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Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): o2738.
Published online 2009 October 17. doi:  10.1107/S1600536809041269
PMCID: PMC2970976

N-(1H-1,2,4-Triazol-5-yl)pyridine-2-carboxamide

Abstract

In the structure of the title compound, C8H7N5O, the pyridine ring and the imidazole ring are nearly coplanar, making a dihedral angle of 2.97 (15)°. An intra­molecular N—H(...)O hydrogen bond occurs. In the crystal mol­ecules are connected by inter­molecular hydrogen bonds and π–π stacking inter­actions between neighboring imidazole rings [centroid–centroid distance = 3.5842 (5) Å and off-set angle = 21.77°], leading to the formation of a two-dimensional supra­molecular sheet.

Related literature

For an alternative preparative method for the title compound, see: Browne & Polya (1968 [triangle]). For the potential bioinorganic applications of 1,2,4-triazole derivatives, see: Bohm & Karow (1981 [triangle]); Bahel et al. (1984 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2738-scheme1.jpg

Experimental

Crystal data

  • C8H7N5O
  • M r = 189.19
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2738-efi1.jpg
  • a = 8.6906 (17) Å
  • b = 5.2854 (10) Å
  • c = 17.880 (4) Å
  • β = 90.700 (3)°
  • V = 821.2 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.11 mm−1
  • T = 273 K
  • 0.26 × 0.24 × 0.18 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 1998 [triangle]) T min = 0.972, T max = 0.980
  • 3938 measured reflections
  • 1443 independent reflections
  • 961 reflections with I > 2σ(I)
  • R int = 0.095

Refinement

  • R[F 2 > 2σ(F 2)] = 0.046
  • wR(F 2) = 0.106
  • S = 1.00
  • 1443 reflections
  • 128 parameters
  • H-atom parameters constrained
  • Δρmax = 0.17 e Å−3
  • Δρmin = −0.16 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT (Bruker, 2004 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809041269/ez2185sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809041269/ez2185Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We gratefully acknowledge the financial support of the Guangxi Natural Science Foundation (No. 0991008) and the Innovation Project of Guangxi Graduate Education (2009106020703M43), China.

supplementary crystallographic information

Comment

1,2,4-Triazoles derivatives represent an interesting class of heterocycles. They present various potential applications in bioinorganic chemistry (Bohm & Karow, 1981; Bahel, et al., 1984). The preparation of the title compound has been reported previously (Browne & Polya, 1968), but its crystal structure has not yet been reported. Thus we report here the structure (Fig. 1) of the title compound obtained using an alternative method.

The pyridine ring and the imidazole ring are nearly co-planar with a dihedral angle of 2.97 (15)°. An intramolecular N—H···O hydrogen bond is present in the molecule. Adjacent molecules are connected alternatively by intermolecular N—H···N and N—H···O hydrogen bonds into one dimensional supramolecular chains (Fig. 2). The neighboring imidazole rings from adjacent one dimensional chains are parallel to each other with a perpendicular distance of 3.3285 (1) Å, a centroid-to-centroid distance of 3.5842 (5) Å and an off-set angle of 21.774° (calculated as the angle formed by the line through the two centroids of the two imidazole rings and the normal of the imidazole plane). This indicates the presence of a π–π stacking interaction between the neighboring imidazole rings from adjacent one dimensional chains, which leads to the construction of a two dimensional supramolecular sheet (Fig. 2).

Experimental

A mixture of 1,2-di-2-pyridyl-ethane-dione (0.2122 g, 1 mmol), 5-amino-1,2,4-triazole (0.1682 g, 2 mmol) and methanol (20 ml) was refluxed at 343 K for three hours. It was then filtered and the filtrate was left at ambient temperature to evaporate for three days, yielding crystals of the product. The overall yield is 70%. Elemental analysis for C8H7N5, calculated: C 55.48, H 4.07, N 40.44%; found: C 55.12, H 4.35, N 40.82%.

Refinement

H atoms on the N atoms were located in an electron density map and and allowed to ride on the N atoms with Uiso(H) = 1.5Ueq(N). H atoms on the carbon atoms were placed at calculated positions (C–H = 0.93 Å) and were included in the refinement in the riding model approximation, with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of the title compound with the atom-numbering scheme and 30% displacement ellipsoids.
Fig. 2.
A view of the two-dimensional supramolecular sheet assembled by hydrogen bonds and π–π stacking interactions (indicated by dashed lines).

Crystal data

C8H7N5OF(000) = 392
Mr = 189.19Dx = 1.530 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1623 reflections
a = 8.6906 (17) Åθ = 3.0–28.0°
b = 5.2854 (10) ŵ = 0.11 mm1
c = 17.880 (4) ÅT = 273 K
β = 90.700 (3)°Block, colorless
V = 821.2 (3) Å30.26 × 0.24 × 0.18 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer1443 independent reflections
Radiation source: fine-focus sealed tube961 reflections with I > 2σ(I)
graphiteRint = 0.095
[var phi] and ω scansθmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1998)h = −8→10
Tmin = 0.972, Tmax = 0.980k = −6→5
3938 measured reflectionsl = −21→21

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046H-atom parameters constrained
wR(F2) = 0.106w = 1/[σ2(Fo2) + (0.0259P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
1443 reflectionsΔρmax = 0.17 e Å3
128 parametersΔρmin = −0.16 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.024 (3)

Special details

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)

xyzUiso*/Ueq
N10.6956 (2)0.7443 (3)0.35815 (9)0.0470 (5)
N20.77449 (17)0.4023 (3)0.46730 (8)0.0410 (5)
H210.84060.51810.45390.061*
C50.5911 (2)0.5707 (4)0.37611 (10)0.0389 (5)
C60.6318 (2)0.3877 (4)0.43697 (10)0.0391 (5)
N40.74724 (18)0.0445 (3)0.54961 (8)0.0438 (5)
H410.6579−0.01300.53700.066*
N50.83128 (19)−0.0771 (3)0.60411 (9)0.0481 (5)
N30.96153 (18)0.2595 (3)0.55752 (9)0.0454 (5)
C30.4141 (3)0.7178 (5)0.28387 (12)0.0529 (7)
H30.31980.70830.25890.063*
C40.4492 (2)0.5512 (4)0.34098 (11)0.0478 (6)
H40.37890.42860.35550.057*
C10.6574 (3)0.9042 (4)0.30331 (12)0.0547 (6)
H10.72811.02840.29050.066*
C70.8255 (2)0.2395 (4)0.52329 (11)0.0380 (5)
C20.5196 (3)0.8965 (5)0.26449 (12)0.0534 (7)
H20.49901.01040.22600.064*
C80.9568 (2)0.0599 (4)0.60561 (11)0.0490 (6)
H81.03850.02290.63790.059*
O10.53795 (16)0.2298 (3)0.45747 (8)0.0520 (5)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0448 (11)0.0521 (13)0.0439 (10)−0.0024 (9)−0.0056 (8)0.0052 (10)
N20.0348 (10)0.0466 (12)0.0414 (10)−0.0067 (8)−0.0051 (8)0.0074 (9)
C50.0382 (12)0.0424 (13)0.0360 (11)0.0004 (10)−0.0015 (9)−0.0021 (10)
C60.0346 (11)0.0436 (14)0.0390 (12)−0.0060 (10)−0.0031 (9)−0.0033 (10)
N40.0371 (10)0.0510 (13)0.0431 (10)−0.0086 (9)−0.0042 (8)0.0068 (9)
N50.0419 (10)0.0541 (13)0.0481 (10)−0.0055 (10)−0.0077 (8)0.0132 (9)
N30.0391 (10)0.0500 (12)0.0469 (10)−0.0077 (9)−0.0092 (8)0.0089 (9)
C30.0490 (14)0.0611 (18)0.0482 (13)0.0082 (12)−0.0150 (11)−0.0033 (12)
C40.0438 (13)0.0529 (15)0.0465 (13)−0.0028 (11)−0.0065 (10)−0.0015 (11)
C10.0580 (15)0.0517 (16)0.0542 (14)−0.0055 (12)−0.0027 (11)0.0127 (12)
C70.0320 (11)0.0441 (14)0.0379 (11)−0.0058 (10)−0.0014 (9)−0.0008 (10)
C20.0620 (16)0.0542 (17)0.0439 (12)0.0088 (13)−0.0074 (11)0.0059 (12)
C80.0438 (13)0.0582 (16)0.0447 (13)−0.0034 (12)−0.0128 (10)0.0109 (12)
O10.0390 (9)0.0594 (11)0.0574 (10)−0.0141 (8)−0.0100 (7)0.0117 (8)

Geometric parameters (Å, °)

N1—C51.333 (2)N5—C81.309 (3)
N1—C11.333 (3)N3—C71.329 (2)
N2—C61.349 (2)N3—C81.362 (2)
N2—C71.388 (2)C3—C21.364 (3)
N2—H210.8751C3—C41.379 (3)
C5—C41.381 (3)C3—H30.9300
C5—C61.495 (3)C4—H40.9300
C6—O11.226 (2)C1—C21.377 (3)
N4—C71.324 (2)C1—H10.9300
N4—N51.371 (2)C2—H20.9300
N4—H410.8612C8—H80.9300
C5—N1—C1116.71 (19)C4—C3—H3120.4
C6—N2—C7122.55 (17)C3—C4—C5118.5 (2)
C6—N2—H21122.2C3—C4—H4120.7
C7—N2—H21115.2C5—C4—H4120.7
N1—C5—C4123.29 (19)N1—C1—C2124.0 (2)
N1—C5—C6117.68 (18)N1—C1—H1118.0
C4—C5—C6119.02 (19)C2—C1—H1118.0
O1—C6—N2122.01 (19)N4—C7—N3110.85 (18)
O1—C6—C5120.34 (18)N4—C7—N2125.30 (17)
N2—C6—C5117.65 (18)N3—C7—N2123.85 (18)
C7—N4—N5110.26 (16)C3—C2—C1118.4 (2)
C7—N4—H41130.3C3—C2—H2120.8
N5—N4—H41119.4C1—C2—H2120.8
C8—N5—N4101.06 (17)N5—C8—N3116.56 (18)
C7—N3—C8101.28 (17)N5—C8—H8121.7
C2—C3—C4119.1 (2)N3—C8—H8121.7
C2—C3—H3120.4
C1—N1—C5—C40.0 (3)C5—N1—C1—C2−1.0 (3)
C1—N1—C5—C6179.44 (19)N5—N4—C7—N3−0.1 (2)
C7—N2—C6—O10.4 (3)N5—N4—C7—N2179.57 (17)
C7—N2—C6—C5−178.98 (17)C8—N3—C7—N40.3 (2)
N1—C5—C6—O1177.46 (18)C8—N3—C7—N2−179.40 (19)
C4—C5—C6—O1−3.1 (3)C6—N2—C7—N44.8 (3)
N1—C5—C6—N2−3.1 (3)C6—N2—C7—N3−175.51 (19)
C4—C5—C6—N2176.30 (17)C4—C3—C2—C1−0.4 (3)
C7—N4—N5—C8−0.1 (2)N1—C1—C2—C31.2 (4)
C2—C3—C4—C5−0.5 (3)N4—N5—C8—N30.3 (2)
N1—C5—C4—C30.7 (3)C7—N3—C8—N5−0.4 (2)
C6—C5—C4—C3−178.68 (19)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H21···N3i0.882.092.946 (2)164
N4—H41···O1ii0.862.062.873 (2)158
N4—H41···O10.862.172.629 (2)113

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: EZ2185).

References

  • Bahel, S. C., Dubey, B. L., Nath, N. & Srivastava, J. K. (1984). Inorg. Chim. Acta, 91, L43–L45.
  • Bohm, R. & Karow, C. (1981). Pharmazie, 4, 243–247. [PubMed]
  • Browne, E. J. & Polya, J. B. (1968). J. Chem. Soc. (C), 23, 2904–2908.
  • Bruker (1998). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2004). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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