3,5-Dimethyl-4-[(E)-(2-nitro­phenyl)diazenyl]-1-(2,3,4,5,6-penta­fluoro­phenyl)-1H-pyrazole

The title compound, C₁₇H₁₀F₅N₅O₂, is described and com­pared with its 4-nitro­phenyl isomer [Bustos, Sánchez, Schott, Alvarez-Thon & Fuentealba (2007). Acta Cryst. E63, o1138–o1139]. The title mol­ecule presents its nitro group split into two rotationally disordered components, which in conjunction with the rotation of the `unclamped' rings constitute the main mol­ecular differences. Packing is directed by a head-to-tail type `I' C—F...F—C inter­action, generating double-chain strips running along [100]. These substructures are inter­linked by a variety of weak F...F, O...F, F...π and O...π inter­actions.

S1. Comment

The biological activity of substituted pyrazoles has been the subject of much research in medicine aimed at authenticating their potential properties. In fact, these compounds constitute an important class of bioactive drug targets in the pharmaceutical industry that includes blockbuster drugs such as celebrex (Penning et al., 1997) and viagra (Terrett et al., 1996). Pyrazole nuclei have attractive 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). Pyrazole compounds have also been used as ligands for obtaining transition metal complexes, since their heterocyclic nuclei may coordinate to the metal directly via one or both of the vicinal N atoms (Rojas et al., 2004). In a previous paper, we reported preliminary results of the synthesis of a large library of pyrazoles by reaction of β-diketohydrazones with substituted arylhydrazines (Bustos et al., 2009). We present here the structure of a new member of this family, the title compound, (I), and compare it with that of the previously reported 3,5-dimethyl-1-(2,3,4,5,6-pentafluorophenyl)-4-[(E)-(4-nitrophenyl)diazenyl]-1H-pyrazole, (II) (Bustos et al., 2007).

Scheme 1 shows the difference between the isomeric molecules, (I) having the nitro group in position 2 cis to the N—C bond, while (II) presents it in a trans position, namely position 4. In particular, the nitro group in (I) is rotationally disordered around the C—N bond (Fig. 1), with occupancy factors of 0.615 (3) and 0.385 (3) for components A and B, respectively. Although the N—O distances in (I) and (II) present some differences, this may be an artifact due to the disorder. The remaining interatomic bonds and angles are almost indistinguishable and do not depart from commonly found values [Cambridge Structural Database (CSD), Version 5.33; Allen 2002]. There are, however, conformational differences at those sites with a low torsional energy barrier. Both facts can be clearly seen in Fig. 2, which presents a least-squares overlap of (I) and (II) where only the central core (labelled atoms in the figure) has been fitted. The rotational differences in the nitro groups and benzene rings are apparent, and can be quantified by the dihedral angles subtended [values are given for (I) and (II), respectively]: Cg1—Cg2 = 72.16 (8) and 63.20 (16)°, Cg1—Cg3 = 7.26 (8) and 12.95 (16)°, and X1—Cg3 = 34.02 (12)/43.96 (15) and 4.19 (8)°, where X1 represents the nitro plane(s) and Cg the centroids of the planar rings as defined in Fig. 1].

Since there are no conventional hydrogen-bond donors present in (I) or (II), the supramolecular organization in both structures is due to weaker interactions. Fig. 3 presents a view of (I) perpendicular to (110), where the leading interactions (labelled in bold upper case) are clearly visible, viz. two F···F contacts (A and B, first and second entries in Table 1) which concatenate pentafluorophenyl groups along the [100] direction in an extremely planar fashion. This this can be assessed by inspection of the rightmost part of Fig. 3, where a side-on view of the pentafluorophenyl linkage is presented and quantified by the rather small zigzag dihedral angle of 12.3 (2)°. 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 types `I' and `II' (see Scheme 2); both cases analysed herein correspond to the first type. Although only type II contacts had originally been ascribed a stabilizing effect, further studies have begun to disclose a stabilizing character for many type I cases. For further details on this subject, see Baker et al. (2012, and references therein).

The F···F interactions define comb-like chains (heavy lines, Fig. 3, left), interdigitated by their centrosymmetrically related ones (light lines, Fig. 3) and this particular set-up enables neighbouring rings 1 and 3 to lie almost parallel to each other in a favourable disposition for a π–π stacking interaction (C in Fig. 3, first entry in Table 2). The result is a family of double-chain strips running along a.

Fig. 4, in turn, shows a view of the structure down the chain direction, displaying the way in which these strips interact with each other (one of them has been highlighted for clarity). Here, the responsible interactions are identified with bold upper-case labels; they run preferentially along [011] and are all weak contacts of very different types, viz. F···F (D) or O···F (E) (Table 1, third and fourth entries), or F···π (F) or O···π (G) (Table 2, second to fourth entries). The final result is a weakly but evenly connected three-dimensional structure.

It is interesting to analyse in parallel the closely related structure, (II), which in spite of the extreme analogies in molecular structure to (I) presents a substantially different packing scheme. As described by Bustos et al. (2007), the main interactions responsible for the supramolecular arrangement in (II) are two different π–π contacts linking rings 2 and 3, defining a family of π-bonded planes parallel to (100) (Fig. 5). These planes, in turn, are connected via F···F contacts between C₆F₅– groups in a head-to-tail fashion (Fig. 6, left), resembling the way in which the link in (I) is achieved but with two significant differences:

(i) The F-bonded strips they give rise to are not planar, but run in a definite zigzag fashion instead [Fig. 6, right; zigzag dihedral angle = 79.1 (2)°].

(ii) F···F contact distances between symmetry-related C₆F₅– groups are longer in (II) than in (I) [F2···F4' = 2.838 (2) and 2.931 (3)Å, and F1···F5' = 2.833 (2) and 3.009 (3)Å, for (I) and (II), respectively], suggesting their character is of second-order interactions in (II).

Although this packing diversity is obviously due to differences in the nitro-group disposition, it is not clear if it is also a consequence of steric effects [e.g. the fact that molecule (II) is longer than (I)] or due to intrinsic interactions of the nitro groups; while there are no obvious interactions in (II), there are a few in (I), viz. a conspicuous contact between the minor component of the disordered NO₂ and a neighburing F atom (Table 1, fourth entry), and some O···Cg contacts (Table 2, third or fourth entries).

Even if this fact could be left as an open issue, a definite conclusion from what is described above is that the structures discussed here provide further examples of type I C—F···F—C interactions that should be given due consideration as effective synthons in supramolecular organization.

Related literature

For related literature, see: Allen (2002); Baker et al. (2012); Bustos et al. (2007, 2009); Card et al. (2005); Elguero et al. (2002); Penning (1997); Rojas et al. (2004); Terrett et al. (1996).

S2. Experimental

3-[2-(2-Nitrophenyl)hydrazinylidene]pentane-2,4-dione (0.62 g, 2.5 mmol), perfluorophenylhydrazine (0.50 g), HOAc (5 ml) and ethanol (50 ml) were added to a 100 ml round-bottomed flask. The reaction mixture was stirred magnetically and heated under reflux for 36 h. After cooling to room temperature, the solid which formed was filtered off by suction and dried at 318 K for 24 h (yield 77%). Single crystals were obtained by saturation of tetrahydrofuran (20–25 ml) with the crude product and the insoluble impurities were removed by filtration. The filtered product was treated with charcoal (0.1 g) and the mixture was heated gently near boiling for 5 min, after which the hot solution was filtered again. Finally, maintaining heating, the product was filtered again and treated with an EtOH–H₂O mixture (15 ml, 1:1 v/v). The hot solution was covered with a watch glass and allowed to stand at room temperature. After 4–5 d, orange crystals of (I) were separated by filtration and dried at room temperature (m.p. 453–454 K).

S3. Refinement

The nitro group showed rotational disorder [occupancy factors = 0.615 (3) and 0.385 (3)]. Its refinement required some metric similarity restraints for equivalent N—O distances, but in spite of this some residual effects remained, mostly in the form of rather large Hirshfeld factors. All H atoms attached to C atoms were originally found in a difference Fourier map, but were subsequently repositioned in their expected positions and thereafter allowed to ride, with C—H = 0.96 Å and U_iso(H) = 1.5U_eq(C) for methyl H atoms, and with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) for aromatic H atoms. Methyl groups were allowed to rotate around their C—C bond.

Computing details

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 molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level. Dashed lines indicate the minor component of the NO₂ group. [Added text OK?]

Fig. 2. A least-squares fit of (I) (solid lines) and (II) (broken lines). Only labelled atoms are included in the fit. Double-dashed lines indicate the minor component of the NO₂ group. [Added text OK?]

Fig. 3. (Left) An (011) packing view of (I), showing the two chains (in heavy and light lines) forming the double-chain strip. Labels A, B and C correspond to different interaction types (see Comment). (Right) A side-on view of the almost planar 2,3,4,5,6-pentafluorophenyl chain [cf. that for (II) in Fig. 6].

Fig. 4. A (100) packing view of (I), along the chain direction, showing the way in which strips interact with each other via the contacts labelled D to G (see Comment).

Fig. 5. A (100) view of (II), showing the planes generated by the main interaction scheme in (II).

Fig. 6. (Left) An (010) view of (II), showing a sideways view of the planes presented in Fig. 5. Interactions between planes are mainly of the C—F···F—C type. (Right) The heavily corrugated 2,3,4,5,6-pentafluorophenyl chain [cf. that for (I) in Fig. 3].

3,5-Dimethyl-4-[(E)-(2-nitrophenyl)diazenyl]- 1-(2,3,4,5,6-pentafluorophenyl)-1H-pyrazole

Crystal data

C17H10F5N5O2	Z = 2
Mr = 411.30	F(000) = 416
Triclinic, P1	Dx = 1.628 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4932 (8) Å	Cell parameters from 2565 reflections
b = 10.5834 (11) Å	θ = 2.4–27.4°
c = 11.4141 (12) Å	µ = 0.15 mm^−1
α = 102.690 (2)°	T = 150 K
β = 100.459 (2)°	Polyhedron, orange
γ = 101.986 (2)°	0.31 × 0.20 × 0.16 mm
V = 838.99 (15) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	3591 independent reflections
Radiation source: sealed tube	2729 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
CCD rotation images, thin slices scans	θmax = 27.8°, θmin = 1.9°
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2002)	h = −9→9
Tmin = 0.96, Tmax = 0.98	k = −13→13
6844 measured reflections	l = −14→14

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.108	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0595P)^2] where P = (Fo^2 + 2Fc^2)/3
3591 reflections	(Δ/σ)max < 0.001
283 parameters	Δρmax = 0.27 e Å^−3
3 restraints	Δρmin = −0.15 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
F1	0.58756 (13)	0.26945 (11)	0.56969 (9)	0.0480 (3)
F2	0.55531 (15)	0.35863 (12)	0.36433 (10)	0.0590 (3)
F3	0.23662 (15)	0.42285 (10)	0.27315 (8)	0.0497 (3)
F4	−0.05348 (14)	0.39303 (10)	0.38431 (9)	0.0466 (3)
F5	−0.02132 (13)	0.30653 (10)	0.59100 (9)	0.0433 (3)
O1A	0.1439 (3)	0.09954 (18)	1.17384 (17)	0.0428 (6)	0.615 (3)
O2A	0.2749 (7)	0.0278 (3)	1.3204 (2)	0.0867 (13)	0.615 (3)
O1B	0.3871 (4)	0.1135 (3)	1.2283 (3)	0.0509 (11)	0.385 (3)
O2B	0.1594 (6)	0.0290 (5)	1.2975 (4)	0.0549 (13)	0.385 (3)
N1	0.29939 (18)	0.24157 (12)	0.69392 (11)	0.0302 (3)
N2	0.31069 (19)	0.33024 (13)	0.80596 (11)	0.0341 (3)
N3	0.27021 (18)	0.00236 (12)	0.86307 (12)	0.0324 (3)
N4	0.26878 (18)	0.01658 (12)	0.97441 (11)	0.0325 (3)
N5	0.2304 (2)	0.01844 (14)	1.21648 (13)	0.0493 (4)
C1	0.4292 (2)	0.30066 (15)	0.52578 (14)	0.0324 (4)
C2	0.4139 (2)	0.34546 (16)	0.42068 (14)	0.0355 (4)
C3	0.2520 (2)	0.37766 (15)	0.37404 (13)	0.0335 (4)
C4	0.1052 (2)	0.36377 (15)	0.43134 (14)	0.0326 (4)
C5	0.1230 (2)	0.31937 (15)	0.53640 (14)	0.0300 (3)
C6	0.2850 (2)	0.28766 (14)	0.58598 (13)	0.0282 (3)
C7	0.2861 (2)	0.11419 (14)	0.70145 (14)	0.0308 (3)
C8	0.2900 (2)	0.11934 (14)	0.82414 (13)	0.0279 (3)
C9	0.3057 (2)	0.25563 (15)	0.88536 (13)	0.0304 (3)
C10	0.2409 (2)	−0.10698 (14)	1.00775 (13)	0.0280 (3)
C11	0.2337 (2)	−0.23004 (15)	0.92880 (15)	0.0371 (4)
H11	0.2465	−0.2342	0.8486	0.044*
C12	0.2080 (2)	−0.34541 (16)	0.96790 (16)	0.0417 (4)
H12	0.2045	−0.4264	0.9142	0.050*
C13	0.1875 (2)	−0.34155 (17)	1.08668 (16)	0.0399 (4)
H13	0.1699	−0.4198	1.1123	0.048*
C14	0.1931 (2)	−0.22225 (16)	1.16675 (15)	0.0363 (4)
H14	0.1786	−0.2191	1.2465	0.044*
C15	0.2205 (2)	−0.10678 (15)	1.12672 (14)	0.0306 (3)
C16	0.2687 (3)	−0.00097 (16)	0.59531 (15)	0.0477 (5)
H16A	0.1666	−0.0051	0.5290	0.072*
H16B	0.2450	−0.0825	0.6204	0.072*
H16C	0.3833	0.0101	0.5678	0.072*
C17	0.3124 (3)	0.31649 (16)	1.01682 (14)	0.0383 (4)
H17A	0.3498	0.4124	1.0341	0.057*
H17B	0.4013	0.2871	1.0692	0.057*
H17C	0.1902	0.2893	1.0322	0.057*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F1	0.0382 (6)	0.0651 (7)	0.0508 (6)	0.0249 (5)	0.0135 (5)	0.0227 (5)
F2	0.0555 (7)	0.0835 (8)	0.0563 (7)	0.0239 (6)	0.0363 (6)	0.0316 (6)
F3	0.0744 (7)	0.0530 (6)	0.0315 (5)	0.0214 (6)	0.0175 (5)	0.0226 (5)
F4	0.0467 (6)	0.0579 (6)	0.0398 (6)	0.0266 (5)	0.0030 (5)	0.0163 (5)
F5	0.0362 (5)	0.0582 (6)	0.0444 (6)	0.0154 (5)	0.0186 (4)	0.0215 (5)
O1A	0.0483 (13)	0.0379 (11)	0.0456 (12)	0.0159 (9)	0.0143 (9)	0.0112 (9)
O2A	0.177 (4)	0.0525 (16)	0.0255 (13)	0.038 (3)	0.0029 (19)	0.0086 (11)
O1B	0.061 (2)	0.0328 (18)	0.048 (2)	−0.0073 (15)	0.0205 (16)	0.0006 (14)
O2B	0.061 (3)	0.062 (3)	0.046 (3)	0.009 (2)	0.034 (2)	0.013 (2)
N1	0.0393 (8)	0.0280 (7)	0.0256 (7)	0.0102 (6)	0.0089 (6)	0.0098 (5)
N2	0.0474 (8)	0.0294 (7)	0.0271 (7)	0.0134 (6)	0.0083 (6)	0.0080 (5)
N3	0.0400 (8)	0.0297 (7)	0.0320 (7)	0.0101 (6)	0.0130 (6)	0.0124 (6)
N4	0.0409 (8)	0.0298 (7)	0.0287 (7)	0.0096 (6)	0.0071 (6)	0.0125 (5)
N5	0.0823 (12)	0.0352 (8)	0.0349 (9)	0.0106 (8)	0.0252 (9)	0.0137 (7)
C1	0.0307 (8)	0.0339 (8)	0.0343 (8)	0.0121 (7)	0.0076 (7)	0.0088 (7)
C2	0.0389 (9)	0.0374 (9)	0.0342 (9)	0.0092 (7)	0.0180 (7)	0.0109 (7)
C3	0.0499 (10)	0.0285 (8)	0.0233 (8)	0.0093 (7)	0.0099 (7)	0.0094 (6)
C4	0.0378 (9)	0.0308 (8)	0.0300 (8)	0.0137 (7)	0.0048 (7)	0.0074 (7)
C5	0.0310 (8)	0.0310 (8)	0.0302 (8)	0.0077 (6)	0.0117 (7)	0.0091 (6)
C6	0.0358 (8)	0.0238 (7)	0.0262 (8)	0.0079 (6)	0.0075 (6)	0.0086 (6)
C7	0.0355 (8)	0.0256 (8)	0.0342 (8)	0.0091 (6)	0.0112 (7)	0.0106 (6)
C8	0.0295 (8)	0.0267 (8)	0.0301 (8)	0.0084 (6)	0.0084 (6)	0.0108 (6)
C9	0.0344 (8)	0.0303 (8)	0.0287 (8)	0.0117 (7)	0.0063 (7)	0.0105 (6)
C10	0.0272 (8)	0.0275 (8)	0.0309 (8)	0.0070 (6)	0.0053 (6)	0.0123 (6)
C11	0.0482 (10)	0.0340 (9)	0.0320 (8)	0.0143 (8)	0.0090 (7)	0.0118 (7)
C12	0.0517 (11)	0.0303 (9)	0.0438 (10)	0.0144 (8)	0.0078 (8)	0.0103 (7)
C13	0.0422 (10)	0.0324 (9)	0.0487 (10)	0.0099 (7)	0.0072 (8)	0.0209 (8)
C14	0.0362 (9)	0.0401 (9)	0.0364 (9)	0.0067 (7)	0.0098 (7)	0.0199 (7)
C15	0.0302 (8)	0.0297 (8)	0.0312 (8)	0.0050 (6)	0.0065 (6)	0.0097 (6)
C16	0.0803 (14)	0.0307 (9)	0.0359 (10)	0.0150 (9)	0.0219 (10)	0.0093 (7)
C17	0.0557 (11)	0.0321 (9)	0.0297 (8)	0.0161 (8)	0.0100 (8)	0.0091 (7)

Geometric parameters (Å, º)

F1—C1	1.3371 (17)	C5—C6	1.382 (2)
F2—C2	1.3349 (17)	C7—C8	1.384 (2)
F3—C3	1.3360 (16)	C7—C16	1.483 (2)
F4—C4	1.3388 (17)	C8—C9	1.428 (2)
F5—C5	1.3407 (17)	C9—C17	1.484 (2)
O1A—N5	1.301 (2)	C10—C15	1.393 (2)
O2A—N5	1.149 (3)	C10—C11	1.396 (2)
O1B—N5	1.342 (3)	C11—C12	1.378 (2)
O2B—N5	1.144 (3)	C11—H11	0.9300
N1—C7	1.3538 (18)	C12—C13	1.385 (2)
N1—N2	1.3869 (17)	C12—H12	0.9300
N1—C6	1.4160 (17)	C13—C14	1.374 (2)
N2—C9	1.3270 (18)	C13—H13	0.9300
N3—N4	1.2487 (16)	C14—C15	1.385 (2)
N3—C8	1.3934 (18)	C14—H14	0.9300
N4—C10	1.4257 (18)	C16—H16A	0.9600
N5—C15	1.465 (2)	C16—H16B	0.9600
C1—C2	1.378 (2)	C16—H16C	0.9600
C1—C6	1.381 (2)	C17—H17A	0.9600
C2—C3	1.374 (2)	C17—H17B	0.9600
C3—C4	1.376 (2)	C17—H17C	0.9600
C4—C5	1.376 (2)
F1···F5^i	2.8328 (15)	F4···F4^ii	2.9314 (15)
F2···F4^i	2.8384 (16)	O1B···F2^iii	2.625 (2)
C7—N1—N2	113.13 (12)	C7—C8—N3	120.21 (13)
C7—N1—C6	127.52 (12)	C7—C8—C9	106.60 (13)
N2—N1—C6	119.05 (12)	N3—C8—C9	133.10 (13)
C9—N2—N1	104.66 (12)	N2—C9—C8	110.39 (13)
N4—N3—C8	115.45 (13)	N2—C9—C17	120.39 (13)
N3—N4—C10	112.95 (12)	C8—C9—C17	129.21 (13)
O2B—N5—O1A	90.0 (3)	C15—C10—C11	116.97 (13)
O2A—N5—O1A	122.3 (2)	C15—C10—N4	118.79 (13)
O2B—N5—O1B	116.9 (3)	C11—C10—N4	124.24 (14)
O2A—N5—O1B	88.8 (3)	C12—C11—C10	121.02 (15)
O1A—N5—O1B	84.59 (19)	C12—C11—H11	119.5
O2B—N5—C15	126.4 (3)	C10—C11—H11	119.5
O2A—N5—C15	119.7 (2)	C11—C12—C13	120.43 (16)
O1A—N5—C15	115.86 (14)	C11—C12—H12	119.8
O1B—N5—C15	111.90 (18)	C13—C12—H12	119.8
F1—C1—C2	118.86 (13)	C14—C13—C12	120.14 (15)
F1—C1—C6	119.77 (14)	C14—C13—H13	119.9
C2—C1—C6	121.36 (14)	C12—C13—H13	119.9
F2—C2—C3	119.76 (14)	C13—C14—C15	118.90 (15)
F2—C2—C1	120.57 (15)	C13—C14—H14	120.6
C3—C2—C1	119.66 (14)	C15—C14—H14	120.6
F3—C3—C2	120.13 (14)	C14—C15—C10	122.54 (15)
F3—C3—C4	119.78 (14)	C14—C15—N5	116.86 (14)
C2—C3—C4	120.09 (14)	C10—C15—N5	120.60 (13)
F4—C4—C5	120.60 (14)	C7—C16—H16A	109.5
F4—C4—C3	119.87 (14)	C7—C16—H16B	109.5
C5—C4—C3	119.53 (14)	H16A—C16—H16B	109.5
F5—C5—C4	118.70 (14)	C7—C16—H16C	109.5
F5—C5—C6	119.74 (13)	H16A—C16—H16C	109.5
C4—C5—C6	121.56 (14)	H16B—C16—H16C	109.5
C1—C6—C5	117.79 (14)	C9—C17—H17A	109.5
C1—C6—N1	121.77 (14)	C9—C17—H17B	109.5
C5—C6—N1	120.44 (13)	H17A—C17—H17B	109.5
N1—C7—C8	105.22 (13)	C9—C17—H17C	109.5
N1—C7—C16	124.42 (13)	H17A—C17—H17C	109.5
C8—C7—C16	130.36 (14)	H17B—C17—H17C	109.5

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