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

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). For the potential bioinorganic applications of 1,2,4-triazole derivatives, see: Bohm & Karow (1981); Bahel et al. (1984).

Experimental

Crystal data

• C₈H₇N₅O

• M_r = 189.19

• Monoclinic, P 2₁ /n

• a = 8.6906 (17) Å

• b = 5.2854 (10) Å

• c = 17.880 (4) Å

• β = 90.700 (3)°

• V = 821.2 (3) ų

• 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) 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[F² > 2σ(F²)] = 0.046

• wR(F²) = 0.106

• S = 1.00

• 1443 reflections

• 128 parameters

• H-atom parameters constrained

• Δρ_max = 0.17 e Å⁻³

• Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯N3^i	0.88	2.09	2.946 (2)	164
N4—H41⋯O1^ii	0.86	2.06	2.873 (2)	158
N4—H41⋯O1	0.86	2.17	2.629 (2)	113
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) -x+1, -y, -z+1.

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

Supporting information

S1. 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).

Related literature

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

S2. 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%.

S3. Refinement

H atoms on the N atoms were located in an electron density map and and allowed to ride on the N atoms with U_iso(H) = 1.5U_eq(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 U_iso(H) = 1.2U_eq(C).

Computing details

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

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).

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

Crystal data

C8H7N5O	F(000) = 392
Mr = 189.19	Dx = 1.530 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1623 reflections
a = 8.6906 (17) Å	θ = 3.0–28.0°
b = 5.2854 (10) Å	µ = 0.11 mm^−1
c = 17.880 (4) Å	T = 273 K
β = 90.700 (3)°	Block, colorless
V = 821.2 (3) Å^3	0.26 × 0.24 × 0.18 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer	1443 independent reflections
Radiation source: fine-focus sealed tube	961 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.095
φ and ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −8→10
Tmin = 0.972, Tmax = 0.980	k = −6→5
3938 measured reflections	l = −21→21

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.046	H-atom parameters constrained
wR(F^2) = 0.106	w = 1/[σ^2(Fo^2) + (0.0259P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max < 0.001
1443 reflections	Δρmax = 0.17 e Å^−3
128 parameters	Δρmin = −0.16 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction 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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.6956 (2)	0.7443 (3)	0.35815 (9)	0.0470 (5)
N2	0.77449 (17)	0.4023 (3)	0.46730 (8)	0.0410 (5)
H21	0.8406	0.5181	0.4539	0.061*
C5	0.5911 (2)	0.5707 (4)	0.37611 (10)	0.0389 (5)
C6	0.6318 (2)	0.3877 (4)	0.43697 (10)	0.0391 (5)
N4	0.74724 (18)	0.0445 (3)	0.54961 (8)	0.0438 (5)
H41	0.6579	−0.0130	0.5370	0.066*
N5	0.83128 (19)	−0.0771 (3)	0.60411 (9)	0.0481 (5)
N3	0.96153 (18)	0.2595 (3)	0.55752 (9)	0.0454 (5)
C3	0.4141 (3)	0.7178 (5)	0.28387 (12)	0.0529 (7)
H3	0.3198	0.7083	0.2589	0.063*
C4	0.4492 (2)	0.5512 (4)	0.34098 (11)	0.0478 (6)
H4	0.3789	0.4286	0.3555	0.057*
C1	0.6574 (3)	0.9042 (4)	0.30331 (12)	0.0547 (6)
H1	0.7281	1.0284	0.2905	0.066*
C7	0.8255 (2)	0.2395 (4)	0.52329 (11)	0.0380 (5)
C2	0.5196 (3)	0.8965 (5)	0.26449 (12)	0.0534 (7)
H2	0.4990	1.0104	0.2260	0.064*
C8	0.9568 (2)	0.0599 (4)	0.60561 (11)	0.0490 (6)
H8	1.0385	0.0229	0.6379	0.059*
O1	0.53795 (16)	0.2298 (3)	0.45747 (8)	0.0520 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0448 (11)	0.0521 (13)	0.0439 (10)	−0.0024 (9)	−0.0056 (8)	0.0052 (10)
N2	0.0348 (10)	0.0466 (12)	0.0414 (10)	−0.0067 (8)	−0.0051 (8)	0.0074 (9)
C5	0.0382 (12)	0.0424 (13)	0.0360 (11)	0.0004 (10)	−0.0015 (9)	−0.0021 (10)
C6	0.0346 (11)	0.0436 (14)	0.0390 (12)	−0.0060 (10)	−0.0031 (9)	−0.0033 (10)
N4	0.0371 (10)	0.0510 (13)	0.0431 (10)	−0.0086 (9)	−0.0042 (8)	0.0068 (9)
N5	0.0419 (10)	0.0541 (13)	0.0481 (10)	−0.0055 (10)	−0.0077 (8)	0.0132 (9)
N3	0.0391 (10)	0.0500 (12)	0.0469 (10)	−0.0077 (9)	−0.0092 (8)	0.0089 (9)
C3	0.0490 (14)	0.0611 (18)	0.0482 (13)	0.0082 (12)	−0.0150 (11)	−0.0033 (12)
C4	0.0438 (13)	0.0529 (15)	0.0465 (13)	−0.0028 (11)	−0.0065 (10)	−0.0015 (11)
C1	0.0580 (15)	0.0517 (16)	0.0542 (14)	−0.0055 (12)	−0.0027 (11)	0.0127 (12)
C7	0.0320 (11)	0.0441 (14)	0.0379 (11)	−0.0058 (10)	−0.0014 (9)	−0.0008 (10)
C2	0.0620 (16)	0.0542 (17)	0.0439 (12)	0.0088 (13)	−0.0074 (11)	0.0059 (12)
C8	0.0438 (13)	0.0582 (16)	0.0447 (13)	−0.0034 (12)	−0.0128 (10)	0.0109 (12)
O1	0.0390 (9)	0.0594 (11)	0.0574 (10)	−0.0141 (8)	−0.0100 (7)	0.0117 (8)

Geometric parameters (Å, º)

N1—C5	1.333 (2)	N5—C8	1.309 (3)
N1—C1	1.333 (3)	N3—C7	1.329 (2)
N2—C6	1.349 (2)	N3—C8	1.362 (2)
N2—C7	1.388 (2)	C3—C2	1.364 (3)
N2—H21	0.8751	C3—C4	1.379 (3)
C5—C4	1.381 (3)	C3—H3	0.9300
C5—C6	1.495 (3)	C4—H4	0.9300
C6—O1	1.226 (2)	C1—C2	1.377 (3)
N4—C7	1.324 (2)	C1—H1	0.9300
N4—N5	1.371 (2)	C2—H2	0.9300
N4—H41	0.8612	C8—H8	0.9300
C5—N1—C1	116.71 (19)	C4—C3—H3	120.4
C6—N2—C7	122.55 (17)	C3—C4—C5	118.5 (2)
C6—N2—H21	122.2	C3—C4—H4	120.7
C7—N2—H21	115.2	C5—C4—H4	120.7
N1—C5—C4	123.29 (19)	N1—C1—C2	124.0 (2)
N1—C5—C6	117.68 (18)	N1—C1—H1	118.0
C4—C5—C6	119.02 (19)	C2—C1—H1	118.0
O1—C6—N2	122.01 (19)	N4—C7—N3	110.85 (18)
O1—C6—C5	120.34 (18)	N4—C7—N2	125.30 (17)
N2—C6—C5	117.65 (18)	N3—C7—N2	123.85 (18)
C7—N4—N5	110.26 (16)	C3—C2—C1	118.4 (2)
C7—N4—H41	130.3	C3—C2—H2	120.8
N5—N4—H41	119.4	C1—C2—H2	120.8
C8—N5—N4	101.06 (17)	N5—C8—N3	116.56 (18)
C7—N3—C8	101.28 (17)	N5—C8—H8	121.7
C2—C3—C4	119.1 (2)	N3—C8—H8	121.7
C2—C3—H3	120.4
C1—N1—C5—C4	0.0 (3)	C5—N1—C1—C2	−1.0 (3)
C1—N1—C5—C6	179.44 (19)	N5—N4—C7—N3	−0.1 (2)
C7—N2—C6—O1	0.4 (3)	N5—N4—C7—N2	179.57 (17)
C7—N2—C6—C5	−178.98 (17)	C8—N3—C7—N4	0.3 (2)
N1—C5—C6—O1	177.46 (18)	C8—N3—C7—N2	−179.40 (19)
C4—C5—C6—O1	−3.1 (3)	C6—N2—C7—N4	4.8 (3)
N1—C5—C6—N2	−3.1 (3)	C6—N2—C7—N3	−175.51 (19)
C4—C5—C6—N2	176.30 (17)	C4—C3—C2—C1	−0.4 (3)
C7—N4—N5—C8	−0.1 (2)	N1—C1—C2—C3	1.2 (4)
C2—C3—C4—C5	−0.5 (3)	N4—N5—C8—N3	0.3 (2)
N1—C5—C4—C3	0.7 (3)	C7—N3—C8—N5	−0.4 (2)
C6—C5—C4—C3	−178.68 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···N3^i	0.88	2.09	2.946 (2)	164
N4—H41···O1^ii	0.86	2.06	2.873 (2)	158
N4—H41···O1	0.86	2.17	2.629 (2)	113

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