4-Amino-3,5-dimethyl-4H-1,2,4-triazole

Li, D.; Wei, G.-C.; Song, S.-Z.; Wang, H.

doi:10.1107/S1600536808014815

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1144

doi:10.1107/S1600536808014815

Open

access

4-Amino-3,5-dimethyl-4H-1,2,4-triazole

Daojin Li,^a ^* Guo-Chang Wei,^b Shu-Zhi Song ^b and Hui Wang ^b

^aCollege of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, People's Republic of China, and ^bHebei Zhongrun Pharmaceutical Co. Ltd, Shijiazhuang Pharm Group Co. Ltd, Shijiazhuang 050041, People's Republic of China
^*Correspondence e-mail: lidaojin7910@126.com

(Received 22 February 2008; accepted 16 May 2008; online 24 May 2008)

In the title compound, C₄H₈N₄, intermolecular N—H⋯N hydrogen bonds involving the amino groups and triazole N atoms form a two-dimensional sheet.

Related literature

For background, see: Desenko (1995 ); For further synthetic details, see: Van Albada et al. (1984 ). For related literature, see: Allen et al. (1987 ); Ding et al. (2004 ); Steel (2005 ); Van Diemen et al. (1991 ); Yi et al. (2004 ).

Experimental

Crystal data

C₄H₈N₄
M_r = 112.14
Monoclinic, P 2₁ /c
a = 5.8423 (12) Å
b = 7.7540 (16) Å
c = 12.846 (3) Å
β = 96.91 (3)°
V = 577.7 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 (2) K
0.30 × 0.30 × 0.20 mm

Data collection

Rigaku R-AXIS RAPID-S diffractometer
Absorption correction: none
5941 measured reflections
1333 independent reflections
1101 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.142
S = 1.12
1333 reflections
81 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4D⋯N1ⁱ	0.91 (2)	2.25 (2)	3.145 (2)	170 (2)
N)—H4E⋯N2ⁱⁱ	0.96 (2)	2.20 (2)	3.086 (2)	154 (2)
Symmetry codes: (i) x+1, y, z; (ii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); 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: SHELXL97 and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808014815/bv2093sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808014815/bv2093Isup2.hkl

checkCIF report

Comment top

N-containing heterocyclic aromatic compounds are extensively used as bridging ligands in coordination and metallosupramolecular chemistry (Steel, 2005). For its strong σ-donor and weak π-acceptor properties, 1,2,4-triazole and its derivatives possess several coordination modes through three N donor atoms coordinating to metal ions (Van Diemen et al., 1991;Yi et al.,2004; Ding et al., 2004). We herein report the crystal structure of the title compound (I). In the molecule of (I), (Fig. 1), the bond lengths and angles are generally within normal ranges (Allen et al., 1987). The H atoms of the amino group form hydrogen bonds with the N atoms of neighbouring triazole rings. The geometric parameters of the N—H···N (Spek, 2003) hydrogen-bonding interactions are given in Table 1, and a two dimensional sheet is formed by these intermolecular hydrogen bonds (Fig. 2).

Related literature top

For background, see: Desenko (1995); For further synthetic details, see: Van Albada et al. (1984). For related literature, see: Allen et al. (1987); Ding et al. (2004); Steel (2005); Van Diemen, Haasnoot, Hage, Reedijk, Vos & Wang (1991); Yi et al. (2004).

Experimental top

A 80% aqueous solution of 2.6 mol of hydrazine hydrate was added slowly to 2.0 mol of acetic acid. The mixture was heated slowly and kept at 493 K for about 3 h. When the mixture was cooled, colourless block shape crystals 4-amino-3,5-dimethyl-4H-1,2,4-triazole were isolated.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); 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: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003>.

Figures top

	Fig. 1. The structure of the title compound with ellipsoids drawn with 30% displacement probability.
	Fig. 2. Two dimensional sheet formed by intermolecular hydrogen bonds in the title compound, with the hydrogen bonds shown as dashed lines.

4-Amino-3,5-dimethyl-4H-1,2,4-triazole top

Crystal data top

C₄H₈N₄	F(000) = 240
M_r = 112.14	D_x = 1.289 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5363 reflections
a = 5.8423 (12) Å	θ = 3.1–27.5°
b = 7.7540 (16) Å	µ = 0.09 mm⁻¹
c = 12.846 (3) Å	T = 293 K
β = 96.91 (3)°	Block, colourless
V = 577.7 (2) Å³	0.30 × 0.30 × 0.20 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID-S diffractometer	1101 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.031
Graphite monochromator	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −7→7
5941 measured reflections	k = −10→10
1333 independent reflections	l = −16→16

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.142	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ²(F_o²) + (0.068P)² + 0.1583P] where P = (F_o² + 2F_c²)/3
1333 reflections	(Δ/σ)_max < 0.001
81 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₄H₈N₄	V = 577.7 (2) Å³
M_r = 112.14	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.8423 (12) Å	µ = 0.09 mm⁻¹
b = 7.7540 (16) Å	T = 293 K
c = 12.846 (3) Å	0.30 × 0.30 × 0.20 mm
β = 96.91 (3)°

Data collection top

Rigaku R-AXIS RAPID-S diffractometer	1101 reflections with I > 2σ(I)
5941 measured reflections	R_int = 0.031
1333 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.142	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	Δρ_max = 0.20 e Å⁻³
1333 reflections	Δρ_min = −0.19 e Å⁻³
81 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
N3	1.0528 (2)	0.17414 (16)	0.13102 (10)	0.0297 (3)
N4	1.2366 (2)	0.2703 (2)	0.09833 (12)	0.0396 (4)
N2	0.8357 (3)	0.02909 (19)	0.22608 (11)	0.0408 (4)
N1	0.7072 (2)	0.06903 (19)	0.13019 (12)	0.0406 (4)
C2	0.8418 (3)	0.1557 (2)	0.07503 (12)	0.0322 (4)
C1	1.0418 (3)	0.0933 (2)	0.22443 (13)	0.0323 (4)
C3	1.2408 (3)	0.0804 (3)	0.30796 (15)	0.0481 (5)
H3A	1.1950	0.0182	0.3667	0.072*
H3B	1.2906	0.1941	0.3299	0.072*
H3C	1.3651	0.0206	0.2812	0.072*
C4	0.7788 (3)	0.2255 (3)	−0.03203 (14)	0.0467 (5)
H4A	0.6213	0.1969	−0.0559	0.070*
H4B	0.8775	0.1762	−0.0787	0.070*
H4C	0.7968	0.3486	−0.0308	0.070*
H4D	1.362 (4)	0.200 (3)	0.1041 (18)	0.060 (6)*
H4E	1.263 (4)	0.361 (3)	0.1488 (19)	0.064 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N3	0.0243 (7)	0.0317 (7)	0.0332 (7)	−0.0002 (5)	0.0036 (5)	−0.0007 (5)
N4	0.0288 (8)	0.0462 (9)	0.0446 (9)	−0.0059 (7)	0.0082 (6)	0.0035 (7)
N2	0.0359 (8)	0.0444 (8)	0.0421 (9)	−0.0032 (6)	0.0042 (6)	0.0060 (6)
N1	0.0296 (7)	0.0453 (8)	0.0458 (9)	−0.0045 (6)	0.0003 (6)	0.0014 (7)
C2	0.0272 (8)	0.0332 (8)	0.0353 (8)	0.0019 (6)	0.0006 (6)	−0.0042 (6)
C1	0.0301 (8)	0.0323 (8)	0.0342 (9)	0.0017 (6)	0.0029 (6)	0.0009 (6)
C3	0.0413 (10)	0.0579 (11)	0.0426 (10)	0.0024 (9)	−0.0060 (8)	0.0093 (9)
C4	0.0457 (11)	0.0541 (11)	0.0378 (10)	0.0022 (9)	−0.0050 (8)	0.0020 (8)

Geometric parameters (Å, º) top

N3—C2	1.358 (2)	C2—C4	1.482 (2)
N3—C1	1.362 (2)	C1—C3	1.487 (2)
N3—N4	1.4123 (18)	C3—H3A	0.9600
N4—H4D	0.91 (2)	C3—H3B	0.9600
N4—H4E	0.95 (2)	C3—H3C	0.9600
N2—C1	1.305 (2)	C4—H4A	0.9600
N2—N1	1.398 (2)	C4—H4B	0.9600
N1—C2	1.306 (2)	C4—H4C	0.9600

C2—N3—C1	106.40 (13)	N3—C1—C3	123.42 (15)
C2—N3—N4	124.91 (14)	C1—C3—H3A	109.5
C1—N3—N4	128.54 (13)	C1—C3—H3B	109.5
N3—N4—H4D	106.9 (14)	H3A—C3—H3B	109.5
N3—N4—H4E	104.6 (13)	C1—C3—H3C	109.5
H4D—N4—H4E	109 (2)	H3A—C3—H3C	109.5
C1—N2—N1	107.45 (14)	H3B—C3—H3C	109.5
C2—N1—N2	107.31 (13)	C2—C4—H4A	109.5
N1—C2—N3	109.51 (14)	C2—C4—H4B	109.5
N1—C2—C4	126.35 (15)	H4A—C4—H4B	109.5
N3—C2—C4	124.14 (15)	C2—C4—H4C	109.5
N2—C1—N3	109.34 (14)	H4A—C4—H4C	109.5
N2—C1—C3	127.23 (16)	H4B—C4—H4C	109.5

C1—N2—N1—C2	−0.04 (18)	N1—N2—C1—N3	0.12 (18)
N2—N1—C2—N3	−0.05 (18)	N1—N2—C1—C3	−178.51 (17)
N2—N1—C2—C4	−179.82 (16)	C2—N3—C1—N2	−0.15 (18)
C1—N3—C2—N1	0.12 (18)	N4—N3—C1—N2	175.53 (15)
N4—N3—C2—N1	−175.76 (14)	C2—N3—C1—C3	178.54 (16)
C1—N3—C2—C4	179.90 (15)	N4—N3—C1—C3	−5.8 (3)
N4—N3—C2—C4	4.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4D···N1ⁱ	0.91 (2)	2.25 (2)	3.145 (2)	170 (2)
N)—H4E···N2ⁱⁱ	0.96 (2)	2.20 (2)	3.086 (2)	154 (2)

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

Experimental details

Crystal data
Chemical formula	C₄H₈N₄
M_r	112.14
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	5.8423 (12), 7.7540 (16), 12.846 (3)
β (°)	96.91 (3)
V (Å³)	577.7 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.30 × 0.20

Data collection
Diffractometer	Rigaku R-AXIS RAPID-S diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5941, 1333, 1101
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.142, 1.12
No. of reflections	1333
No. of parameters	81
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.19

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003>.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4D···N1ⁱ	0.91 (2)	2.25 (2)	3.145 (2)	170 (2)
N)—H4E···N2ⁱⁱ	0.96 (2)	2.20 (2)	3.086 (2)	154 (2)

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

Acknowledgements

The authors thank Luoyang Normal University for supporting this work.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Desenko, S. M. (1995). Khim. Geterotsikl. Soedin. (Chem. Heterocycl. Compd), pp. 2–24. Google Scholar
Ding, B., Yi, L., Zhu, L.-N., Cheng, P. & Liao, D.-Z. (2004). J. Coord. Chem. 57, 9–16. Web of Science CSD CrossRef CAS Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Steel, P. J. (2005). Acc. Chem. Res. 38, 243–250. Web of Science CrossRef PubMed CAS Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Van Albada, G. A., De Graaff, R. A. G., Haasnoot, J. G. & Reedijk, J. (1984). Inorg. Chem. 23, 1404–1408. CSD CrossRef CAS Web of Science Google Scholar
Van Diemen, J. H., Haasnoot, J. G., Hage, R., Reedijk, J., Vos, J. G. & Wang, R. (1991). Inorg. Chem. 30, 4038–4043. CSD CrossRef CAS Web of Science Google Scholar
Yi, L., Ding, B., Zhao, B., Cheng, P., Liao, D.-Z., Yan, S.-P. & Jiang, Z.-H. (2004). Inorg. Chem. 43, 33–43. Web of Science CSD CrossRef PubMed CAS Google Scholar