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In the title compound, C
18H
13N
5, the two pyridyl rings form dihedral angles of 32.7 (2) and 30.1 (2)° with the triazole ring. The most favoured orientation of the pyridyl rings is that with their N atoms on opposite sides of the triazole ring directed towards the phenyl ring. π–π-Stacking interactions involving pyridyl rings are observed along the
a axis at a perpendicular distance of 3.670 (3) Å. This arrangement is further stabilized by weak intermolecular C—H
N hydrogen bonds.
Supporting information
CCDC reference: 147674
The title compound was prepared by the reaction of equivalent amounts of 4,4'-phenylphosphazoanilide and N,N'-dipyridoylhydrazine in N,N'-dimethylaniline for 3 h at 463–473 K (Grimmel et al., 1946; Klingsberg, 1958). Diffraction-quality crystals were obtained by recrystallization from acetone.
The H atoms were located from the different Fourier map and were refined isotropically; C—H distances are in the range 0.00 (0)–0.00 (0) Å.
Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
4-Phenyl-3,5-bis(2-pyridyl)-4
H-1,2,4-triazole
top
Crystal data top
C18H13N5 | F(000) = 624 |
Mr = 299.33 | Dx = 1.376 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 5.9217 (8) Å | Cell parameters from 57 reflections |
b = 15.3265 (15) Å | θ = 6.7–12.5° |
c = 15.9824 (14) Å | µ = 0.09 mm−1 |
β = 95.188 (10)° | T = 293 K |
V = 1444.6 (3) Å3 | Block, colorless |
Z = 4 | 0.58 × 0.25 × 0.22 mm |
Data collection top
Siemens P4 diffractometer | Rint = 0.028 |
Radiation source: sealed tube | θmax = 25.0°, θmin = 1.8° |
Graphite monochromator | h = −1→7 |
2θ/ω scans | k = −1→18 |
3576 measured reflections | l = −18→18 |
2531 independent reflections | 3 standard reflections every 97 reflections |
1800 reflections with I > 2σ(I) | intensity decay: 6.8% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.042 | All H-atom parameters refined |
wR(F2) = 0.109 | w = 1/[σ2(Fo2) + (0.0443P)2 + 0.1874P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
2531 reflections | Δρmax = 0.13 e Å−3 |
261 parameters | Δρmin = −0.14 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0124 (18) |
Crystal data top
C18H13N5 | V = 1444.6 (3) Å3 |
Mr = 299.33 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.9217 (8) Å | µ = 0.09 mm−1 |
b = 15.3265 (15) Å | T = 293 K |
c = 15.9824 (14) Å | 0.58 × 0.25 × 0.22 mm |
β = 95.188 (10)° | |
Data collection top
Siemens P4 diffractometer | Rint = 0.028 |
3576 measured reflections | 3 standard reflections every 97 reflections |
2531 independent reflections | intensity decay: 6.8% |
1800 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.109 | All H-atom parameters refined |
S = 1.01 | Δρmax = 0.13 e Å−3 |
2531 reflections | Δρmin = −0.14 e Å−3 |
261 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.3306 (3) | 0.84246 (11) | 0.49567 (10) | 0.0482 (5) | |
N2 | −0.2020 (3) | 0.60687 (11) | 0.69336 (10) | 0.0496 (5) | |
N3 | 0.1859 (3) | 0.86351 (12) | 0.70647 (10) | 0.0469 (4) | |
N4 | 0.0210 (3) | 0.81881 (12) | 0.74456 (10) | 0.0470 (4) | |
N5 | 0.0770 (2) | 0.75137 (10) | 0.62623 (9) | 0.0358 (4) | |
C1 | 0.7260 (4) | 0.92555 (15) | 0.55923 (15) | 0.0528 (6) | |
C2 | 0.6804 (4) | 0.91365 (15) | 0.47415 (15) | 0.0537 (6) | |
C3 | 0.4824 (4) | 0.87269 (15) | 0.44526 (14) | 0.0526 (6) | |
C4 | 0.5745 (4) | 0.89531 (13) | 0.61220 (14) | 0.0454 (5) | |
C5 | 0.3807 (3) | 0.85378 (12) | 0.57871 (12) | 0.0392 (5) | |
C6 | 0.2171 (3) | 0.82263 (13) | 0.63602 (11) | 0.0388 (5) | |
C7 | −0.0421 (3) | 0.75221 (13) | 0.69594 (11) | 0.0386 (5) | |
C8 | −0.2166 (3) | 0.69029 (13) | 0.71807 (11) | 0.0394 (5) | |
C9 | −0.3842 (4) | 0.71994 (15) | 0.76649 (13) | 0.0474 (5) | |
C10 | −0.3624 (4) | 0.55241 (16) | 0.71603 (14) | 0.0552 (6) | |
C11 | −0.5364 (4) | 0.57694 (17) | 0.76219 (14) | 0.0559 (6) | |
C12 | −0.5461 (4) | 0.66227 (17) | 0.78824 (15) | 0.0566 (6) | |
C13 | 0.0534 (3) | 0.69175 (12) | 0.55562 (11) | 0.0363 (5) | |
C14 | 0.2325 (4) | 0.63951 (14) | 0.53913 (13) | 0.0447 (5) | |
C15 | 0.2099 (4) | 0.58560 (15) | 0.46972 (14) | 0.0566 (6) | |
C16 | 0.0108 (5) | 0.58402 (16) | 0.41804 (14) | 0.0575 (6) | |
C17 | −0.1670 (4) | 0.63640 (15) | 0.43552 (13) | 0.0524 (6) | |
C18 | −0.1470 (4) | 0.69085 (14) | 0.50468 (12) | 0.0430 (5) | |
H14 | 0.372 (4) | 0.6405 (13) | 0.5774 (12) | 0.048 (6)* | |
H12 | −0.661 (4) | 0.6824 (14) | 0.8235 (13) | 0.059 (6)* | |
H18 | −0.269 (3) | 0.7255 (13) | 0.5178 (12) | 0.045 (6)* | |
H10 | −0.351 (4) | 0.4903 (15) | 0.6970 (13) | 0.058 (6)* | |
H17 | −0.306 (4) | 0.6379 (15) | 0.3991 (14) | 0.069 (7)* | |
H3 | 0.442 (4) | 0.8658 (16) | 0.3838 (15) | 0.074 (7)* | |
H1 | 0.864 (4) | 0.9566 (15) | 0.5813 (13) | 0.061 (7)* | |
H11 | −0.652 (4) | 0.5338 (16) | 0.7744 (14) | 0.069 (7)* | |
H2 | 0.783 (4) | 0.9357 (16) | 0.4375 (14) | 0.071 (7)* | |
H15 | 0.341 (5) | 0.5464 (17) | 0.4575 (15) | 0.081 (8)* | |
H16 | −0.006 (4) | 0.5442 (16) | 0.3670 (15) | 0.077 (7)* | |
H4 | 0.602 (4) | 0.9031 (14) | 0.6713 (14) | 0.057 (6)* | |
H9 | −0.385 (3) | 0.7822 (15) | 0.7848 (12) | 0.050 (6)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0484 (10) | 0.0495 (11) | 0.0466 (10) | −0.0039 (9) | 0.0031 (8) | 0.0007 (8) |
N2 | 0.0590 (12) | 0.0474 (11) | 0.0437 (10) | 0.0009 (10) | 0.0123 (9) | −0.0011 (8) |
N3 | 0.0473 (10) | 0.0476 (10) | 0.0454 (10) | −0.0006 (9) | 0.0024 (8) | −0.0080 (8) |
N4 | 0.0477 (10) | 0.0514 (10) | 0.0423 (9) | 0.0011 (9) | 0.0059 (8) | −0.0072 (8) |
N5 | 0.0357 (9) | 0.0390 (9) | 0.0328 (8) | 0.0019 (8) | 0.0026 (7) | −0.0023 (7) |
C1 | 0.0411 (13) | 0.0463 (13) | 0.0705 (15) | −0.0023 (11) | 0.0015 (12) | 0.0002 (11) |
C2 | 0.0507 (14) | 0.0475 (13) | 0.0651 (15) | −0.0026 (12) | 0.0171 (12) | 0.0022 (11) |
C3 | 0.0555 (14) | 0.0556 (14) | 0.0473 (13) | −0.0034 (12) | 0.0082 (11) | 0.0008 (11) |
C4 | 0.0443 (13) | 0.0418 (11) | 0.0486 (13) | 0.0011 (10) | −0.0040 (10) | 0.0015 (10) |
C5 | 0.0399 (11) | 0.0347 (10) | 0.0428 (10) | 0.0039 (9) | 0.0025 (9) | 0.0004 (9) |
C6 | 0.0362 (10) | 0.0390 (11) | 0.0402 (10) | 0.0023 (9) | −0.0015 (8) | −0.0015 (9) |
C7 | 0.0379 (11) | 0.0435 (11) | 0.0341 (10) | 0.0082 (10) | 0.0016 (8) | −0.0006 (9) |
C8 | 0.0413 (11) | 0.0444 (12) | 0.0324 (10) | 0.0053 (10) | 0.0020 (8) | 0.0020 (8) |
C9 | 0.0486 (13) | 0.0461 (13) | 0.0491 (12) | 0.0084 (11) | 0.0137 (10) | 0.0053 (10) |
C10 | 0.0711 (16) | 0.0463 (13) | 0.0497 (12) | −0.0042 (13) | 0.0134 (12) | 0.0009 (11) |
C11 | 0.0573 (15) | 0.0600 (15) | 0.0515 (13) | −0.0050 (13) | 0.0113 (11) | 0.0118 (12) |
C12 | 0.0548 (14) | 0.0631 (16) | 0.0550 (13) | 0.0132 (13) | 0.0210 (12) | 0.0135 (11) |
C13 | 0.0406 (11) | 0.0340 (10) | 0.0345 (9) | −0.0010 (9) | 0.0057 (8) | 0.0011 (8) |
C14 | 0.0430 (12) | 0.0471 (12) | 0.0443 (11) | 0.0073 (10) | 0.0057 (10) | −0.0006 (10) |
C15 | 0.0628 (15) | 0.0531 (14) | 0.0567 (14) | 0.0088 (13) | 0.0200 (12) | −0.0084 (11) |
C16 | 0.0726 (17) | 0.0551 (14) | 0.0463 (13) | −0.0099 (13) | 0.0144 (12) | −0.0138 (11) |
C17 | 0.0549 (14) | 0.0585 (14) | 0.0427 (12) | −0.0116 (12) | −0.0025 (11) | −0.0009 (11) |
C18 | 0.0397 (12) | 0.0447 (12) | 0.0441 (11) | 0.0011 (11) | 0.0020 (9) | −0.0004 (10) |
Geometric parameters (Å, º) top
N1—C3 | 1.343 (3) | C4—C5 | 1.378 (3) |
N1—C5 | 1.345 (2) | C5—C6 | 1.472 (3) |
N2—C10 | 1.339 (3) | C7—C8 | 1.470 (3) |
N2—C8 | 1.343 (3) | C8—C9 | 1.389 (3) |
N3—C6 | 1.316 (2) | C9—C12 | 1.372 (3) |
N3—N4 | 1.378 (2) | C10—C11 | 1.373 (3) |
N4—C7 | 1.316 (2) | C11—C12 | 1.375 (3) |
N5—C7 | 1.372 (2) | C13—C14 | 1.373 (3) |
N5—C6 | 1.372 (2) | C13—C18 | 1.377 (3) |
N5—C13 | 1.449 (2) | C14—C15 | 1.380 (3) |
C1—C4 | 1.369 (3) | C15—C16 | 1.377 (3) |
C1—C2 | 1.374 (3) | C16—C17 | 1.373 (3) |
C2—C3 | 1.373 (3) | C17—C18 | 1.381 (3) |
| | | |
C3—N1—C5 | 116.6 (2) | N4—C7—C8 | 121.8 (2) |
C10—N2—C8 | 116.6 (2) | N5—C7—C8 | 127.9 (2) |
C6—N3—N4 | 107.5 (2) | N2—C8—C9 | 122.9 (2) |
C7—N4—N3 | 107.4 (2) | N2—C8—C7 | 118.6 (2) |
C7—N5—C6 | 104.5 (2) | C9—C8—C7 | 118.4 (2) |
C7—N5—C13 | 128.2 (2) | C12—C9—C8 | 118.8 (2) |
C6—N5—C13 | 127.3 (2) | N2—C10—C11 | 124.0 (2) |
C4—C1—C2 | 119.1 (2) | C10—C11—C12 | 118.5 (2) |
C3—C2—C1 | 118.6 (2) | C9—C12—C11 | 119.1 (2) |
N1—C3—C2 | 123.6 (2) | C14—C13—C18 | 121.3 (2) |
C1—C4—C5 | 119.1 (2) | C14—C13—N5 | 119.7 (2) |
N1—C5—C4 | 123.0 (2) | C18—C13—N5 | 119.0 (2) |
N1—C5—C6 | 118.3 (2) | C13—C14—C15 | 118.9 (2) |
C4—C5—C6 | 118.7 (2) | C16—C15—C14 | 120.5 (2) |
N3—C6—N5 | 110.3 (2) | C17—C16—C15 | 119.9 (2) |
N3—C6—C5 | 122.0 (2) | C16—C17—C18 | 120.3 (2) |
N5—C6—C5 | 127.8 (2) | C13—C18—C17 | 119.1 (2) |
N4—C7—N5 | 110.3 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···N3 | 0.95 (2) | 2.65 (2) | 2.904 (3) | 96 (2) |
C9—H9···N4 | 1.00 (2) | 2.61 (2) | 2.886 (3) | 96 (1) |
C17—H17···N4i | 0.96 (2) | 2.67 (2) | 3.490 (3) | 143 (2) |
C11—H11···N3ii | 0.98 (3) | 2.64 (3) | 3.437 (3) | 138 (2) |
Symmetry codes: (i) x−1/2, −y+3/2, z−1/2; (ii) −x−1/2, y−1/2, −z+3/2. |
Experimental details
Crystal data |
Chemical formula | C18H13N5 |
Mr | 299.33 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 5.9217 (8), 15.3265 (15), 15.9824 (14) |
β (°) | 95.188 (10) |
V (Å3) | 1444.6 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.58 × 0.25 × 0.22 |
|
Data collection |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3576, 2531, 1800 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.109, 1.01 |
No. of reflections | 2531 |
No. of parameters | 261 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.13, −0.14 |
Selected geometric parameters (Å, º) topN1—C3 | 1.343 (3) | N3—N4 | 1.378 (2) |
N1—C5 | 1.345 (2) | N4—C7 | 1.316 (2) |
N2—C10 | 1.339 (3) | N5—C7 | 1.372 (2) |
N2—C8 | 1.343 (3) | N5—C6 | 1.372 (2) |
N3—C6 | 1.316 (2) | N5—C13 | 1.449 (2) |
| | | |
C6—N3—N4 | 107.5 (2) | N3—C6—C5 | 122.0 (2) |
C7—N4—N3 | 107.4 (2) | N5—C6—C5 | 127.8 (2) |
C7—N5—C6 | 104.5 (2) | N4—C7—N5 | 110.3 (2) |
N3—C6—N5 | 110.3 (2) | N4—C7—C8 | 121.8 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···N3 | 0.95 (2) | 2.65 (2) | 2.904 (3) | 96 (2) |
C9—H9···N4 | 1.00 (2) | 2.61 (2) | 2.886 (3) | 96 (1) |
C17—H17···N4i | 0.96 (2) | 2.67 (2) | 3.490 (3) | 143 (2) |
C11—H11···N3ii | 0.98 (3) | 2.64 (3) | 3.437 (3) | 138 (2) |
Symmetry codes: (i) x−1/2, −y+3/2, z−1/2; (ii) −x−1/2, y−1/2, −z+3/2. |
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Substituted 1,2,4-triazoles have been actively studied as bridging ligands coordinating through their vicinal N atoms. It is of interest that some complexes containing 1,2,4-triazole ligands have particular structures and specific magnetic properties (Vreugdenhil et al., 1987; Albada et al., 1984; Vos et al., 1983; Kahn & Martinez, 1998). On the other hand, some of the 1,2,4-triazole derivatives have anti-inflammatory activities (Mazzone et al., 1987) and some are antifungal agents (Massa et al., 1992). As a continuation of our intestigation on the structure of triaryltriazole compounds (Wang et al., 1998; Chen et al., 1998; Fun et al., 1999; Shao et al., 1999), we describe herein the structure of the title compound, (I).
The title structure (Fig. 1) consists of two pyridyl rings, one triazole ring and one phenyl ring. The four rings do not share a common plane; the dihedral angle between the phenyl and central triazole rings is 65.2 (3)° and the pyridyl rings form dihedral angles of 32.7 (2) and 30.1 (2)° with the triazole ring. The most favoured orientation of the pyridyl rings is that with their N atoms on opposite sides of the triazole-ring plane and oriented towards the phenyl ring. This orientation is due to the weak hydrogen-bond interactions the pyridyl and the triazole ring are involved in, in particular the C4—H4···N3 and C9—H9···N4 interactions (Table 2). Bond lengths and angles in (I) are comparable with those reported for related structures (Wang et al., 1998; Fun et al., 1999). In contrast to these related structures, however, in (I), intermolecular π–π stacking interactions between the N1-pyridyl ring and its symmetry partner at (1 − x, 2 − y, 1 − z) are observed along the a axis, with a perpendicular distance of 3.670 (3) Å. This arrangement is further stabilized by weak intermolecular C17—H17···N4 and C11—H11···N3 hydrogen bonds. The geometry of these interactions is given in Table 2.
In order to investigate how far packing interactions can influence the conformation of the molecule, molecular-mechanics calculations were carried out by using the MM+ force field of HYPERCHEM (Autodesk Inc., 1992). The best calculated model for the isolated molecule so obtained differs from that found experimentally for the molecule packed in the crystal because in the isolated molecule, the two pyridyl rings are practically coplanar with the central triazole ring, while in the crystal, they are rotated by an angle of about 32°. Another relevant difference is shown by the plane of the phenyl ring which is practically perpendicular to the plane of triazole ring in the isolated molecule, while it is twisted by about 65° in the crystal. This means that conjugation between the two pyridyl and triazole rings is favoured in the isolated molecule, but is in some way hindered by interactions with the surrounding molecules in the crystal. Conjugation with the phenyl ring is hindered in both cases.