N3A—C8A—C9A125.20 (16)N3B—C8B—C9B125.40 (16)
N3A—C8A—C7A128.25 (16)N3B—C8B—C7B127.56 (15)
C9A—C8A—C7A106.51 (15)C9B—C8B—C7B106.72 (14)
N2A—C9A—C8A111.59 (16)N2B—C9B—C8B111.13 (15)
N2A—C9A—C11A122.00 (18)N2B—C9B—C11B121.15 (16)
C8A—C9A—C11A126.40 (17)C8B—C9B—C11B127.72 (16)
C9A—C11A—H11A109.5C9B—C11B—H11D109.5
C9A—C11A—H11B109.5C9B—C11B—H11E109.5
H11A—C11A—H11B109.5H11D—C11B—H11E109.5
C9A—C11A—H11C109.5C9B—C11B—H11F109.5
H11A—C11A—H11C109.5H11D—C11B—H11F109.5
H11B—C11A—H11C109.5H11E—C11B—H11F109.5
C17A—C12A—C13A120.47 (16)C13B—C12B—C17B119.86 (15)
C17A—C12A—N4A117.83 (15)C13B—C12B—N4B121.62 (16)
C13A—C12A—N4A121.69 (16)C17B—C12B—N4B118.50 (15)
C12A—C13A—C14A118.98 (17)C12B—C13B—C14B119.02 (17)
C12A—C13A—H13A120.5C12B—C13B—H13B120.5
C14A—C13A—H13A120.5C14B—C13B—H13B120.5
C15A—C14A—C13A121.60 (16)C15B—C14B—C13B122.24 (17)
C15A—C14A—H14A119.2C15B—C14B—H14B118.9
C13A—C14A—H14A119.2C13B—C14B—H14B118.9
C14A—C15A—C16A117.23 (17)C14B—C15B—C16B117.11 (16)
C14A—C15A—C18A121.54 (19)C14B—C15B—C18B121.03 (18)
C16A—C15A—C18A121.2 (2)C16B—C15B—C18B121.85 (19)
C17A—C16A—C15A122.28 (19)C17B—C16B—C15B121.41 (18)
C17A—C16A—H16A118.9C17B—C16B—H16B119.3
C15A—C16A—H16A118.9C15B—C16B—H16B119.3
C12A—C17A—C16A119.44 (17)C16B—C17B—C12B120.27 (17)
C12A—C17A—H17A120.3C16B—C17B—H17B119.9
C16A—C17A—H17A120.3C12B—C17B—H17B119.9
C15A—C18A—H18A109.5C15B—C18B—H18D109.5
C15A—C18A—H18B109.5C15B—C18B—H18E109.5
H18A—C18A—H18B109.5H18D—C18B—H18E109.5
C15A—C18A—H18C109.5C15B—C18B—H18F109.5
H18A—C18A—H18C109.5H18D—C18B—H18F109.5
H18B—C18A—H18C109.5H18E—C18B—H18F109.5
C7A—N1A—N2A—C9A1.0 (2)C7B—N1B—N2B—C9B1.9 (2)
C6A—N1A—N2A—C9A170.15 (17)C6B—N1B—N2B—C9B173.91 (15)
C8A—N3A—N4A—C12A178.65 (14)C8B—N3B—N4B—C12B173.28 (14)
F1A—C1A—C2A—F2A0.3 (2)F1B—C1B—C2B—F2B0.6 (2)
C6A—C1A—C2A—F2A179.51 (15)C6B—C1B—C2B—F2B179.86 (15)
F1A—C1A—C2A—C3A179.63 (16)F1B—C1B—C2B—C3B178.45 (15)
C6A—C1A—C2A—C3A0.6 (3)C6B—C1B—C2B—C3B1.1 (3)
F2A—C2A—C3A—F3A0.7 (3)F2B—C2B—C3B—F3B1.1 (3)
C1A—C2A—C3A—F3A179.38 (16)C1B—C2B—C3B—F3B179.91 (15)
F2A—C2A—C3A—C4A178.92 (17)F2B—C2B—C3B—C4B179.96 (16)
C1A—C2A—C3A—C4A1.1 (3)C1B—C2B—C3B—C4B1.0 (3)
F3A—C3A—C4A—F4A0.0 (3)F3B—C3B—C4B—F4B1.6 (3)
C2A—C3A—C4A—F4A178.21 (17)C2B—C3B—C4B—F4B177.32 (16)
F3A—C3A—C4A—C5A179.42 (17)F3B—C3B—C4B—C5B179.22 (15)
C2A—C3A—C4A—C5A1.2 (3)C2B—C3B—C4B—C5B0.3 (3)
F4A—C4A—C5A—F5A0.0 (3)F4B—C4B—C5B—F5B0.3 (3)
C3A—C4A—C5A—F5A179.42 (17)C3B—C4B—C5B—F5B177.35 (15)
F4A—C4A—C5A—C6A178.77 (17)F4B—C4B—C5B—C6B177.91 (15)
C3A—C4A—C5A—C6A0.6 (3)C3B—C4B—C5B—C6B0.3 (3)
F5A—C5A—C6A—C1A178.83 (15)F5B—C5B—C6B—C1B177.42 (14)
C4A—C5A—C6A—C1A0.1 (3)C4B—C5B—C6B—C1B0.2 (2)
F5A—C5A—C6A—N1A0.4 (3)F5B—C5B—C6B—N1B0.2 (2)
C4A—C5A—C6A—N1A179.20 (16)C4B—C5B—C6B—N1B177.83 (15)
F1A—C1A—C6A—C5A179.83 (15)F1B—C1B—C6B—C5B179.05 (14)
C2A—C1A—C6A—C5A0.0 (3)C2B—C1B—C6B—C5B0.5 (2)
F1A—C1A—C6A—N1A0.6 (2)F1B—C1B—C6B—N1B3.3 (2)
C2A—C1A—C6A—N1A179.25 (15)C2B—C1B—C6B—N1B177.09 (15)
C7A—N1A—C6A—C5A108.5 (2)C7B—N1B—C6B—C5B110.3 (2)
N2A—N1A—C6A—C5A58.9 (2)N2B—N1B—C6B—C5B60.4 (2)
C7A—N1A—C6A—C1A70.7 (2)C7B—N1B—C6B—C1B67.2 (2)
N2A—N1A—C6A—C1A121.86 (18)N2B—N1B—C6B—C1B122.02 (18)
C6A—N1A—C7A—O10A11.6 (3)C6B—N1B—C7B—O10B7.4 (3)
N2A—N1A—C7A—O10A179.68 (17)N2B—N1B—C7B—O10B178.75 (16)
C6A—N1A—C7A—C8A168.41 (16)C6B—N1B—C7B—C8B172.48 (15)
N2A—N1A—C7A—C8A0.28 (19)N2B—N1B—C7B—C8B1.11 (18)
N4A—N3A—C8A—C9A175.80 (16)N4B—N3B—C8B—C9B174.23 (16)
N4A—N3A—C8A—C7A1.5 (3)N4B—N3B—C8B—C7B1.6 (2)
O10A—C7A—C8A—N3A2.8 (3)O10B—C7B—C8B—N3B6.1 (3)
N1A—C7A—C8A—N3A177.21 (16)N1B—C7B—C8B—N3B173.72 (16)
O10A—C7A—C8A—C9A179.58 (18)O10B—C7B—C8B—C9B179.89 (18)
N1A—C7A—C8A—C9A0.45 (19)N1B—C7B—C8B—C9B0.04 (18)
N1A—N2A—C9A—C8A1.3 (2)N1B—N2B—C9B—C8B1.9 (2)
N1A—N2A—C9A—C11A179.31 (19)N1B—N2B—C9B—C11B178.53 (17)
N3A—C8A—C9A—N2A176.63 (17)N3B—C8B—C9B—N2B172.68 (16)
C7A—C8A—C9A—N2A1.1 (2)C7B—C8B—C9B—N2B1.3 (2)
N3A—C8A—C9A—C11A2.8 (3)N3B—C8B—C9B—C11B6.9 (3)
C7A—C8A—C9A—C11A179.5 (2)C7B—C8B—C9B—C11B179.19 (19)
N3A—N4A—C12A—C17A166.96 (16)N3B—N4B—C12B—C13B18.4 (2)
N3A—N4A—C12A—C13A13.2 (2)N3B—N4B—C12B—C17B160.29 (15)
C17A—C12A—C13A—C14A0.3 (2)C17B—C12B—C13B—C14B2.3 (3)
N4A—C12A—C13A—C14A179.78 (14)N4B—C12B—C13B—C14B176.44 (15)
C12A—C13A—C14A—C15A0.1 (3)C12B—C13B—C14B—C15B0.2 (3)
C13A—C14A—C15A—C16A0.7 (3)C13B—C14B—C15B—C16B2.6 (3)
C13A—C14A—C15A—C18A179.54 (17)C13B—C14B—C15B—C18B175.97 (16)
C14A—C15A—C16A—C17A0.9 (3)C14B—C15B—C16B—C17B2.5 (3)
C18A—C15A—C16A—C17A179.30 (19)C18B—C15B—C16B—C17B176.00 (17)
C13A—C12A—C17A—C16A0.1 (3)C15B—C16B—C17B—C12B0.2 (3)
N4A—C12A—C17A—C16A179.99 (17)C13B—C12B—C17B—C16B2.3 (3)
C15A—C16A—C17A—C12A0.5 (3)N4B—C12B—C17B—C16B176.44 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4a—H4a···O10a0.86 (2)2.16 (1)2.833 (2)134 (2)
N4a—H4a···O10b0.86 (2)2.49 (2)3.044 (2)122 (1)
N4b—H4b···O10a0.86 (2)2.56 (2)3.036 (2)116 (1)
N4b—H4b···O10b0.86 (2)2.17 (1)2.818 (2)133 (1)
C11a—H11b···F3ai0.962.553.264 (3)132
Symmetry code: (i) x+1/2, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC17H11F5N4O
Mr382.30
Crystal system, space groupMonoclinic, P21/n
Temperature (K)297
a, b, c (Å)11.6678 (12), 16.6283 (17), 17.8362 (18)
β (°) 97.368 (2)
V3)3431.9 (6)
Z8
Radiation typeMo Kα
µ (mm1)0.13
Crystal size (mm)0.32 × 0.22 × 0.22
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS in SAINT-NT; Bruker, 2002)
Tmin, Tmax0.96, 0.98
No. of measured, independent and
observed [I > 2σ(I)] reflections
28507, 7711, 4062
Rint0.032
(sin θ/λ)max1)0.660
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.123, 0.92
No. of reflections7711
No. of parameters495
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.18, 0.12

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Comparative data for selected parameters in (I), (II) and (III) top
Bond(Ia)(Ib)(II)(III)
N1—C71.374 (2)1.377 (2)1.344 (4)1.354 (2)
C7—C81.447 (2)1.447 (2)1.377 (4)1.384 (2)
C8—C91.426 (2)1.428 (2)1.417 (4)1.428 (2)
C9—N21.294 (2)1.305 (2)1.310 (3)1.326 (2)
C8—N31.328 (2)1.326 (2)1.388 (4)1.393 (2)
N3—N41.293 (2)1.303 (2)1.258 (3)1.249 (2)
N4—C121.422 (2)1.411 (2)1.423 (4)1.426 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4a—H4a···O10a0.864 (16)2.164 (14)2.833 (2)134.0 (15)
N4a—H4a···O10b0.864 (16)2.493 (17)3.044 (2)122.3 (14)
N4b—H4b···O10a0.855 (15)2.561 (18)3.036 (2)116.1 (13)
N4b—H4b···O10b0.855 (15)2.168 (14)2.818 (2)132.7 (13)
C11a—H11b···F3ai0.962.553.264 (3)132
Symmetry code: (i) x+1/2, y+1/2, z1/2.
ππ contacts in (I) (Å, °) top
Group 1···Group 2CCD (Å)DA (°)IPD (Å)
Cg2a···Cg3b3.6853 (13)10.68 (10)3.50 (6)
Cg2b···Cg3a3.6982 (12)9.67 (10)3.47 (1)
Ring-centroid codes (see also Fig. 1): Cg2a is the centroid of the ring C1a–C6a, Cg3a that of C12a–C17a, Cg2b that of C1b–C6b and Cg3b that of C12b–C17b. CCD is the centre-to-centre distance, DA is the dihedral angle between rings and IPD is the interplanar distance, or the (mean) distance from one plane to the neighbouring centroid. For details, see Janiak (2000).
 

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