1H-1,2,4-Triazole-3-carboxamide

Xie, Q.-R.

doi:10.1107/S1600536808014013

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1110

doi:10.1107/S1600536808014013

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1H-1,2,4-Triazole-3-carboxamide

Qing-Ruo Xie ^a ^*

^aDepartment of Biological and Chemical Engineering, Guangxi University of Technology, Liuzhou 545006, People's Republic of China
^*Correspondence e-mail: chemical2008@yeah.net

(Received 3 April 2008; accepted 10 May 2008; online 17 May 2008)

Planar molecules of the title compound, C₃H₄N₄O, are organized into sheets by extensive N—H⋯O and N—H⋯N hydrogen bonding in the (101) plane of the crystal structure. These hydrogen bonds may also stabilize the molecule in the Z form. The title compound is in the amide form, as shown by the C=O bond length [1.252 (2) Å].

Related literature

Azo compounds are widely utilized as dyes and analytical reagents (Malinauskas et al., 2000 ). The interactions of amide groups are of interest because of their importance in biochemical systems (Crespo et al., 2005 ).

Experimental

Crystal data

C₃H₄N₄O
M_r = 112.10
Monoclinic, P 2₁ /n
a = 3.6944 (4) Å
b = 17.527 (3) Å
c = 7.0520 (17) Å
β = 94.4670 (10)°
V = 455.24 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 298 (2) K
0.22 × 0.18 × 0.09 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.972, T_max = 0.988
2199 measured reflections
807 independent reflections
657 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.101
S = 1.05
807 reflections
73 parameters
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.86	2.21	3.065 (2)	173
N1—H1B⋯N4ⁱⁱ	0.86	2.22	3.010 (2)	154
N2—H2⋯O1ⁱⁱⁱ	0.86	2.07	2.909 (2)	163
N2—H2⋯N3ⁱⁱⁱ	0.86	2.54	3.055 (2)	120
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) -x, -y+2, -z+2; (iii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2003); 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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808014013/cs2075sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808014013/cs2075Isup2.hkl

checkCIF report

Comment top

The title compound was obtained by the reaction of methyl 1H-1,2,4-triazole-3-carboxylate and ammonium hydroxide. The C=O bond length of 1.2524 (18) Å suggests that the title compound is in the amide form. N—H···O and N—H···N hydrogen bonds link molecules into infinite sheets. These sheets provide the two-dimensional network in and paralell to the {101} plane of the cell.

Related literature top

Azo compounds are widely utilized as dyes and analytical reagents (Malinauskas et al., 2000). The interactions of amide groups are of interest because of their importance in biochemical system (Crespo et al., 2005).

Experimental top

Added 20 ml 25% ammonium hydroxide to methyl 1H-1,2,4-triazole-3-carboxylate (20 mmol, 2540 mg) while stirring for 8 h at 353 K. The resulting white precipitate was filtered and washed several times with ethanol and dried in vacuo (yield 85%). Single crystals of C₃H₄N₄O suitable for X-ray diffraction were obtained by slow evaporation of an 50% ethanol solution at room temperature over a period of one week.

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); 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 top

	Fig. 1. The structure of the title compound showing 30% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. Crystal packing showing the hydrogen bonded interactions as dashed lines.

1H-1,2,4-Triazole-3-carboxamide top

Crystal data top

C₃H₄N₄O	F(000) = 232
M_r = 112.10	D_x = 1.636 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1200 reflections
a = 3.6944 (4) Å	θ = 2.3–27.5°
b = 17.527 (3) Å	µ = 0.13 mm⁻¹
c = 7.0520 (17) Å	T = 298 K
β = 94.467 (1)°	Prism, colourless
V = 455.24 (14) Å³	0.22 × 0.18 × 0.09 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	807 independent reflections
Radiation source: fine-focus sealed tube	657 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −4→3
T_min = 0.972, T_max = 0.988	k = −20→18
2199 measured reflections	l = −8→8

Refinement top

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0653P)² + 0.058P] where P = (F_o² + 2F_c²)/3
807 reflections	(Δ/σ)_max < 0.001
73 parameters	Δρ_max = 0.13 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₃H₄N₄O	V = 455.24 (14) Å³
M_r = 112.10	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 3.6944 (4) Å	µ = 0.13 mm⁻¹
b = 17.527 (3) Å	T = 298 K
c = 7.0520 (17) Å	0.22 × 0.18 × 0.09 mm
β = 94.467 (1)°

Data collection top

Bruker SMART CCD diffractometer	807 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	657 reflections with I > 2σ(I)
T_min = 0.972, T_max = 0.988	R_int = 0.020
2199 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.101	H-atom parameters constrained
S = 1.05	Δρ_max = 0.13 e Å⁻³
807 reflections	Δρ_min = −0.23 e Å⁻³
73 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.2702 (4)	0.99272 (7)	0.7168 (2)	0.0381 (4)
H1A	0.3404	1.0240	0.6332	0.046*
H1B	0.1763	1.0098	0.8163	0.046*
N2	0.0498 (4)	0.77481 (8)	1.00884 (19)	0.0330 (4)
H2	0.0162	0.7288	1.0460	0.040*
N3	0.1784 (4)	0.79443 (7)	0.84073 (18)	0.0329 (4)
N4	0.0595 (4)	0.89955 (8)	1.01228 (18)	0.0349 (4)
O1	0.4402 (3)	0.88844 (6)	0.55202 (16)	0.0386 (4)
C1	0.3067 (4)	0.91813 (8)	0.6923 (2)	0.0289 (4)
C2	0.1793 (4)	0.87021 (8)	0.8491 (2)	0.0271 (4)
C3	−0.0168 (5)	0.83716 (9)	1.1079 (2)	0.0360 (4)
H3	−0.1048	0.8370	1.2279	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0594 (10)	0.0241 (8)	0.0333 (8)	0.0011 (6)	0.0202 (7)	0.0017 (5)
N2	0.0449 (9)	0.0220 (7)	0.0331 (8)	−0.0010 (5)	0.0098 (6)	0.0056 (5)
N3	0.0434 (8)	0.0250 (8)	0.0314 (7)	−0.0006 (5)	0.0093 (6)	0.0010 (5)
N4	0.0494 (9)	0.0259 (8)	0.0310 (8)	0.0004 (6)	0.0145 (6)	0.0004 (5)
O1	0.0566 (8)	0.0267 (6)	0.0347 (7)	0.0030 (5)	0.0176 (5)	−0.0001 (5)
C1	0.0339 (9)	0.0259 (9)	0.0274 (8)	0.0006 (6)	0.0055 (6)	−0.0007 (6)
C2	0.0307 (8)	0.0243 (8)	0.0268 (8)	0.0016 (6)	0.0052 (6)	−0.0009 (6)
C3	0.0495 (10)	0.0292 (9)	0.0308 (8)	−0.0012 (7)	0.0131 (7)	0.0013 (7)

Geometric parameters (Å, º) top

N1—C1	1.3270 (19)	N3—C2	1.3294 (19)
N1—H1A	0.8600	N4—C3	1.326 (2)
N1—H1B	0.8600	N4—C2	1.366 (2)
N2—C3	1.330 (2)	O1—C1	1.2524 (18)
N2—N3	1.3553 (19)	C1—C2	1.493 (2)
N2—H2	0.8600	C3—H3	0.9300

C1—N1—H1A	120.0	O1—C1—C2	121.15 (14)
C1—N1—H1B	120.0	N1—C1—C2	114.62 (14)
H1A—N1—H1B	120.0	N3—C2—N4	114.43 (13)
C3—N2—N3	110.03 (13)	N3—C2—C1	121.94 (13)
C3—N2—H2	125.0	N4—C2—C1	123.62 (14)
N3—N2—H2	125.0	N4—C3—N2	110.81 (15)
C2—N3—N2	102.40 (13)	N4—C3—H3	124.6
C3—N4—C2	102.33 (13)	N2—C3—H3	124.6
O1—C1—N1	124.23 (15)

C3—N2—N3—C2	−0.33 (17)	N1—C1—C2—N3	176.10 (15)
N2—N3—C2—N4	0.05 (17)	O1—C1—C2—N4	174.46 (15)
N2—N3—C2—C1	179.30 (13)	N1—C1—C2—N4	−4.7 (2)
C3—N4—C2—N3	0.23 (18)	C2—N4—C3—N2	−0.43 (18)
C3—N4—C2—C1	−179.00 (14)	N3—N2—C3—N4	0.50 (19)
O1—C1—C2—N3	−4.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.86	2.21	3.065 (2)	173
N1—H1B···N4ⁱⁱ	0.86	2.22	3.010 (2)	154
N2—H2···O1ⁱⁱⁱ	0.86	2.07	2.909 (2)	163
N2—H2···N3ⁱⁱⁱ	0.86	2.54	3.055 (2)	120

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x, −y+2, −z+2; (iii) x−1/2, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₃H₄N₄O
M_r	112.10
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	3.6944 (4), 17.527 (3), 7.0520 (17)
β (°)	94.467 (1)
V (Å³)	455.24 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.22 × 0.18 × 0.09

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.972, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	2199, 807, 657
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.101, 1.05
No. of reflections	807
No. of parameters	73
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.23

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.86	2.21	3.065 (2)	173
N1—H1B···N4ⁱⁱ	0.86	2.22	3.010 (2)	154
N2—H2···O1ⁱⁱⁱ	0.86	2.07	2.909 (2)	163
N2—H2···N3ⁱⁱⁱ	0.86	2.54	3.055 (2)	120

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x, −y+2, −z+2; (iii) x−1/2, −y+3/2, z+1/2.

Acknowledgements

This work was supported by the Adult–Young Science Foundation of Guangxi Province (0447009), P. R. China.

References

Bruker (2003). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Crespo, L., Sanclimens, G., Pons, M., Giralt, E., Royo, M. & Albericio, F. (2005). Chem. Rev. 105, 1663–1681. Web of Science CrossRef PubMed CAS Google Scholar
Malinauskas, A., Niaura, G. & Bloxham, S. (2000). J. Colloid Interface Sci. 230, 122–127. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar