PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 June 1; 64(Pt 6): o1144.
Published online 2008 May 24. doi:  10.1107/S1600536808014815
PMCID: PMC2961470

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

Abstract

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

An external file that holds a picture, illustration, etc.
Object name is e-64-o1144-scheme1.jpg

Experimental

Crystal data

  • C4H8N4
  • M r = 112.14
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1144-efi1.jpg
  • 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[F 2 > 2σ(F 2)] = 0.051
  • wR(F 2) = 0.142
  • S = 1.12
  • 1333 reflections
  • 81 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.20 e Å−3
  • Δρmin = −0.19 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

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

Acknowledgments

The authors thank Luoyang Normal University for supporting this work.

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

Methyl H atoms were included in calculated positions and treated in the subsequent refinement as riding atoms, with C—H = 0.96Å and Uiso(H) = 1.5Ueq(C). Atoms H4D and H4E, which are involved in hydrogen-bonding interactions, were located in a difference Fourier map and refined freely with isotropic displacement parameters.

Figures

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.

Crystal data

C4H8N4F000 = 240
Mr = 112.14Dx = 1.289 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5363 reflections
a = 5.8423 (12) Åθ = 3.1–27.5º
b = 7.7540 (16) ŵ = 0.09 mm1
c = 12.846 (3) ÅT = 293 (2) K
β = 96.91 (3)ºBlock, colourless
V = 577.7 (2) Å30.30 × 0.30 × 0.20 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID-S diffractometer1101 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.031
Monochromator: graphiteθmax = 27.5º
T = 293(2) Kθmin = 3.1º
ω scansh = −7→7
Absorption correction: nonek = −10→10
5941 measured reflectionsl = −16→16
1333 independent reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.051H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.142  w = 1/[σ2(Fo2) + (0.068P)2 + 0.1583P] where P = (Fo2 + 2Fc2)/3
S = 1.12(Δ/σ)max < 0.001
1333 reflectionsΔρmax = 0.20 e Å3
81 parametersΔρmin = −0.19 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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
N31.0528 (2)0.17414 (16)0.13102 (10)0.0297 (3)
N41.2366 (2)0.2703 (2)0.09833 (12)0.0396 (4)
N20.8357 (3)0.02909 (19)0.22608 (11)0.0408 (4)
N10.7072 (2)0.06903 (19)0.13019 (12)0.0406 (4)
C20.8418 (3)0.1557 (2)0.07503 (12)0.0322 (4)
C11.0418 (3)0.0933 (2)0.22443 (13)0.0323 (4)
C31.2408 (3)0.0804 (3)0.30796 (15)0.0481 (5)
H3A1.19500.01820.36670.072*
H3B1.29060.19410.32990.072*
H3C1.36510.02060.28120.072*
C40.7788 (3)0.2255 (3)−0.03203 (14)0.0467 (5)
H4A0.62130.1969−0.05590.070*
H4B0.87750.1762−0.07870.070*
H4C0.79680.3486−0.03080.070*
H4D1.362 (4)0.200 (3)0.1041 (18)0.060 (6)*
H4E1.263 (4)0.361 (3)0.1488 (19)0.064 (7)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N30.0243 (7)0.0317 (7)0.0332 (7)−0.0002 (5)0.0036 (5)−0.0007 (5)
N40.0288 (8)0.0462 (9)0.0446 (9)−0.0059 (7)0.0082 (6)0.0035 (7)
N20.0359 (8)0.0444 (8)0.0421 (9)−0.0032 (6)0.0042 (6)0.0060 (6)
N10.0296 (7)0.0453 (8)0.0458 (9)−0.0045 (6)0.0003 (6)0.0014 (7)
C20.0272 (8)0.0332 (8)0.0353 (8)0.0019 (6)0.0006 (6)−0.0042 (6)
C10.0301 (8)0.0323 (8)0.0342 (9)0.0017 (6)0.0029 (6)0.0009 (6)
C30.0413 (10)0.0579 (11)0.0426 (10)0.0024 (9)−0.0060 (8)0.0093 (9)
C40.0457 (11)0.0541 (11)0.0378 (10)0.0022 (9)−0.0050 (8)0.0020 (8)

Geometric parameters (Å, °)

N3—C21.358 (2)C2—C41.482 (2)
N3—C11.362 (2)C1—C31.487 (2)
N3—N41.4123 (18)C3—H3A0.9600
N4—H4D0.91 (2)C3—H3B0.9600
N4—H4E0.95 (2)C3—H3C0.9600
N2—C11.305 (2)C4—H4A0.9600
N2—N11.398 (2)C4—H4B0.9600
N1—C21.306 (2)C4—H4C0.9600
C2—N3—C1106.40 (13)N3—C1—C3123.42 (15)
C2—N3—N4124.91 (14)C1—C3—H3A109.5
C1—N3—N4128.54 (13)C1—C3—H3B109.5
N3—N4—H4D106.9 (14)H3A—C3—H3B109.5
N3—N4—H4E104.6 (13)C1—C3—H3C109.5
H4D—N4—H4E109 (2)H3A—C3—H3C109.5
C1—N2—N1107.45 (14)H3B—C3—H3C109.5
C2—N1—N2107.31 (13)C2—C4—H4A109.5
N1—C2—N3109.51 (14)C2—C4—H4B109.5
N1—C2—C4126.35 (15)H4A—C4—H4B109.5
N3—C2—C4124.14 (15)C2—C4—H4C109.5
N2—C1—N3109.34 (14)H4A—C4—H4C109.5
N2—C1—C3127.23 (16)H4B—C4—H4C109.5
C1—N2—N1—C2−0.04 (18)N1—N2—C1—N30.12 (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—N10.12 (18)N4—N3—C1—N2175.53 (15)
N4—N3—C2—N1−175.76 (14)C2—N3—C1—C3178.54 (16)
C1—N3—C2—C4179.90 (15)N4—N3—C1—C3−5.8 (3)
N4—N3—C2—C44.0 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N4—H4D···N1i0.91 (2)2.25 (2)3.145 (2)170 (2)
N)—H4E···N2ii0.96 (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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BV2093).

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.
  • Desenko, S. M. (1995). Khim. Geterotsikl. Soedin. (Chem. Heterocycl. Compd), pp. 2–24.
  • Ding, B., Yi, L., Zhu, L.-N., Cheng, P. & Liao, D.-Z. (2004). J. Coord. Chem.57, 9–16.
  • Rigaku (1998). RAPID-AUTO Rigaku Corporation, Tokyo, Japan.
  • Rigaku/MSC (2002). CrystalStructure Rigaku/MSC Inc., The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Steel, P. J. (2005). Acc. Chem. Res.38, 243–250. [PubMed]
  • Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.
  • Van Albada, G. A., De Graaff, R. A. G., Haasnoot, J. G. & Reedijk, J. (1984). Inorg. Chem.23, 1404–1408.
  • Van Diemen, J. H., Haasnoot, J. G., Hage, R., Reedijk, J., Vos, J. G. & Wang, R. (1991). Inorg. Chem.30, 4038–4043.
  • Yi, L., Ding, B., Zhao, B., Cheng, P., Liao, D.-Z., Yan, S.-P. & Jiang, Z.-H. (2004). Inorg. Chem.43, 33–43. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography