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In the title compound, C28H18FN5, mol­ecules are linked by a combination of N-H...N, C-H...N and C-H...[pi](arene) hydrogen bonds into complex double chains. The chains enclose cavities, four per unit cell, each of volume ca 102 Å3 and apparently containing disordered solvent.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109025566/su3034sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109025566/su3034Isup2.hkl
Contains datablock I

CCDC reference: 746071

Comment top

We report here the structure of the title compound, (I), which we compare with the three analogues (II)–(IV) (see Scheme) whose structures were reported fairly recently (Low et al., 2007). As in the synthesis of compounds (II)–(IV), compound (I) was prepared by a multicomponent condensation reaction between 5-amino-3-methyl-1-henylpyrazole [phenyl?], 3-(2-cyanoacetyl)indole and an aryl aldehyde, here 2-fluorobenzaldehyde, using microwave irradiation under solvent-free conditions. This method has been developed (Quiroga et al., 2007) as a route for the introduction of an indolyl residue into substituted pyrazolo[3,4-b]pyridines, in order to assess the influence of the naturally occurring indolyl group on the biological activity of the resulting synthetic products. The crystallization characteristics of compounds (I)–(IV) show some interesting variations, which cannot be readily predicted or explained. Compounds (I) and (II) both crystallize in space group C2/c, while (II) ? and (IV) both crystallize in P1: however, while compounds (II) and (III) crystallize as stoichiometric 1:1 solvates with dimethylformamide, both (I) and (IV) crystallize in solvent-free forms.

The pyrazolopyridine component of the molecule of (I) is effectively planar, with the maximum deviation from the mean plane that of atom C5, 0.067 (2) Å; this slight deviation may be associated with the presence of three adjacent substituents, two of them bulky, at atoms C4–C6. It is interesting to note that the displacement of atom C51 from the mean plane of the bicyclic ring system, 0.270 (2) Å, is in the direction opposite from those of the displacements of C41 and C63, -0.053 (2) Å and -0.174 (2) Å, respectively, indicating that non-bonded repulsions between these substituents are probably the cause of the displacements. Due to this effective planarity, the molecular conformation can therefore be described in terms of just the three torsional angles (Table 1) defining the orientation of the substituents relative to the pyrazolopyridine unit. The dihedral angles between the mean planes of the substituents and that of the pyrazolopyridine unit are, for the unsubstituted phenyl ring at N1, 45.6 (2)°, for the substituted phenyl ring at C4, 70.8 (2)°, and for the indolyl unit at C6, 25.1 (2)°. Accordingly, the molecule of (I) has no internal symmetry and thus it is conformationally chiral, although the centrosymmetric space group accommodates equal numbers of the two conformational enantiomers. The bond distances and angles within the molecule of compound (I) show no unexpected values.

Three independent hydrogen bonds, one each of N—H···N, C—H···N and C—H···π(arene) types (Table 2), link the molecules of (I) into a complex chain of rings, or molecular ladder. The N—H···N hydrogen bond links molecules related by translation into a C(9) (Bernstein et al., 1995) chain running parallel to the [010] direction; this chain formation is augmented by the C—H···π(arene) hydrogen bond, so forming a chain of rings along [010]. Pairs of antiparallel chains, related to one another by inversion, are then linked by paired C—H···N hydrogen bonds to form a complex chain of edge-fused rings in which R22(14) rings centred at (1/4, n + 1/4, 1/2), where n represents an integer, alternate with R44(26) rings centred at (1/4, n - 1/4, 1/2) where n again represents an integer (Fig. 2). The formation of the chain is weakly augmented by a π···π stacking interaction involving pairs of pyridine rings: the pyridyl rings of the molecules at (x, y, z) and (1/2 - x, 1/2, - y, 1 - z), which form the R22(14) motif, are strictly parallel with an interplanar spacing of 3.674 (2) Å; the ring–centroid separation is 3.840 (2) Å, corresponding to a ring–centroid offset of 1.117 (2) Å.

Four chains of this type run through each unit cell, along the lines (1/4, y, 0), (1/4, y, 1/2), (3/4, y, 0) and (3/4, y, 1/2) (Fig. 3): there are no direction-specific interactions between adjacent chains, but instead these chains enclose cavities, totalling ca 9% of the unit-cell volume. There are four symmetry-related cavities per unit cell, each of volume ca 104 Å3, located on twofold rotation axes and centred close to (0, 0.335, 1/4), (0. 0.665, 3/4), (1/2, 0.835, 1/4) and (1/2, 0.165, 3/4). Each cavity is bounded by a number of aromatic C—H bonds, along with F atoms and the N atoms belonging to nitrile units (Fig. 3). While significant electron density is located within the cavities, calculated by the SQUEEZE option in PLATON (Spek, 2009) as 7 electrons per cavity, it did not prove possible to reconcile the distribution of electron density with any plausible array of disordered solvent molecules.

The supramolecular aggregation in compound (I) differs markedly from that observed for compounds (II) and (III) (Low et al., 2007) as in these structures the single N—H bond is engaged in a hydrogen bond to the dimethylformamide component. Thus, in compound (II), a single C—H···π(arene) hydrogen bond links the pyrazolopyridine units into centrosymmetric dimers from which the dimethylformamide units are pendent, while in compound (III), a combination of C—H···N and C—H···π(arene) hydrogen bonds links the pyrazolopyridine units into a chain containing two types of ring, again with pendent solvent molecules. By contrast, the molecules of compound (IV), where no solvent component is present, are linked into simple C(12) chains by an N—H···O hydrogen bond. Hence, the hydrogen-bonding behaviour is different in each of compounds (I)–(IV). On the other hand, all four compounds exhibit a π···π stacking interaction involving the pyridyl rings in pairs of molecules related by inversion. In compound (II), as in (I), this interaction augments the formation of a hydrogen-bonded dimer unit, in (III) it augments the chain formation, and in compound (IV), this interaction links a pair of antiparallel C(12) chains.

Related literature top

For related literature, see: Bernstein et al. (1995); Low et al. (2007); Quiroga et al. (2007); Spek (2009).

Experimental top

An equimolar mixture of 2-fluorobenzaldehyde, 5-amino-3-methyl-1-henylpyrazole [phenyl?] and 3-(2-cyanoacetyl)indole was subjected to microwave irradiation in the absence of solvent, using a focused microwave reaction (CEM Discover), with maximum power 300 W during 9 min at a controlled temperature of 473 K. The reaction mixture was allowed to cool to ambient temperature, and it was then extracted with hot ethanol/dimethylformamide (2:1, v/v); the combined extracts were reduced to small volume and the resulting solid product was collected by filtration, and washed successively with ethanol and diethyl ether to provide colourless crystals of the title compound (I) suitable for single-crystal X-ray diffraction (yield 83%, m.p. 570–571 K). MS (EI, 70 eV) m/z (%) = 443 (100, M+), 350 (44), 140 (11), 77 (43), 51 (30).

Refinement top

All H atoms were located in difference electron-density maps, and then treated as riding atoms in geometrically idealized positions with distances C—H 0.95 Å (aromatic and heteroaromatic), or 0.98 Å (methyl) and N—H 0.88 Å, and with Uiso(H) = kUeq(carrier), where k = 1.5 for the methyl group, which was permitted to rotate but not to tilt, and 1.2 for all other H atoms. Refinement based on the presence only of the pyrazolopyridine molecule converged to R = 0.141, with several unacceptably large peaks in the difference electron-density map. At this point, examination of the refined structure using PLATON (Spek, 2009) indicated the presence of four symmetry-related voids per cell, each of volume ca 104 Å3, located at (0, 0.335, 1/4), (0. 0.665, 3/4), (1/2, 0.835, 1/4) and (1/2, 0.165, 3/4). Within each void, there were four residual peaks in a T-shaped arrangement, with the shaft of the T lying along a twofold rotation axis, and an angle of ca 92° between the shaft and the crosspieces of the T: no plausible solvent model, for example based upon two partially occupied methanol sites, could be developed from these peaks, hence the SQUEEZE option in PLATON was applied, which indicated 7 electrons per void, and which led to an acceptable R factor, with satisfactory values for the electron-density residuals.

Computing details top

Data collection: COLLECT (Hooft, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of compound (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. A stereoview of part of the crystal structure of compound (I) showing the formation of a complex hydrogen-bonded chain running parallel to the [010] direction. For the sake of clarity, the H atoms not involved in the motifs shown have been omitted.
[Figure 3] Fig. 3. Projection of the hydrogen-bonded chains onto (010) indicating the location of the cavities. Accordingly, the H atoms have all been included.
4-(2-Fluorophenyl)-6-(1H-indol-1-yl)-3-methyl-1-phenyl-1H- pyrazolo[3,4-b]pyridine-5-carbonitrile top
Crystal data top
C28H18FN5F(000) = 1840
Mr = 443.47Dx = 1.280 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 5280 reflections
a = 24.155 (3) Åθ = 3.2–27.5°
b = 10.5830 (7) ŵ = 0.08 mm1
c = 18.712 (3) ÅT = 120 K
β = 105.743 (10)°Block, colourless
V = 4604.0 (10) Å30.45 × 0.26 × 0.25 mm
Z = 8
Data collection top
Bruker Nonius KappaCCD
diffractometer
5280 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode3346 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.065
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.2°
ϕ & ω scansh = 3131
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1313
Tmin = 0.968, Tmax = 0.979l = 2424
51259 measured reflections
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)] = 0.069Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.211H-atom parameters constrained
S = 1.10 w = 1/[σ2(Fo2) + (0.1279P)2]
where P = (Fo2 + 2Fc2)/3
5280 reflections(Δ/σ)max = 0.001
308 parametersΔρmax = 0.38 e Å3
0 restraintsΔρmin = 0.29 e Å3
Crystal data top
C28H18FN5V = 4604.0 (10) Å3
Mr = 443.47Z = 8
Monoclinic, C2/cMo Kα radiation
a = 24.155 (3) ŵ = 0.08 mm1
b = 10.5830 (7) ÅT = 120 K
c = 18.712 (3) Å0.45 × 0.26 × 0.25 mm
β = 105.743 (10)°
Data collection top
Bruker Nonius KappaCCD
diffractometer
5280 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
3346 reflections with I > 2σ(I)
Tmin = 0.968, Tmax = 0.979Rint = 0.065
51259 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0690 restraints
wR(F2) = 0.211H-atom parameters constrained
S = 1.10Δρmax = 0.38 e Å3
5280 reflectionsΔρmin = 0.29 e Å3
308 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.23023 (8)0.05625 (16)0.59693 (11)0.0260 (4)
N20.25698 (8)0.04293 (18)0.57125 (11)0.0284 (5)
C30.30434 (10)0.0025 (2)0.55817 (13)0.0266 (5)
C3A0.30961 (9)0.1348 (2)0.57526 (12)0.0252 (5)
C40.35003 (9)0.2307 (2)0.57830 (12)0.0248 (5)
C50.33732 (9)0.3477 (2)0.60517 (12)0.0251 (5)
C60.28349 (9)0.3700 (2)0.62212 (12)0.0255 (5)
N70.24613 (8)0.27690 (16)0.62049 (10)0.0253 (4)
C7A0.26120 (9)0.1643 (2)0.60033 (12)0.0247 (5)
C110.17574 (9)0.0383 (2)0.61160 (13)0.0262 (5)
C120.16577 (10)0.0889 (2)0.67510 (13)0.0304 (5)
H120.19540.13310.70990.036*
C130.11224 (11)0.0744 (2)0.68726 (15)0.0379 (6)
H130.10500.10810.73090.046*
C140.06897 (11)0.0106 (3)0.63568 (16)0.0424 (7)
H140.03200.00230.64370.051*
C150.07947 (11)0.0404 (3)0.57333 (16)0.0409 (7)
H150.04980.08470.53860.049*
C160.13338 (10)0.0275 (2)0.56082 (13)0.0313 (6)
H160.14100.06340.51790.038*
C310.34417 (10)0.0832 (2)0.53262 (14)0.0334 (6)
H31A0.32960.17000.52990.050*
H31B0.38250.07940.56780.050*
H31C0.34660.05650.48340.050*
C410.40241 (10)0.2080 (2)0.55290 (13)0.0278 (5)
C420.45715 (10)0.2061 (2)0.60056 (14)0.0320 (6)
F420.46346 (6)0.22698 (15)0.67355 (8)0.0459 (4)
C430.50512 (11)0.1817 (2)0.57729 (16)0.0402 (6)
H430.54210.17920.61180.048*
C440.49875 (11)0.1608 (2)0.50246 (16)0.0407 (7)
H440.53160.14510.48520.049*
C450.44480 (10)0.1627 (2)0.45284 (15)0.0367 (6)
H450.44070.14870.40150.044*
C460.39693 (10)0.1848 (2)0.47759 (13)0.0307 (6)
H460.35980.18430.44330.037*
C510.38009 (10)0.4463 (2)0.61782 (13)0.0297 (5)
N510.41494 (9)0.5227 (2)0.62936 (12)0.0372 (5)
N610.24804 (8)0.70441 (18)0.63413 (11)0.0323 (5)
H610.25100.78530.62490.039*
C620.27979 (10)0.6102 (2)0.61538 (13)0.0295 (5)
H620.30840.62230.58980.035*
C630.26477 (9)0.4950 (2)0.63852 (13)0.0252 (5)
C63A0.21983 (9)0.5210 (2)0.67422 (12)0.0267 (5)
C640.18794 (10)0.4470 (2)0.71095 (13)0.0298 (5)
H640.19350.35810.71520.036*
C650.14832 (10)0.5058 (2)0.74078 (13)0.0331 (6)
H650.12680.45650.76620.040*
C660.13909 (10)0.6368 (2)0.73442 (13)0.0337 (6)
H660.11080.67400.75450.040*
C670.17025 (10)0.7122 (2)0.69965 (13)0.0326 (6)
H670.16460.80110.69600.039*
C67A0.21044 (10)0.6523 (2)0.67000 (12)0.0274 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0259 (10)0.0202 (10)0.0327 (11)0.0005 (8)0.0094 (8)0.0027 (8)
N20.0283 (11)0.0263 (10)0.0321 (11)0.0004 (8)0.0106 (8)0.0027 (8)
C30.0254 (12)0.0288 (12)0.0257 (12)0.0018 (10)0.0070 (9)0.0031 (9)
C3A0.0232 (11)0.0267 (12)0.0248 (12)0.0003 (9)0.0050 (9)0.0025 (9)
C40.0223 (11)0.0275 (12)0.0246 (11)0.0021 (9)0.0067 (9)0.0025 (9)
C50.0237 (11)0.0263 (12)0.0260 (12)0.0032 (9)0.0079 (9)0.0019 (9)
C60.0230 (11)0.0296 (12)0.0238 (12)0.0015 (9)0.0060 (9)0.0031 (9)
N70.0245 (10)0.0235 (10)0.0281 (10)0.0005 (8)0.0074 (8)0.0008 (8)
C7A0.0236 (11)0.0254 (12)0.0255 (12)0.0002 (9)0.0072 (9)0.0021 (9)
C110.0211 (11)0.0263 (12)0.0323 (12)0.0016 (9)0.0091 (9)0.0051 (10)
C120.0292 (12)0.0294 (13)0.0315 (13)0.0009 (10)0.0064 (10)0.0021 (10)
C130.0351 (14)0.0426 (15)0.0422 (15)0.0013 (11)0.0210 (12)0.0039 (12)
C140.0273 (13)0.0467 (16)0.0566 (18)0.0016 (12)0.0173 (13)0.0084 (13)
C150.0289 (13)0.0397 (15)0.0511 (16)0.0079 (11)0.0057 (12)0.0027 (13)
C160.0302 (13)0.0304 (13)0.0325 (13)0.0046 (10)0.0071 (10)0.0011 (10)
C310.0336 (13)0.0286 (13)0.0396 (14)0.0017 (10)0.0127 (11)0.0021 (11)
C410.0246 (12)0.0266 (12)0.0340 (13)0.0009 (9)0.0109 (10)0.0026 (10)
C420.0299 (13)0.0342 (14)0.0318 (13)0.0019 (10)0.0081 (10)0.0000 (10)
F420.0350 (8)0.0667 (11)0.0320 (8)0.0009 (7)0.0021 (7)0.0013 (7)
C430.0250 (13)0.0389 (15)0.0547 (17)0.0003 (11)0.0075 (12)0.0044 (13)
C440.0338 (14)0.0361 (15)0.0583 (18)0.0021 (11)0.0231 (13)0.0025 (12)
C450.0361 (14)0.0395 (15)0.0379 (14)0.0009 (11)0.0160 (12)0.0004 (12)
C460.0302 (13)0.0303 (13)0.0334 (13)0.0013 (10)0.0119 (11)0.0001 (10)
C510.0290 (13)0.0300 (13)0.0306 (13)0.0007 (11)0.0086 (10)0.0002 (10)
N510.0300 (11)0.0373 (12)0.0453 (13)0.0072 (10)0.0119 (10)0.0042 (10)
N610.0338 (11)0.0251 (10)0.0392 (12)0.0016 (8)0.0121 (9)0.0004 (9)
C620.0289 (12)0.0280 (12)0.0344 (13)0.0003 (10)0.0131 (10)0.0003 (10)
C630.0252 (12)0.0227 (11)0.0284 (12)0.0006 (9)0.0083 (10)0.0000 (9)
C63A0.0235 (12)0.0316 (13)0.0238 (11)0.0009 (9)0.0045 (9)0.0016 (10)
C640.0320 (13)0.0283 (13)0.0304 (12)0.0015 (10)0.0104 (10)0.0020 (10)
C650.0291 (13)0.0420 (15)0.0297 (13)0.0025 (11)0.0107 (10)0.0012 (11)
C660.0306 (13)0.0412 (15)0.0300 (13)0.0037 (11)0.0094 (10)0.0060 (11)
C670.0319 (13)0.0338 (14)0.0284 (13)0.0062 (10)0.0018 (10)0.0056 (10)
C67A0.0302 (12)0.0270 (12)0.0250 (12)0.0005 (10)0.0077 (10)0.0012 (9)
Geometric parameters (Å, º) top
N1—C7A1.358 (3)C41—C421.380 (3)
N1—N21.385 (2)C41—C461.401 (3)
N1—C111.428 (3)C42—F421.351 (3)
N2—C31.323 (3)C42—C431.368 (3)
C3—C3A1.435 (3)C43—C441.384 (4)
C3—C311.492 (3)C43—H430.9500
C3A—C41.399 (3)C44—C451.380 (4)
C3A—C7A1.408 (3)C44—H440.9500
C4—C51.401 (3)C45—C461.377 (3)
C4—C411.487 (3)C45—H450.9500
C5—C61.439 (3)C46—H460.9500
C5—C511.442 (3)C51—N511.145 (3)
C6—N71.331 (3)N61—C621.361 (3)
C6—C631.457 (3)N61—C67A1.382 (3)
N7—C7A1.330 (3)N61—H610.8800
C11—C161.381 (3)C62—C631.375 (3)
C11—C121.383 (3)C62—H620.9500
C12—C131.381 (3)C63—C63A1.447 (3)
C12—H120.9500C63A—C641.402 (3)
C13—C141.390 (4)C63A—C67A1.406 (3)
C13—H130.9500C64—C651.380 (3)
C14—C151.370 (4)C64—H640.9500
C14—H140.9500C65—C661.404 (3)
C15—C161.391 (3)C65—H650.9500
C15—H150.9500C66—C671.376 (3)
C16—H160.9500C66—H660.9500
C31—H31A0.9800C67—C67A1.395 (3)
C31—H31B0.9800C67—H670.9500
C31—H31C0.9800
C7A—N1—N2110.56 (18)C42—C41—C46117.4 (2)
C7A—N1—C11128.88 (18)C42—C41—C4123.0 (2)
N2—N1—C11120.44 (17)C46—C41—C4119.6 (2)
C3—N2—N1107.28 (18)F42—C42—C43118.7 (2)
N2—C3—C3A110.01 (19)F42—C42—C41118.5 (2)
N2—C3—C31120.2 (2)C43—C42—C41122.9 (2)
C3A—C3—C31129.7 (2)C42—C43—C44118.7 (2)
C4—C3A—C7A117.4 (2)C42—C43—H43120.6
C4—C3A—C3137.4 (2)C44—C43—H43120.6
C7A—C3A—C3105.01 (19)C45—C44—C43120.2 (2)
C3A—C4—C5115.92 (19)C45—C44—H44119.9
C3A—C4—C41121.0 (2)C43—C44—H44119.9
C5—C4—C41123.08 (19)C46—C45—C44120.1 (2)
C4—C5—C6121.55 (19)C46—C45—H45119.9
C4—C5—C51118.8 (2)C44—C45—H45119.9
C6—C5—C51119.6 (2)C45—C46—C41120.6 (2)
N7—C6—C5121.4 (2)C45—C46—H46119.7
N7—C6—C63115.44 (19)C41—C46—H46119.7
C5—C6—C63123.10 (19)N51—C51—C5178.2 (3)
C7A—N7—C6115.71 (19)C62—N61—C67A108.84 (19)
N7—C7A—N1125.3 (2)C62—N61—H61125.6
N7—C7A—C3A127.5 (2)C67A—N61—H61125.6
N1—C7A—C3A107.14 (19)N61—C62—C63110.7 (2)
C16—C11—C12121.2 (2)N61—C62—H62124.7
C16—C11—N1119.0 (2)C63—C62—H62124.7
C12—C11—N1119.9 (2)C62—C63—C63A105.77 (19)
C13—C12—C11119.2 (2)C62—C63—C6128.0 (2)
C13—C12—H12120.4C63A—C63—C6125.76 (19)
C11—C12—H12120.4C64—C63A—C67A118.5 (2)
C12—C13—C14120.1 (2)C64—C63A—C63134.5 (2)
C12—C13—H13120.0C67A—C63A—C63106.96 (19)
C14—C13—H13120.0C65—C64—C63A118.7 (2)
C15—C14—C13120.3 (2)C65—C64—H64120.7
C15—C14—H14119.9C63A—C64—H64120.7
C13—C14—H14119.9C64—C65—C66121.5 (2)
C14—C15—C16120.2 (2)C64—C65—H65119.2
C14—C15—H15119.9C66—C65—H65119.2
C16—C15—H15119.9C67—C66—C65121.2 (2)
C11—C16—C15119.1 (2)C67—C66—H66119.4
C11—C16—H16120.4C65—C66—H66119.4
C15—C16—H16120.4C66—C67—C67A116.9 (2)
C3—C31—H31A109.5C66—C67—H67121.5
C3—C31—H31B109.5C67A—C67—H67121.5
H31A—C31—H31B109.5N61—C67A—C67129.2 (2)
C3—C31—H31C109.5N61—C67A—C63A107.7 (2)
H31A—C31—H31C109.5C67—C67A—C63A123.1 (2)
H31B—C31—H31C109.5
C7A—N1—N2—C30.3 (2)N1—C11—C16—C15177.2 (2)
C11—N1—N2—C3176.09 (19)C14—C15—C16—C110.6 (4)
N1—N2—C3—C3A0.1 (2)C3A—C4—C41—C42112.1 (3)
N1—N2—C3—C31177.51 (19)C5—C4—C41—C4269.0 (3)
N2—C3—C3A—C4174.5 (3)C3A—C4—C41—C4666.5 (3)
C31—C3—C3A—C42.8 (5)C5—C4—C41—C46112.3 (3)
N2—C3—C3A—C7A0.4 (2)C46—C41—C42—F42179.4 (2)
C31—C3—C3A—C7A176.9 (2)C4—C41—C42—F420.6 (3)
C7A—C3A—C4—C51.0 (3)C46—C41—C42—C430.6 (4)
C3—C3A—C4—C5174.5 (2)C4—C41—C42—C43178.2 (2)
C7A—C3A—C4—C41179.9 (2)F42—C42—C43—C44179.7 (2)
C3—C3A—C4—C416.6 (4)C41—C42—C43—C441.5 (4)
C3A—C4—C5—C65.4 (3)C42—C43—C44—C451.0 (4)
C41—C4—C5—C6173.5 (2)C43—C44—C45—C460.3 (4)
C3A—C4—C5—C51173.0 (2)C44—C45—C46—C411.3 (4)
C41—C4—C5—C518.1 (3)C42—C41—C46—C450.8 (3)
C4—C5—C6—N77.2 (3)C4—C41—C46—C45179.6 (2)
C51—C5—C6—N7171.1 (2)C67A—N61—C62—C630.6 (3)
C4—C5—C6—C63169.7 (2)N61—C62—C63—C63A0.2 (3)
C51—C5—C6—C6311.9 (3)N61—C62—C63—C6172.3 (2)
C5—C6—N7—C7A1.8 (3)N7—C6—C63—C62150.6 (2)
C63—C6—N7—C7A175.36 (19)C5—C6—C63—C6226.5 (4)
C6—N7—C7A—N1178.1 (2)N7—C6—C63—C63A20.0 (3)
C6—N7—C7A—C3A5.3 (3)C5—C6—C63—C63A162.9 (2)
N2—N1—C7A—N7177.7 (2)C62—C63—C63A—C64177.7 (2)
C11—N1—C7A—N71.7 (4)C6—C63—C63A—C6410.0 (4)
N2—N1—C7A—C3A0.6 (2)C62—C63—C63A—C67A0.2 (3)
C11—N1—C7A—C3A175.4 (2)C6—C63—C63A—C67A172.1 (2)
C4—C3A—C7A—N76.9 (3)C67A—C63A—C64—C650.6 (3)
C3—C3A—C7A—N7177.7 (2)C63—C63A—C64—C65178.3 (2)
C4—C3A—C7A—N1176.06 (19)C63A—C64—C65—C660.6 (4)
C3—C3A—C7A—N10.6 (2)C64—C65—C66—C671.6 (4)
C7A—N1—C11—C16131.2 (2)C65—C66—C67—C67A1.2 (3)
N2—N1—C11—C1644.5 (3)C62—N61—C67A—C67179.3 (2)
C7A—N1—C11—C1247.4 (3)C62—N61—C67A—C63A0.6 (3)
N2—N1—C11—C12136.9 (2)C66—C67—C67A—N61178.4 (2)
C16—C11—C12—C130.7 (3)C66—C67—C67A—C63A0.1 (3)
N1—C11—C12—C13177.8 (2)C64—C63A—C67A—N61177.75 (19)
C11—C12—C13—C140.6 (4)C63—C63A—C67A—N610.5 (3)
C12—C13—C14—C151.3 (4)C64—C63A—C67A—C671.0 (3)
C13—C14—C15—C160.7 (4)C63—C63A—C67A—C67179.3 (2)
C12—C11—C16—C151.3 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N61—H61···N2i0.882.102.953 (3)163
C46—H46···N7ii0.952.553.469 (3)164
C67—H67···Cgi0.952.773.652 (2)155
Symmetry codes: (i) x, y+1, z; (ii) x+1/2, y+1/2, z+1.

Experimental details

Crystal data
Chemical formulaC28H18FN5
Mr443.47
Crystal system, space groupMonoclinic, C2/c
Temperature (K)120
a, b, c (Å)24.155 (3), 10.5830 (7), 18.712 (3)
β (°) 105.743 (10)
V3)4604.0 (10)
Z8
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.45 × 0.26 × 0.25
Data collection
DiffractometerBruker Nonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.968, 0.979
No. of measured, independent and
observed [I > 2σ(I)] reflections
51259, 5280, 3346
Rint0.065
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.069, 0.211, 1.10
No. of reflections5280
No. of parameters308
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.38, 0.29

Computer programs: COLLECT (Hooft, 1999), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Selected torsion angles (º) top
N2—N1—C11—C12136.9 (2)C5—C6—C63—C63A162.9 (2)
C3A—C4—C41—C42112.1 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N61—H61···N2i0.882.102.953 (3)163
C46—H46···N7ii0.952.553.469 (3)164
C67—H67···Cgi0.952.773.652 (2)155
Symmetry codes: (i) x, y+1, z; (ii) x+1/2, y+1/2, z+1.
 

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