organic compounds
3-(2-Pyridyl)-5-(4-pyridyl)-4-(p-tolyl)-1H-1,2,4-triazole
aBenxi Health School of Liaoning, Liaoning 117022, People's Republic of China, and bOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
*Correspondence e-mail: quzr@seu.edu.cn
In the molecule of the title compound, C19H15N5, the dihedral angles formed by the plane of the triazole ring with those of the 2-pyridyl, 4-pyridyl and p-tolyl rings are 28.12 (10), 34.62 (10) and 71.43 (9)°, respectively. The is consolidated by C—H⋯π hydrogen-bonding interactions and by π–π stacking interactions, with a centroid–centroid distance of 3.794 (4) Å.
Related literature
For the pharmaceutical and agricultural applications of triazoles, see: Grénman et al. (2003). For general background on the coordination chemistry of triazoles, see: Haasnoot (2000); Klingele & Brooker (2003); Beckmann & Brooker (2003). For the synthesis of the title compound, see: Erwin (1958).
Experimental
Crystal data
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Refinement
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Data collection: CrystalClear (Rigaku, 2005); cell CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999).
Supporting information
10.1107/S1600536809016432/rz2317sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809016432/rz2317Isup2.hkl
A mixture of 4,4'-dimethylphenylphosphazoanilide (3.60 g, 14.9 mmol) and N-(2-pyridyl)-N'-(4-pyridyl)hydrazine (3.00 g, 12.4 mmol) in o-dichlorobenzene (30 ml) was refluxed for 3 h, then conc. HCl (5 ml) and H2O (5 ml) were added to the system after the removal of the solvent under reduced pressure. After refluxing for 1 h, the mixture was filtered and the fietrate was neutralized with K2CO3 to pH 8–9 to achieve a white solid. Colourless crystals of the title compound suitable for X-ray diffraction were obtained by slow evaporation of an ethanol solution.
Positional parameters of all the H atoms were calculated geometrically and were allowed to ride on the C atoms to which they are bonded with, C—H = 0.93 Å (aromatic) or 0.96 Å (methyl), and with Uiso(H) = 1.2Ueq(Caromatic) or Uiso(H) = 1.5Ueq(Cmethyl).
Data collection: CrystalClear (Rigaku, 2005); cell
CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999).Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. |
C19H15N5 | F(000) = 656 |
Mr = 313.36 | Dx = 1.394 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1730 reflections |
a = 5.6104 (11) Å | θ = 3.0–27.5° |
b = 16.312 (3) Å | µ = 0.09 mm−1 |
c = 16.902 (4) Å | T = 293 K |
β = 105.07 (3)° | Prism, colourless |
V = 1493.6 (6) Å3 | 0.20 × 0.20 × 0.20 mm |
Z = 4 |
Rigaku SCXmini diffractometer | 2918 independent reflections |
Radiation source: fine-focus sealed tube | 1734 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.105 |
CCD_Profile_fitting scans | θmax = 26.0°, θmin = 3.5° |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | h = −6→6 |
Tmin = 0.982, Tmax = 0.983 | k = −20→20 |
13896 measured reflections | l = −20→20 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.071 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.159 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0527P)2 + 0.6603P] where P = (Fo2 + 2Fc2)/3 |
2918 reflections | (Δ/σ)max < 0.001 |
217 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C19H15N5 | V = 1493.6 (6) Å3 |
Mr = 313.36 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.6104 (11) Å | µ = 0.09 mm−1 |
b = 16.312 (3) Å | T = 293 K |
c = 16.902 (4) Å | 0.20 × 0.20 × 0.20 mm |
β = 105.07 (3)° |
Rigaku SCXmini diffractometer | 2918 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 1734 reflections with I > 2σ(I) |
Tmin = 0.982, Tmax = 0.983 | Rint = 0.105 |
13896 measured reflections |
R[F2 > 2σ(F2)] = 0.071 | 0 restraints |
wR(F2) = 0.159 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.32 e Å−3 |
2918 reflections | Δρmin = −0.26 e Å−3 |
217 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 1.0349 (6) | 0.66367 (18) | 0.84606 (18) | 0.0362 (8) | |
C2 | 0.7141 (5) | 0.73132 (19) | 0.78095 (17) | 0.0349 (7) | |
C3 | 0.5160 (6) | 0.79095 (19) | 0.75540 (17) | 0.0360 (8) | |
C4 | 0.3738 (7) | 0.9211 (2) | 0.7518 (2) | 0.0508 (9) | |
H4B | 0.4004 | 0.9757 | 0.7673 | 0.061* | |
C5 | 0.1503 (6) | 0.9004 (2) | 0.7039 (2) | 0.0480 (9) | |
H5B | 0.0273 | 0.9396 | 0.6870 | 0.058* | |
C6 | 0.1094 (6) | 0.8215 (2) | 0.6810 (2) | 0.0522 (10) | |
H6A | −0.0430 | 0.8056 | 0.6478 | 0.063* | |
C7 | 0.2918 (6) | 0.7655 (2) | 0.70656 (19) | 0.0453 (8) | |
H7A | 0.2658 | 0.7108 | 0.6914 | 0.054* | |
C8 | 1.2577 (6) | 0.63716 (17) | 0.90639 (19) | 0.0346 (7) | |
C9 | 1.4365 (6) | 0.59609 (18) | 0.8799 (2) | 0.0418 (8) | |
H9A | 1.4153 | 0.5859 | 0.8243 | 0.050* | |
C10 | 1.6455 (6) | 0.5704 (2) | 0.9356 (2) | 0.0471 (9) | |
H10A | 1.7648 | 0.5428 | 0.9167 | 0.056* | |
C11 | 1.5079 (6) | 0.6215 (2) | 1.0397 (2) | 0.0455 (9) | |
H11A | 1.5303 | 0.6301 | 1.0956 | 0.055* | |
C12 | 1.2956 (6) | 0.64888 (19) | 0.98817 (19) | 0.0406 (8) | |
H12A | 1.1774 | 0.6754 | 1.0086 | 0.049* | |
C13 | 0.9579 (5) | 0.79279 (17) | 0.91387 (17) | 0.0310 (7) | |
C14 | 1.1613 (6) | 0.84102 (19) | 0.92208 (19) | 0.0407 (8) | |
H14A | 1.2539 | 0.8385 | 0.8838 | 0.049* | |
C15 | 1.2267 (6) | 0.8930 (2) | 0.9874 (2) | 0.0481 (9) | |
H15A | 1.3659 | 0.9258 | 0.9935 | 0.058* | |
C16 | 1.0920 (6) | 0.89820 (18) | 1.04469 (19) | 0.0421 (8) | |
C17 | 0.8873 (6) | 0.84945 (19) | 1.03423 (19) | 0.0429 (8) | |
H17A | 0.7930 | 0.8520 | 1.0720 | 0.052* | |
C18 | 0.8200 (5) | 0.79711 (19) | 0.96907 (17) | 0.0362 (7) | |
H18A | 0.6802 | 0.7645 | 0.9625 | 0.043* | |
C19 | 1.1735 (8) | 0.9536 (2) | 1.1171 (2) | 0.0689 (12) | |
H19A | 1.3198 | 0.9824 | 1.1138 | 0.103* | |
H19B | 1.2082 | 0.9216 | 1.1665 | 0.103* | |
H19C | 1.0450 | 0.9923 | 1.1176 | 0.103* | |
N1 | 0.9349 (5) | 0.62309 (16) | 0.77955 (16) | 0.0446 (7) | |
N2 | 0.7292 (5) | 0.66575 (17) | 0.73835 (16) | 0.0443 (7) | |
N3 | 0.9026 (4) | 0.73278 (14) | 0.84991 (14) | 0.0324 (6) | |
N4 | 0.5604 (5) | 0.86832 (16) | 0.77874 (16) | 0.0453 (7) | |
N5 | 1.6862 (5) | 0.58304 (17) | 1.01564 (19) | 0.0508 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.044 (2) | 0.0345 (17) | 0.0313 (17) | −0.0008 (15) | 0.0120 (15) | −0.0043 (14) |
C2 | 0.0358 (18) | 0.0410 (18) | 0.0263 (16) | −0.0069 (14) | 0.0054 (14) | −0.0005 (15) |
C3 | 0.0404 (18) | 0.0421 (19) | 0.0238 (15) | −0.0069 (15) | 0.0054 (14) | −0.0014 (14) |
C4 | 0.056 (2) | 0.040 (2) | 0.051 (2) | 0.0005 (17) | 0.0052 (19) | 0.0049 (17) |
C5 | 0.043 (2) | 0.050 (2) | 0.047 (2) | 0.0048 (17) | 0.0052 (17) | 0.0093 (17) |
C6 | 0.040 (2) | 0.062 (3) | 0.047 (2) | −0.0066 (18) | −0.0017 (17) | 0.0049 (19) |
C7 | 0.046 (2) | 0.0430 (19) | 0.0419 (19) | −0.0092 (16) | 0.0016 (16) | −0.0041 (16) |
C8 | 0.0388 (19) | 0.0289 (16) | 0.0374 (18) | −0.0048 (13) | 0.0122 (15) | 0.0015 (14) |
C9 | 0.049 (2) | 0.0355 (18) | 0.0425 (19) | −0.0032 (16) | 0.0153 (17) | −0.0008 (15) |
C10 | 0.048 (2) | 0.0399 (19) | 0.059 (2) | −0.0016 (16) | 0.0227 (19) | 0.0037 (17) |
C11 | 0.045 (2) | 0.047 (2) | 0.042 (2) | −0.0038 (17) | 0.0087 (17) | −0.0008 (16) |
C12 | 0.0382 (19) | 0.047 (2) | 0.0371 (18) | 0.0025 (15) | 0.0114 (15) | 0.0003 (16) |
C13 | 0.0326 (17) | 0.0314 (16) | 0.0264 (15) | −0.0044 (13) | 0.0030 (13) | −0.0009 (13) |
C14 | 0.0410 (19) | 0.0423 (19) | 0.0382 (18) | −0.0073 (15) | 0.0094 (15) | −0.0019 (16) |
C15 | 0.044 (2) | 0.0390 (19) | 0.055 (2) | −0.0101 (16) | 0.0024 (18) | −0.0039 (17) |
C16 | 0.055 (2) | 0.0289 (17) | 0.0324 (18) | 0.0048 (16) | −0.0056 (17) | 0.0024 (14) |
C17 | 0.056 (2) | 0.0401 (19) | 0.0331 (18) | 0.0051 (16) | 0.0132 (16) | −0.0022 (15) |
C18 | 0.0342 (17) | 0.0413 (18) | 0.0317 (17) | −0.0066 (14) | 0.0060 (14) | −0.0033 (14) |
C19 | 0.098 (3) | 0.045 (2) | 0.046 (2) | 0.005 (2) | −0.013 (2) | −0.0117 (18) |
N1 | 0.0515 (18) | 0.0429 (16) | 0.0381 (15) | −0.0024 (13) | 0.0093 (14) | −0.0070 (13) |
N2 | 0.0477 (17) | 0.0464 (16) | 0.0360 (15) | −0.0020 (14) | 0.0057 (13) | −0.0070 (14) |
N3 | 0.0372 (15) | 0.0337 (14) | 0.0257 (13) | −0.0043 (11) | 0.0070 (11) | −0.0043 (11) |
N4 | 0.0505 (18) | 0.0413 (16) | 0.0396 (16) | −0.0045 (14) | 0.0036 (14) | −0.0006 (13) |
N5 | 0.0429 (17) | 0.0485 (18) | 0.060 (2) | −0.0045 (14) | 0.0115 (15) | 0.0045 (15) |
C1—N1 | 1.300 (4) | C10—H10A | 0.9300 |
C1—N3 | 1.361 (4) | C11—N5 | 1.331 (4) |
C1—C8 | 1.458 (4) | C11—C12 | 1.356 (4) |
C2—N2 | 1.304 (4) | C11—H11A | 0.9300 |
C2—N3 | 1.355 (3) | C12—H12A | 0.9300 |
C2—C3 | 1.456 (4) | C13—C18 | 1.360 (4) |
C3—N4 | 1.326 (4) | C13—C14 | 1.363 (4) |
C3—C7 | 1.377 (4) | C13—N3 | 1.431 (3) |
C4—N4 | 1.340 (4) | C14—C15 | 1.365 (4) |
C4—C5 | 1.347 (4) | C14—H14A | 0.9300 |
C4—H4B | 0.9300 | C15—C16 | 1.376 (5) |
C5—C6 | 1.345 (5) | C15—H15A | 0.9300 |
C5—H5B | 0.9300 | C16—C17 | 1.370 (5) |
C6—C7 | 1.356 (5) | C16—C19 | 1.494 (4) |
C6—H6A | 0.9300 | C17—C18 | 1.367 (4) |
C7—H7A | 0.9300 | C17—H17A | 0.9300 |
C8—C12 | 1.356 (4) | C18—H18A | 0.9300 |
C8—C9 | 1.375 (4) | C19—H19A | 0.9600 |
C9—C10 | 1.365 (4) | C19—H19B | 0.9600 |
C9—H9A | 0.9300 | C19—H19C | 0.9600 |
C10—N5 | 1.328 (4) | N1—N2 | 1.372 (4) |
N1—C1—N3 | 110.2 (3) | C11—C12—H12A | 120.4 |
N1—C1—C8 | 123.6 (3) | C8—C12—H12A | 120.4 |
N3—C1—C8 | 126.3 (3) | C18—C13—C14 | 120.7 (3) |
N2—C2—N3 | 109.9 (3) | C18—C13—N3 | 120.2 (3) |
N2—C2—C3 | 122.6 (3) | C14—C13—N3 | 118.9 (3) |
N3—C2—C3 | 127.5 (3) | C13—C14—C15 | 118.9 (3) |
N4—C3—C7 | 122.5 (3) | C13—C14—H14A | 120.6 |
N4—C3—C2 | 118.5 (3) | C15—C14—H14A | 120.6 |
C7—C3—C2 | 119.0 (3) | C14—C15—C16 | 121.7 (3) |
N4—C4—C5 | 124.5 (3) | C14—C15—H15A | 119.1 |
N4—C4—H4B | 117.8 | C16—C15—H15A | 119.1 |
C5—C4—H4B | 117.8 | C17—C16—C15 | 117.9 (3) |
C6—C5—C4 | 118.4 (3) | C17—C16—C19 | 121.6 (3) |
C6—C5—H5B | 120.8 | C15—C16—C19 | 120.4 (3) |
C4—C5—H5B | 120.8 | C18—C17—C16 | 120.9 (3) |
C5—C6—C7 | 119.6 (3) | C18—C17—H17A | 119.6 |
C5—C6—H6A | 120.2 | C16—C17—H17A | 119.6 |
C7—C6—H6A | 120.2 | C13—C18—C17 | 119.9 (3) |
C6—C7—C3 | 118.9 (3) | C13—C18—H18A | 120.1 |
C6—C7—H7A | 120.5 | C17—C18—H18A | 120.1 |
C3—C7—H7A | 120.5 | C16—C19—H19A | 109.5 |
C12—C8—C9 | 117.8 (3) | C16—C19—H19B | 109.5 |
C12—C8—C1 | 123.3 (3) | H19A—C19—H19B | 109.5 |
C9—C8—C1 | 118.8 (3) | C16—C19—H19C | 109.5 |
C10—C9—C8 | 119.5 (3) | H19A—C19—H19C | 109.5 |
C10—C9—H9A | 120.2 | H19B—C19—H19C | 109.5 |
C8—C9—H9A | 120.2 | C1—N1—N2 | 107.3 (3) |
N5—C10—C9 | 123.0 (3) | C2—N2—N1 | 107.6 (2) |
N5—C10—H10A | 118.5 | C2—N3—C1 | 104.9 (2) |
C9—C10—H10A | 118.5 | C2—N3—C13 | 129.0 (2) |
N5—C11—C12 | 124.3 (3) | C1—N3—C13 | 126.1 (2) |
N5—C11—H11A | 117.9 | C3—N4—C4 | 116.1 (3) |
C12—C11—H11A | 117.9 | C10—N5—C11 | 116.2 (3) |
C11—C12—C8 | 119.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11A···Cg1i | 0.93 | 2.79 | 3.630 (4) | 150 |
C12—H12A···Cg3 | 0.93 | 2.90 | 3.532 (4) | 126 |
C14—H14A···Cg1ii | 0.93 | 2.76 | 3.628 (4) | 156 |
C18—H18A···Cg2iii | 0.93 | 2.78 | 3.615 (4) | 149 |
C19—H19C···Cg3iv | 0.96 | 3.08 | 3.698 (4) | 124 |
Symmetry codes: (i) x+1, −y−3/2, z−1/2; (ii) x+1, y, z; (iii) x−1, y, z; (iv) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | C19H15N5 |
Mr | 313.36 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 5.6104 (11), 16.312 (3), 16.902 (4) |
β (°) | 105.07 (3) |
V (Å3) | 1493.6 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.20 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Rigaku SCXmini diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2005) |
Tmin, Tmax | 0.982, 0.983 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13896, 2918, 1734 |
Rint | 0.105 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.071, 0.159, 1.07 |
No. of reflections | 2918 |
No. of parameters | 217 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.26 |
Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL/PC (Sheldrick, 2008), PRPKAPPA (Ferguson, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11A···Cg1i | 0.93 | 2.79 | 3.630 (4) | 150.0 |
C12—H12A···Cg3 | 0.93 | 2.90 | 3.532 (4) | 125.8 |
C14—H14A···Cg1ii | 0.93 | 2.76 | 3.628 (4) | 155.9 |
C18—H18A···Cg2iii | 0.93 | 2.78 | 3.615 (4) | 149.2 |
C19—H19C···Cg3iv | 0.96 | 3.08 | 3.698 (4) | 123.6 |
Symmetry codes: (i) x+1, −y−3/2, z−1/2; (ii) x+1, y, z; (iii) x−1, y, z; (iv) −x, −y, −z. |
Group 1 | Group 2 | α (°) | DCC (Å) | τ (°) |
Cg2 | Cg2i | 0.0 | 3.794 (3) | 31.30 |
Symmetry code: (i) 3-x, 1-y, 2-z. |
Acknowledgements
This work was supported by the Technical Fund Financing Projects (grant Nos. 9207042464 and 9207041482) from Southeast University to ZRQ.
References
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The main interest in triazoles lies in their pharmaceutical and agricultural applications (Grénman et al., 2003). The utilization of 1,2,4-triazole derivatives as bridging ligands in transition-metal complexes is currently of considerable interest because of the fact that it represents a hybrid of pyrazole and imidazole with regard to the arrangement of its heteroatoms, thus promising a rich and versatile coordination chemistry (Haasnoot, 2000; Klingele & Brooker, 2003; Beckmann & Brooker, 2003). We report here the crystal structure of the title compound, which is a substituted 1,2,4-triazole synthesized by the reaction of 4,4'-dimethylphenylphosphazoanilide with N-(2-pyridyl)-N'-(4-pyridyl)hydrazine in o-dichlorobenzene (Erwin, 1958).
The structure of the title compound (Fig. 1) features a dihedral angle of 28.12 (10)° between the 2-pyridyl and triazole rings, a dihedral angle of 34.62 (10)° between the 4-pyridyl and triazole rings, and a dihedral angle of 71.43 (9) ° between the p-tolyl and the triazole rings. The crystal structure is stabilized by C—H···π hydrogen interactions (Table 1) and π–π stacking interactions (Table 2).