5,6-Dimethyl-1,2,4-triazin-3-amine

Wu, M.-H.; Qiu, Q.-M.; Gao, S.; Jin, Q.-H.; Zhang, C.-L.

doi:10.1107/S1600536811051920

organic compounds

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doi:10.1107/S1600536811051920

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5,6-Dimethyl-1,2,4-triazin-3-amine

Man-Hua Wu,^a Qi-Ming Qiu,^a Sen Gao,^a Qiong-Hua Jin ^a ^* and Cun-Lin Zhang ^b

^aDepartment of Chemistry, Capital Normal University, Beijing 100048, People's Republic of China, and ^bKey Laboratory of Terahertz Optoelectronic, Ministry of Education, Department of Physics, Capital Normal University, Beijing 100048, People's Republic of China
^*Correspondence e-mail: jinqh204@163.com

(Received 9 October 2011; accepted 1 December 2011; online 7 December 2011)

In the crystal structure of the title compound, C₅H₈N₄, adjacent molecules are connected through N—H⋯N hydrogen bonds, resulting in a zigzag chain along [100]. The amino groups and heterocyclic N atoms are involved in further N—H⋯N hydrogen bonds, forming R₂²(8) motifs.

Related literature

For the biological and medical applications of triazine, see: Anderson et al.(2003 ); Gavai et al. (2009 ); Hunt et al. (2004 ). For the structures of complexes containing triazine, see: Drew et al. (2001 ); Li et al. (2009 ); Machura et al. (2008 ). For the structures of complexes containing the title compound, see: Jiang et al. (2011 ); Self et al. (1991 ); Wu et al. (2011 ). For the structures of compounds containing R₂²(8)-type hydrogen bonds, see: Etter (1990 ); Glidewell et al. (2003 ).

Experimental

Crystal data

C₅H₈N₄
M_r = 124.14
Orthorhombic, P n m a
a = 7.4877 (8) Å
b = 6.7530 (7) Å
c = 12.6615 (13) Å
V = 640.22 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.50 × 0.39 × 0.38 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.960, T_max = 0.969
2997 measured reflections
614 independent reflections
421 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.157
S = 1.11
614 reflections
58 parameters
H-atom parameters constrained
Δρ_max = 0.26 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
N4—H4A⋯N3ⁱ	0.86	2.19	3.045 (4)	179
N4—H4B⋯N2ⁱⁱ	0.86	2.09	2.947 (4)	176
Symmetry codes: (i) $[x+{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; 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 global, I. DOI: 10.1107/S1600536811051920/rn2097sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811051920/rn2097Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811051920/rn2097Isup3.cml

checkCIF report

Comment top

The heterocyclic nitrogen compounds containing 1,2,4-triazine moieties have drawn much attention in recent years, owing to their interesting biological and medicinal properties (Anderson et al., 2003; Gavai et al., 2009; Hunt et al.,2004). They usually act as efficient ligands in supramolecular compounds (Drew et al., 2001; Li et al., 2009; Machura et al., 2008). The title compound (I) has been used as a multidentate ligand to form poly-nuclear complexes (Self et al., 1991). In (I), hydrogen bonds are formed between the NH groups of amino group and the N atoms.

We are interested in synthesizing new transition metal complexes containing (I) (Jiang et al., 2011; Wu et al., 2011). The title compound was unexpectedly obtained in the course of synthesizing Cu(I) complexes.

In the title compound, adjacent molecules are connected by intermolecular N—H···N hydrogen bonds to form a zigzag structure (Fig. 2). In the crystal structure, the amino groups and heterocyclic N atoms are involved in hydrogen bonds,forming R₂²(8) type hydrogen bonds (Etter, 1990; Glidewell et al., 2003).

Related literature top

For the biological and medical applications of triazine, see: Anderson et al.(2003); Gavai et al. (2009); Hunt et al. (2004). For the structures of complexes containing triazine, see: Drew et al. (2001); Li et al. (2009); Machura et al. (2008). For the structures of complexes containing the title compound, see: Jiang et al.(2011); Self et al. (1991); Wu et al. (2011). For the structures of compounds containing R₂²(8)-type hydrogen bonds, see: Etter (1990); Glidewell et al. (2003).

Experimental top

A mixture of CuCN and ADMT (ADMT=3-amino-5,6-dimethyl- 1,2,4-triazine) in molar ratio of 1:1 in the mixed solution of CH₃CN (7 ml)/ CH₃OH (3 ml) was stirred for 3 h,then filtered. Pale yellow crystals were obtained from the filtrate after standing at room temperature for several days.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); 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. Molecular structure of (I) with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Crystal packing for (I) with hydrogen bonds shown as dashed lines.

5,6-Dimethyl-1,2,4-triazin-3-amine top

Crystal data top

C₅H₈N₄	D_x = 1.278 Mg m⁻³
M_r = 124.14	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 1029 reflections
a = 7.4877 (8) Å	θ = 2.7–28.0°
b = 6.7530 (7) Å	µ = 0.08 mm⁻¹
c = 12.6615 (13) Å	T = 293 K
V = 640.22 (12) Å³	Block, yellow
Z = 4	0.50 × 0.39 × 0.38 mm
F(000) = 264

Data collection top

Bruker SMART CCD area-detector diffractometer	614 independent reflections
Radiation source: fine-focus sealed tube	421 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
phi and ω scans	θ_max = 25.0°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −7→8
T_min = 0.960, T_max = 0.969	k = −8→7
2997 measured reflections	l = −14→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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.157	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0627P)² + 0.3625P] where P = (F_o² + 2F_c²)/3
614 reflections	(Δ/σ)_max < 0.001
58 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₅H₈N₄	V = 640.22 (12) Å³
M_r = 124.14	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 7.4877 (8) Å	µ = 0.08 mm⁻¹
b = 6.7530 (7) Å	T = 293 K
c = 12.6615 (13) Å	0.50 × 0.39 × 0.38 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	614 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	421 reflections with I > 2σ(I)
T_min = 0.960, T_max = 0.969	R_int = 0.034
2997 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.157	H-atom parameters constrained
S = 1.11	Δρ_max = 0.26 e Å⁻³
614 reflections	Δρ_min = −0.16 e Å⁻³
58 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	Occ. (<1)
N1	1.0561 (4)	0.2500	0.5062 (2)	0.0514 (9)
N2	1.0506 (4)	0.2500	0.6123 (2)	0.0499 (8)
N3	0.7314 (4)	0.2500	0.60746 (19)	0.0466 (8)
N4	0.8858 (4)	0.2500	0.7657 (2)	0.0609 (10)
H4A	0.9838	0.2500	0.8011	0.073*
H4B	0.7850	0.2500	0.7982	0.073*
C1	0.8903 (4)	0.2500	0.6589 (2)	0.0447 (9)
C2	0.7407 (5)	0.2500	0.5030 (2)	0.0469 (9)
C3	0.9072 (5)	0.2500	0.4511 (2)	0.0477 (9)
C4	0.5682 (5)	0.2500	0.4422 (3)	0.0678 (12)
H4C	0.5720	0.3512	0.3890	0.102*	0.50
H4D	0.4708	0.2755	0.4896	0.102*	0.50
H4E	0.5516	0.1233	0.4093	0.102*	0.50
C5	0.9233 (5)	0.2500	0.3332 (2)	0.0624 (11)
H5A	0.8506	0.1461	0.3044	0.094*	0.50
H5B	1.0456	0.2286	0.3137	0.094*	0.50
H5C	0.8839	0.3753	0.3060	0.094*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0485 (19)	0.063 (2)	0.0425 (16)	0.000	0.0087 (13)	0.000
N2	0.0412 (17)	0.069 (2)	0.0395 (16)	0.000	0.0016 (12)	0.000
N3	0.0431 (16)	0.062 (2)	0.0346 (15)	0.000	−0.0012 (11)	0.000
N4	0.0382 (16)	0.105 (3)	0.0391 (16)	0.000	−0.0064 (12)	0.000
C1	0.0417 (19)	0.057 (2)	0.0350 (17)	0.000	−0.0008 (13)	0.000
C2	0.054 (2)	0.050 (2)	0.0374 (19)	0.000	−0.0014 (14)	0.000
C3	0.055 (2)	0.049 (2)	0.0397 (19)	0.000	0.0031 (16)	0.000
C4	0.060 (2)	0.097 (3)	0.047 (2)	0.000	−0.0118 (17)	0.000
C5	0.075 (3)	0.074 (3)	0.0376 (19)	0.000	0.0075 (18)	0.000

Geometric parameters (Å, º) top

N1—C3	1.315 (4)	C2—C4	1.503 (5)
N1—N2	1.344 (4)	C3—C5	1.498 (4)
N2—C1	1.338 (4)	C4—H4C	0.9600
N3—C2	1.325 (4)	C4—H4D	0.9600
N3—C1	1.356 (4)	C4—H4E	0.9600
N4—C1	1.353 (4)	C5—H5A	0.9600
N4—H4A	0.8600	C5—H5B	0.9600
N4—H4B	0.8600	C5—H5C	0.9600
C2—C3	1.409 (5)

C3—N1—N2	120.2 (3)	C2—C3—C5	122.4 (3)
C1—N2—N1	117.9 (3)	C2—C4—H4C	109.5
C2—N3—C1	115.7 (3)	C2—C4—H4D	109.5
C1—N4—H4A	120.0	H4C—C4—H4D	109.5
C1—N4—H4B	120.0	C2—C4—H4E	109.5
H4A—N4—H4B	120.0	H4C—C4—H4E	109.5
N2—C1—N4	117.6 (3)	H4D—C4—H4E	109.5
N2—C1—N3	125.2 (3)	C3—C5—H5A	109.5
N4—C1—N3	117.3 (3)	C3—C5—H5B	109.5
N3—C2—C3	120.8 (3)	H5A—C5—H5B	109.5
N3—C2—C4	117.7 (3)	C3—C5—H5C	109.5
C3—C2—C4	121.5 (3)	H5A—C5—H5C	109.5
N1—C3—C2	120.2 (3)	H5B—C5—H5C	109.5
N1—C3—C5	117.4 (3)

C3—N1—N2—C1	0.0	N2—N1—C3—C2	0.0
N1—N2—C1—N4	180.0	N2—N1—C3—C5	180.0
N1—N2—C1—N3	0.000 (1)	N3—C2—C3—N1	0.0
C2—N3—C1—N2	0.000 (1)	C4—C2—C3—N1	180.0
C2—N3—C1—N4	180.0	N3—C2—C3—C5	180.0
C1—N3—C2—C3	0.0	C4—C2—C3—C5	0.0
C1—N3—C2—C4	180.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N3ⁱ	0.86	2.19	3.045 (4)	179
N4—H4B···N2ⁱⁱ	0.86	2.09	2.947 (4)	176

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

Experimental details

Crystal data
Chemical formula	C₅H₈N₄
M_r	124.14
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	293
a, b, c (Å)	7.4877 (8), 6.7530 (7), 12.6615 (13)
V (Å³)	640.22 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.50 × 0.39 × 0.38

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.960, 0.969
No. of measured, independent and observed [I > 2σ(I)] reflections	2997, 614, 421
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.157, 1.11
No. of reflections	614
No. of parameters	58
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.16

Computer programs: SMART (Bruker, 2007), SAINT-Plus (Bruker, 2007), 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
N4—H4A···N3ⁱ	0.86	2.19	3.045 (4)	179.4
N4—H4B···N2ⁱⁱ	0.86	2.09	2.947 (4)	175.7

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

Acknowledgements

This work was supported by the National Natural Science Foundation of China (No. 21171119), the CAIQ Basic Research Program (No. 2010 J K022), the National Keystone Basic Research Program (973 Program) under grant Nos. 2007CB310408 and 2006CB302901, the Funding Project for Academic Human Resources Development in Institutions of Higher Learning under the Jurisdiction of Beijing Municipality and the State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences.

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page o39

doi:10.1107/S1600536811051920

Open

access