3-Nitro-1H-1,2,4-triazole

Hemamalini, M.; Fun, H.-K.

doi:10.1107/S1600536810049287

organic compounds

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Volume 67| Part 1| January 2011| Page o15

https://doi.org/10.1107/S1600536810049287

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3-Nitro-1H-1,2,4-triazole

Madhukar Hemamalini ^a and Hoong-Kun Fun ^a ^*‡

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 22 November 2010; accepted 25 November 2010; online 4 December 2010)

The asymmetric unit of the title compound, C₂H₂N₄O₂, contains two crystallographically independent molecules in which the triazole rings are essentially planar, with maximum deviations of 0.003 (1) Å in both molecules. The dihedral angle between the two 1H-1,2,4-triazole rings is 56.58 (5)°. In the crystal, molecules are linked via intermolecular N—H⋯N and C—H⋯O hydrogen bonds, forming a supramolecular chain along the b axis.

Related literature

For details and applications of 1H-1,2,4-triazole derivatives, see: Desenko (1995 ); Vos et al. (1983 ); van Albada et al. (1984 ); Al-Kharafi et al. (1986 ); Gupta & Bhargava (1978 ); Jones et al. (1965 ); Bennur et al. (1976 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₂H₂N₄O₂
M_r = 114.08
Monoclinic, P 2₁ /c
a = 8.7818 (1) Å
b = 10.0726 (2) Å
c = 9.9703 (1) Å
β = 107.081 (1)°
V = 843.03 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 100 K
0.48 × 0.33 × 0.30 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.928, T_max = 0.954
11450 measured reflections
3081 independent reflections
2768 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.092
S = 1.05
3081 reflections
153 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2A—H1N1⋯N1Aⁱ	0.885 (15)	1.995 (15)	2.8540 (9)	163.4 (15)
N2B—H1N2⋯N1Bⁱⁱ	0.857 (16)	2.057 (16)	2.9128 (10)	176.0 (16)
C1A—H1AA⋯O2Aⁱⁱⁱ	0.93	2.50	3.1129 (10)	124
C1B—H1BA⋯O2Bⁱⁱ	0.93	2.51	3.0451 (11)	117
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810049287/is2634sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810049287/is2634Isup2.hkl

checkCIF report

Comment top

1H-1,2,4-Triazole ring systems are typical planar six-π-electron partially aromatic systems, and are used, along with their derivatives, as starting materials for the synthesis of many heterocycles (Desenko, 1995). Substituted 1H-1,2,4-triazoles have also been actively studied as bridging ligands coordinating through their vicinal N atoms and some have special structures with interesting magnetic properties (Vos et al., 1983; van Albada et al., 1984). Studies also indicate that the 1H-1,2,4-triazole system is associated with anticorrosion (Al-Kharafi et al., 1986) and anti-inflammatory action (Gupta & Bhargava, 1978) and other pharmacological activities by exhibiting antiviral, anti-asthmatic, diuretic, analgesic, antimicrobial, antidepressant and antifungal effects (Jones et al., 1965; Bennur et al., 1976).

The asymmetric unit of the title compound consists of two crystallographically independent 3-nitro-1H-1,2,4-triazole molecules (A & B) with very similar geometry (Fig. 1). The 1H-1,2,4-triazole units are essentially planar with maximum deviations of 0.003 (1) Å for atom N1A (molecule A) and 0.003 (1) Å for atom C2B (molecule B). The dihedral angle between the two 1H-1,2,4-triazole (N1A—N3A/ C1A–C2A) and (N1B—N3B/C1B–C2B) rings is 56.58 (5)°.

In the crystal structure (Fig. 2), molecules are connected via N2A—H1N1···N1A, N2B—H1N2···N1B, C1A—H1AA···O2A and C1B—H1BA···O2B (Table 1) hydrogen bonds to form a one-dimensional supramolecular chain along the b-axis.

Related literature top

For details and applications of 1H-1,2,4-triazole derivatives, see: Desenko (1995); Vos et al. (1983); van Albada et al. (1984); Al-Kharafi et al. (1986); Gupta & Bhargava (1978); Jones et al. (1965); Bennur et al. (1976). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Experimental top

Hot methanol solution (20 ml) of 3-nitro-1H-1,2,4-triazole (57 mg, Aldrich) was warmed over a heating magnetic stirrer for 5 minutes. The resulting solution was allowed to cool slowly at room temperature. Crystals of the title compound appeared from the mother liquor after a few days.

Structure description top

For details and applications of 1H-1,2,4-triazole derivatives, see: Desenko (1995); Vos et al. (1983); van Albada et al. (1984); Al-Kharafi et al. (1986); Gupta & Bhargava (1978); Jones et al. (1965); Bennur et al. (1976). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The crystal packing of the title compound, showing a hydrogen-bonded (dashed lines) molecular chain.

3-Nitro-1H-1,2,4-triazole top

Crystal data top

C₂H₂N₄O₂	F(000) = 464
M_r = 114.08	D_x = 1.798 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7180 reflections
a = 8.7818 (1) Å	θ = 2.9–32.6°
b = 10.0726 (2) Å	µ = 0.16 mm⁻¹
c = 9.9703 (1) Å	T = 100 K
β = 107.081 (1)°	Block, colourless
V = 843.03 (2) Å³	0.48 × 0.33 × 0.30 mm
Z = 8

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3081 independent reflections
Radiation source: fine-focus sealed tube	2768 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
φ and ω scans	θ_max = 32.7°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −13→11
T_min = 0.928, T_max = 0.954	k = −15→13
11450 measured reflections	l = −15→15

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) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0495P)² + 0.2412P] where P = (F_o² + 2F_c²)/3
3081 reflections	(Δ/σ)_max = 0.001
153 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

C₂H₂N₄O₂	V = 843.03 (2) Å³
M_r = 114.08	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.7818 (1) Å	µ = 0.16 mm⁻¹
b = 10.0726 (2) Å	T = 100 K
c = 9.9703 (1) Å	0.48 × 0.33 × 0.30 mm
β = 107.081 (1)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3081 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2768 reflections with I > 2σ(I)
T_min = 0.928, T_max = 0.954	R_int = 0.022
11450 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.50 e Å⁻³
3081 reflections	Δρ_min = −0.40 e Å⁻³
153 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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) top

	x	y	z	U_iso*/U_eq
O1A	0.73082 (8)	−0.04055 (7)	0.51717 (7)	0.01914 (13)
O2A	0.85716 (9)	0.01680 (7)	0.73151 (6)	0.01888 (14)
N1A	1.01266 (8)	0.21389 (7)	0.64087 (7)	0.01307 (13)
N2A	0.99857 (9)	0.24376 (7)	0.42001 (7)	0.01273 (13)
N3A	0.89747 (8)	0.14183 (7)	0.41773 (7)	0.01286 (13)
N4A	0.82618 (9)	0.02813 (7)	0.60358 (7)	0.01348 (13)
C1A	1.06543 (10)	0.28585 (8)	0.55150 (8)	0.01356 (14)
H1AA	1.1381	0.3552	0.5768	0.016*
C2A	0.91199 (9)	0.13008 (8)	0.55271 (8)	0.01167 (14)
O1B	0.75840 (8)	0.41600 (7)	0.50676 (7)	0.02046 (14)
O2B	0.68377 (9)	0.58439 (6)	0.60867 (7)	0.01985 (14)
N1B	0.51771 (8)	0.42579 (7)	0.73353 (7)	0.01312 (13)
N2B	0.51813 (9)	0.20833 (7)	0.72132 (7)	0.01419 (13)
N3B	0.60998 (9)	0.24714 (7)	0.64058 (7)	0.01375 (13)
N4B	0.68913 (8)	0.46461 (7)	0.58504 (7)	0.01361 (13)
C1B	0.46484 (10)	0.31423 (8)	0.77581 (8)	0.01436 (15)
H1BA	0.4002	0.3102	0.8347	0.017*
C2B	0.60451 (9)	0.37710 (8)	0.65365 (8)	0.01189 (14)
H1N1	1.0120 (19)	0.2722 (16)	0.3403 (16)	0.034 (4)*
H1N2	0.5028 (18)	0.1259 (16)	0.7343 (15)	0.030 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1A	0.0195 (3)	0.0170 (3)	0.0203 (3)	−0.0044 (2)	0.0049 (2)	−0.0008 (2)
O2A	0.0278 (3)	0.0179 (3)	0.0136 (3)	0.0007 (2)	0.0102 (2)	0.0037 (2)
N1A	0.0164 (3)	0.0135 (3)	0.0103 (3)	−0.0005 (2)	0.0055 (2)	−0.0003 (2)
N2A	0.0164 (3)	0.0133 (3)	0.0099 (3)	0.0001 (2)	0.0060 (2)	0.0011 (2)
N3A	0.0156 (3)	0.0128 (3)	0.0107 (3)	0.0004 (2)	0.0048 (2)	0.0009 (2)
N4A	0.0161 (3)	0.0118 (3)	0.0144 (3)	0.0020 (2)	0.0072 (2)	0.0018 (2)
C1A	0.0163 (3)	0.0142 (3)	0.0115 (3)	−0.0007 (3)	0.0060 (3)	−0.0005 (2)
C2A	0.0146 (3)	0.0109 (3)	0.0107 (3)	0.0013 (2)	0.0056 (2)	0.0010 (2)
O1B	0.0240 (3)	0.0185 (3)	0.0245 (3)	0.0046 (2)	0.0158 (3)	0.0025 (2)
O2B	0.0264 (3)	0.0106 (3)	0.0260 (3)	−0.0006 (2)	0.0131 (3)	0.0004 (2)
N1B	0.0151 (3)	0.0111 (3)	0.0143 (3)	0.0010 (2)	0.0062 (2)	0.0004 (2)
N2B	0.0178 (3)	0.0101 (3)	0.0161 (3)	−0.0002 (2)	0.0072 (2)	0.0006 (2)
N3B	0.0163 (3)	0.0111 (3)	0.0149 (3)	0.0009 (2)	0.0062 (2)	0.0007 (2)
N4B	0.0144 (3)	0.0119 (3)	0.0153 (3)	0.0015 (2)	0.0055 (2)	0.0018 (2)
C1B	0.0166 (3)	0.0119 (3)	0.0160 (3)	0.0006 (3)	0.0070 (3)	0.0005 (2)
C2B	0.0128 (3)	0.0103 (3)	0.0127 (3)	0.0007 (2)	0.0041 (2)	0.0007 (2)

Geometric parameters (Å, º) top

O1A—N4A	1.2241 (10)	O1B—N4B	1.2239 (9)
O2A—N4A	1.2289 (9)	O2B—N4B	1.2329 (9)
N1A—C1A	1.3329 (10)	N1B—C1B	1.3307 (10)
N1A—C2A	1.3455 (10)	N1B—C2B	1.3462 (10)
N2A—C1A	1.3383 (10)	N2B—C1B	1.3421 (10)
N2A—N3A	1.3531 (10)	N2B—N3B	1.3539 (9)
N2A—H1N1	0.885 (15)	N2B—H1N2	0.857 (16)
N3A—C2A	1.3194 (9)	N3B—C2B	1.3178 (10)
N4A—C2A	1.4506 (10)	N4B—C2B	1.4476 (10)
C1A—H1AA	0.9300	C1B—H1BA	0.9300

C1A—N1A—C2A	101.26 (6)	C1B—N1B—C2B	100.99 (7)
C1A—N2A—N3A	110.72 (6)	C1B—N2B—N3B	110.52 (7)
C1A—N2A—H1N1	129.9 (10)	C1B—N2B—H1N2	128.3 (10)
N3A—N2A—H1N1	119.4 (10)	N3B—N2B—H1N2	121.2 (10)
C2A—N3A—N2A	100.64 (6)	C2B—N3B—N2B	100.52 (6)
O1A—N4A—O2A	125.11 (7)	O1B—N4B—O2B	124.56 (7)
O1A—N4A—C2A	118.18 (6)	O1B—N4B—C2B	118.56 (7)
O2A—N4A—C2A	116.70 (7)	O2B—N4B—C2B	116.86 (6)
N1A—C1A—N2A	110.12 (7)	N1B—C1B—N2B	110.33 (7)
N1A—C1A—H1AA	124.9	N1B—C1B—H1BA	124.8
N2A—C1A—H1AA	124.9	N2B—C1B—H1BA	124.8
N3A—C2A—N1A	117.27 (7)	N3B—C2B—N1B	117.63 (7)
N3A—C2A—N4A	121.04 (7)	N3B—C2B—N4B	121.29 (7)
N1A—C2A—N4A	121.66 (6)	N1B—C2B—N4B	121.08 (7)

C1A—N2A—N3A—C2A	−0.05 (8)	C1B—N2B—N3B—C2B	0.10 (9)
C2A—N1A—C1A—N2A	−0.45 (9)	C2B—N1B—C1B—N2B	−0.54 (9)
N3A—N2A—C1A—N1A	0.33 (10)	N3B—N2B—C1B—N1B	0.30 (10)
N2A—N3A—C2A—N1A	−0.27 (9)	N2B—N3B—C2B—N1B	−0.49 (9)
N2A—N3A—C2A—N4A	−178.46 (7)	N2B—N3B—C2B—N4B	179.31 (7)
C1A—N1A—C2A—N3A	0.46 (9)	C1B—N1B—C2B—N3B	0.66 (9)
C1A—N1A—C2A—N4A	178.64 (7)	C1B—N1B—C2B—N4B	−179.14 (7)
O1A—N4A—C2A—N3A	−5.31 (11)	O1B—N4B—C2B—N3B	4.58 (12)
O2A—N4A—C2A—N3A	173.84 (7)	O2B—N4B—C2B—N3B	−176.50 (8)
O1A—N4A—C2A—N1A	176.57 (7)	O1B—N4B—C2B—N1B	−175.62 (8)
O2A—N4A—C2A—N1A	−4.27 (11)	O2B—N4B—C2B—N1B	3.29 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2A—H1N1···N1Aⁱ	0.885 (15)	1.995 (15)	2.8540 (9)	163.4 (15)
N2B—H1N2···N1Bⁱⁱ	0.857 (16)	2.057 (16)	2.9128 (10)	176.0 (16)
C1A—H1AA···O2Aⁱⁱⁱ	0.93	2.50	3.1129 (10)	124
C1B—H1BA···O2Bⁱⁱ	0.93	2.51	3.0451 (11)	117

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

Experimental details

Crystal data
Chemical formula	C₂H₂N₄O₂
M_r	114.08
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	8.7818 (1), 10.0726 (2), 9.9703 (1)
β (°)	107.081 (1)
V (Å³)	843.03 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.16
Crystal size (mm)	0.48 × 0.33 × 0.30

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.928, 0.954
No. of measured, independent and observed [I > 2σ(I)] reflections	11450, 3081, 2768
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.760

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.092, 1.05
No. of reflections	3081
No. of parameters	153
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.40

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2A—H1N1···N1Aⁱ	0.885 (15)	1.995 (15)	2.8540 (9)	163.4 (15)
N2B—H1N2···N1Bⁱⁱ	0.857 (16)	2.057 (16)	2.9128 (10)	176.0 (16)
C1A—H1AA···O2Aⁱⁱⁱ	0.9300	2.5000	3.1129 (10)	124.00
C1B—H1BA···O2Bⁱⁱ	0.9300	2.5100	3.0451 (11)	117.00

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

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

MH and HKF thank the Malaysian Government and Universiti Sains Malaysia for the Research University grant No. 1001/PFIZIK/811160. MH also thanks Universiti Sains Malaysia for a post-doctoral research fellowship.

References

Albada, G. A. van, de Graaff, R. A. G., Haasnoot, J. G. & Reedijk, J. (1984). Inorg. Chem. 23, 1404–1408. CSD CrossRef Web of Science Google Scholar
Al-Kharafi, F. M., Al-Hajjar, F. H. & Katrib, A. (1986). Corros. Sci. 26, 257–264. CrossRef CAS Web of Science Google Scholar
Bennur, S. C., Jigajinni, V. B. & Badiger, V. V. (1976). Rev. Roum. Chim. 21, 757–762. CAS Google Scholar
Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107. CrossRef CAS Web of Science IUCr Journals Google Scholar
Desenko, S. M. (1995). Khim. Geterotsikl. Soedin. pp. 2–24. Google Scholar
Gupta, A. K. & Bhargava, K. P. (1978). Pharmazie, 33, 430–431. CAS PubMed Web of Science Google Scholar
Jones, D. H., Slack, R., Squires, S. & Wooldridge, K. R. H. (1965). J. Med. Chem. 8, 676–680. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Vos, G., le Febre, R. A., de Graaff, R. A. G., Haasnoot, J. G. & Reedijk, J. (1983). J. Am. Chem. Soc. 105, 1682–1683. CSD CrossRef CAS Web of Science Google Scholar