Acta Cryst. (2007). E63, o3056 [ doi:10.1107/S1600536807025573 ]
The title compound, C14H11N5S, was prepared by the reaction of 4-amino-5-(3-pyridyl)-1H-1,2,4-triazole-5(4H)-thione and benzaldehyde with ethanol at room temperature. The dihedral angles formed by the benzene and pyridine rings with the triazole ring are 46.2 (1) and 35.1 (2)°. There are weak inter- and intramolecular hydrogen bonds in the crystal structure.
A mixture of 4-amino-5-(3-pyridyl)-1H-1,2,4-triazole-5(4H)-thione (Dallavalle et al., 2002) (0.02 mol) and benzaldehyde (0.02 mol) was stirred with ethanol (50 mL) at 293 K for 5 h, affording the title compound (4.8 g, yield 86%). Single crystals suitable for X-ray measurements were obtained by recrystallization from acetone and ethanol (1:1) at room temperature.
H atoms were positioned geometrically and allowed to ride on their parent atoms, with N—H and C—H distances of 0.86 and 0.93 Å, respectively, and with Uiso(H) = 1.2Ueq of the parent atoms.
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL/PC (Sheldrick, 1997b); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./wn2136fig1thm.gif)
| Fig. 1. The molecular structure of the title compound with the atom-labeling scheme. Displacement ellipsoids are drawn at the 30% probability level. |
| C14H11N5S | F000 = 584 |
| Mr = 281.34 | Dx = 1.365 Mg m−3 |
| Monoclinic, P21/c | Melting point: 221.3 K |
| Hall symbol: -P 2y bc | Mo Kα radiation λ = 0.71073 Å |
| a = 9.2400 (18) Å | Cell parameters from 25 reflections |
| b = 14.217 (3) Å | θ = 4–14º |
| c = 13.302 (4) Å | µ = 0.23 mm−1 |
| β = 128.408 (19)º | T = 295 (2) K |
| V = 1369.3 (7) Å3 | Block, yellow |
| Z = 4 | 0.20 × 0.15 × 0.11 mm |
| Enraf-Nonius CAD-4 diffractometer | Rint = 0.059 |
| Radiation source: fine-focus sealed tube | θmax = 27.0º |
| Monochromator: graphite | θmin = 2.4º |
| T = 295(2) K | h = 0→11 |
| ω scans | k = −16→0 |
| Absorption correction: none | l = −16→12 |
| 3100 measured reflections | 3 standard reflections |
| 2928 independent reflections | every 100 reflections |
| 1176 reflections with I > 2σ(I) | intensity decay: none |
| 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)] = 0.047 | H-atom parameters constrained |
| wR(F2) = 0.129 | w = 1/[σ2(Fo2) + (0.0471P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 0.96 | (Δ/σ)max < 0.001 |
| 2928 reflections | Δρmax = 0.23 e Å−3 |
| 181 parameters | Δρmin = −0.20 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C14H11N5S | V = 1369.3 (7) Å3 |
| Mr = 281.34 | Z = 4 |
| Monoclinic, P21/c | Mo Kα |
| a = 9.2400 (18) Å | µ = 0.23 mm−1 |
| b = 14.217 (3) Å | T = 295 (2) K |
| c = 13.302 (4) Å | 0.20 × 0.15 × 0.11 mm |
| β = 128.408 (19)º |
| Enraf-Nonius CAD-4 diffractometer | Rint = 0.059 |
| Absorption correction: none | 3 standard reflections |
| 3100 measured reflections | every 100 reflections |
| 2928 independent reflections | intensity decay: none |
| 1176 reflections with I > 2σ(I) |
| R[F2 > 2σ(F2)] = 0.047 | 181 parameters |
| wR(F2) = 0.129 | H-atom parameters constrained |
| S = 0.96 | Δρmax = 0.23 e Å−3 |
| 2928 reflections | Δρmin = −0.20 e Å−3 |
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 > 2sigma(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 | ||
| S1 | 0.15884 (15) | 0.05229 (6) | −0.09184 (9) | 0.0697 (3) | |
| N1 | 0.3609 (3) | −0.11339 (15) | −0.0133 (2) | 0.0439 (6) | |
| N2 | 0.2915 (3) | −0.15678 (16) | −0.1301 (2) | 0.0466 (7) | |
| N3 | 0.4956 (4) | −0.11668 (17) | 0.1939 (2) | 0.0518 (7) | |
| N4 | 0.3887 (4) | −0.03778 (17) | 0.1356 (2) | 0.0550 (7) | |
| H4A | 0.3777 | 0.0045 | 0.1767 | 0.066* | |
| N5 | 0.6386 (4) | −0.40531 (18) | 0.2188 (2) | 0.0566 (7) | |
| C1 | 0.1107 (4) | −0.2359 (2) | −0.3790 (3) | 0.0573 (9) | |
| H1A | 0.1192 | −0.2748 | −0.3194 | 0.069* | |
| C2 | 0.0398 (5) | −0.2701 (3) | −0.4985 (3) | 0.0653 (10) | |
| H2B | 0.0010 | −0.3323 | −0.5193 | 0.078* | |
| C3 | 0.0262 (5) | −0.2125 (3) | −0.5872 (3) | 0.0717 (11) | |
| H3B | −0.0216 | −0.2363 | −0.6676 | 0.086* | |
| C4 | 0.0823 (5) | −0.1208 (3) | −0.5585 (4) | 0.0730 (11) | |
| H4B | 0.0724 | −0.0822 | −0.6189 | 0.088* | |
| C5 | 0.1541 (5) | −0.0858 (2) | −0.4383 (3) | 0.0594 (10) | |
| H5B | 0.1921 | −0.0234 | −0.4184 | 0.071* | |
| C6 | 0.1697 (4) | −0.1427 (2) | −0.3478 (3) | 0.0458 (8) | |
| C7 | 0.2484 (4) | −0.1028 (2) | −0.2216 (3) | 0.0477 (8) | |
| H7A | 0.2668 | −0.0383 | −0.2083 | 0.057* | |
| C8 | 0.3023 (4) | −0.03192 (19) | 0.0087 (3) | 0.0473 (8) | |
| C9 | 0.4751 (4) | −0.16280 (19) | 0.1012 (3) | 0.0439 (8) | |
| C10 | 0.5540 (4) | −0.2550 (2) | 0.1144 (3) | 0.0406 (7) | |
| C11 | 0.6108 (4) | −0.2834 (2) | 0.0441 (3) | 0.0569 (9) | |
| H11A | 0.6021 | −0.2427 | −0.0141 | 0.068* | |
| C12 | 0.6804 (5) | −0.3732 (2) | 0.0621 (3) | 0.0675 (10) | |
| H12A | 0.7201 | −0.3938 | 0.0164 | 0.081* | |
| C13 | 0.5736 (4) | −0.3186 (2) | 0.2011 (3) | 0.0477 (8) | |
| H13A | 0.5388 | −0.2992 | 0.2502 | 0.057* | |
| C14 | 0.6901 (5) | −0.4319 (2) | 0.1488 (3) | 0.0679 (11) | |
| H14A | 0.7345 | −0.4927 | 0.1590 | 0.081* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0892 (7) | 0.0522 (5) | 0.0663 (6) | 0.0178 (5) | 0.0476 (6) | 0.0108 (5) |
| N1 | 0.0574 (18) | 0.0360 (14) | 0.0380 (15) | −0.0011 (13) | 0.0295 (14) | −0.0017 (12) |
| N2 | 0.0561 (19) | 0.0466 (15) | 0.0359 (15) | −0.0005 (13) | 0.0279 (14) | −0.0018 (13) |
| N3 | 0.0638 (19) | 0.0446 (16) | 0.0429 (15) | 0.0009 (14) | 0.0312 (15) | −0.0012 (13) |
| N4 | 0.076 (2) | 0.0422 (16) | 0.0499 (17) | −0.0016 (15) | 0.0403 (16) | −0.0089 (13) |
| N5 | 0.063 (2) | 0.0481 (17) | 0.0554 (18) | 0.0104 (14) | 0.0349 (17) | 0.0141 (14) |
| C1 | 0.060 (2) | 0.063 (2) | 0.049 (2) | −0.0082 (19) | 0.034 (2) | −0.0011 (18) |
| C2 | 0.066 (3) | 0.073 (3) | 0.053 (2) | −0.011 (2) | 0.036 (2) | −0.017 (2) |
| C3 | 0.050 (2) | 0.122 (4) | 0.037 (2) | 0.004 (2) | 0.024 (2) | −0.005 (2) |
| C4 | 0.075 (3) | 0.098 (3) | 0.051 (2) | 0.008 (3) | 0.041 (2) | 0.017 (2) |
| C5 | 0.063 (2) | 0.067 (2) | 0.047 (2) | 0.0085 (19) | 0.033 (2) | 0.0136 (18) |
| C6 | 0.042 (2) | 0.054 (2) | 0.039 (2) | 0.0049 (16) | 0.0238 (17) | 0.0068 (16) |
| C7 | 0.055 (2) | 0.0437 (18) | 0.047 (2) | −0.0003 (16) | 0.0332 (18) | 0.0029 (16) |
| C8 | 0.060 (2) | 0.0387 (18) | 0.0483 (19) | −0.0066 (16) | 0.0361 (18) | −0.0047 (15) |
| C9 | 0.053 (2) | 0.0405 (18) | 0.0396 (18) | −0.0048 (16) | 0.0298 (18) | 0.0003 (15) |
| C10 | 0.0418 (19) | 0.0408 (17) | 0.0349 (17) | −0.0020 (15) | 0.0216 (16) | 0.0026 (14) |
| C11 | 0.073 (3) | 0.054 (2) | 0.055 (2) | 0.0044 (18) | 0.045 (2) | 0.0101 (17) |
| C12 | 0.089 (3) | 0.063 (2) | 0.071 (3) | 0.016 (2) | 0.060 (2) | 0.007 (2) |
| C13 | 0.051 (2) | 0.051 (2) | 0.0405 (18) | −0.0034 (17) | 0.0280 (17) | 0.0004 (16) |
| C14 | 0.078 (3) | 0.049 (2) | 0.074 (3) | 0.0158 (19) | 0.046 (2) | 0.0077 (19) |
| S1—C8 | 1.666 (3) | C3—H3B | 0.9300 |
| N1—C8 | 1.385 (3) | C4—C5 | 1.388 (4) |
| N1—C9 | 1.389 (3) | C4—H4B | 0.9300 |
| N1—N2 | 1.403 (3) | C5—C6 | 1.382 (4) |
| N2—C7 | 1.275 (3) | C5—H5B | 0.9300 |
| N3—C9 | 1.302 (3) | C6—C7 | 1.467 (4) |
| N3—N4 | 1.372 (3) | C7—H7A | 0.9300 |
| N4—C8 | 1.349 (3) | C9—C10 | 1.457 (4) |
| N4—H4A | 0.8600 | C10—C13 | 1.386 (4) |
| N5—C13 | 1.327 (4) | C10—C11 | 1.387 (4) |
| N5—C14 | 1.336 (4) | C11—C12 | 1.382 (4) |
| C1—C2 | 1.378 (4) | C11—H11A | 0.9300 |
| C1—C6 | 1.394 (4) | C12—C14 | 1.381 (4) |
| C1—H1A | 0.9300 | C12—H12A | 0.9300 |
| C2—C3 | 1.376 (4) | C13—H13A | 0.9300 |
| C2—H2B | 0.9300 | C14—H14A | 0.9300 |
| C3—C4 | 1.367 (5) | ||
| C8—N1—C9 | 108.7 (2) | C1—C6—C7 | 122.2 (3) |
| C8—N1—N2 | 129.2 (2) | N2—C7—C6 | 119.9 (3) |
| C9—N1—N2 | 120.4 (2) | N2—C7—H7A | 120.1 |
| C7—N2—N1 | 116.7 (2) | C6—C7—H7A | 120.1 |
| C9—N3—N4 | 104.3 (2) | N4—C8—N1 | 102.0 (2) |
| C8—N4—N3 | 114.6 (2) | N4—C8—S1 | 127.3 (2) |
| C8—N4—H4A | 122.7 | N1—C8—S1 | 130.7 (2) |
| N3—N4—H4A | 122.7 | N3—C9—N1 | 110.4 (3) |
| C13—N5—C14 | 117.2 (3) | N3—C9—C10 | 124.9 (3) |
| C2—C1—C6 | 119.8 (3) | N1—C9—C10 | 124.7 (3) |
| C2—C1—H1A | 120.1 | C13—C10—C11 | 117.6 (3) |
| C6—C1—H1A | 120.1 | C13—C10—C9 | 118.9 (3) |
| C3—C2—C1 | 120.3 (3) | C11—C10—C9 | 123.5 (3) |
| C3—C2—H2B | 119.9 | C12—C11—C10 | 118.9 (3) |
| C1—C2—H2B | 119.9 | C12—C11—H11A | 120.6 |
| C4—C3—C2 | 120.7 (3) | C10—C11—H11A | 120.6 |
| C4—C3—H3B | 119.7 | C14—C12—C11 | 118.9 (3) |
| C2—C3—H3B | 119.7 | C14—C12—H12A | 120.5 |
| C3—C4—C5 | 119.4 (3) | C11—C12—H12A | 120.5 |
| C3—C4—H4B | 120.3 | N5—C13—C10 | 124.3 (3) |
| C5—C4—H4B | 120.3 | N5—C13—H13A | 117.8 |
| C6—C5—C4 | 120.7 (3) | C10—C13—H13A | 117.8 |
| C6—C5—H5B | 119.6 | N5—C14—C12 | 123.0 (3) |
| C4—C5—H5B | 119.6 | N5—C14—H14A | 118.5 |
| C5—C6—C1 | 119.1 (3) | C12—C14—H14A | 118.5 |
| C5—C6—C7 | 118.7 (3) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N4—H4A···N5i | 0.86 | 1.96 | 2.823 (4) | 175 |
| C7—H7A···S1 | 0.93 | 2.64 | 3.209 (4) | 120 |
| C11—H11A···N2 | 0.93 | 2.57 | 2.970 (4) | 106 |
| Symmetry codes: (i) −x+1, y+1/2, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N4—H4A···N5i | 0.86 | 1.96 | 2.823 (4) | 175 |
| C7—H7A···S1 | 0.93 | 2.64 | 3.209 (4) | 120 |
| C11—H11A···N2 | 0.93 | 2.57 | 2.970 (4) | 106 |
| Symmetry codes: (i) −x+1, y+1/2, −z+1/2. |
The authors thank the Natural Science Foundation of Shandong Province (grant No. Y2005B04).
Dallavalle, F., Gaccioli, F., Franchi-Gazzola, R., Lanfranchi, M., Marchio, L., Pellinghellia, M. A. & Tegonia, M. (2002). J. Inorg. Biochem. 92, 95–104.
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Jian, F.-F., Zhuang, R.-R., Wang, K.-F., Zhao, P.-S. & Xiao, H.-L. (2006). Acta Cryst. E62, o3198–o3199.
Qin, Y.-Q., Ren, X.-Y., Liang, T.-L. & Jian, F.-F. (2006). Acta Cryst. E62, o5215–o5216.
Rozwadowski, Z., Majewski, E., Dziembowska, T. & Hansen, P. E. (1999). J. Chem. Soc. Perkin Trans. 2, pp. 2809–2817.
Sheldrick, G. M. (1997a). SHELXL97 and SHELXS97. University of Göttingen, Germany.
Sheldrick, G. M. (1997b). SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.
Schiff bases have been used extensively as ligands in the field of coordination chemistry (Jian et al., 2006). They have biochemical and pharmacological applications. The recent growing interest in them is also due to their ability to form intramolecular hydrogen bonds by electron coupling between acid-base centers (Rozwadowski et al.,1999). The title compound has been synthesized and we report here its crystal structure.
In the crystal structure (Fig. 1), the dihedral angles formed by the phenyl and pyridine rings with the plane through the triazole ring and S atom are 46.2 (1) and 35.1 (2)°, respectively. The C═S bond length (1.666 (3) Å) and C7═N2 bond length (1.275 (3) Å) are in agreement with those observed earlier (Qin et al., 2006; Jian et al., 2006). Intramolecular C—H···S and C—H···N as well as intermolecular N—H···N hydrogen bonds are present in the crystal structure.