4-Methyl­sulfanyl-6-(4-pyrid­yl)-1,3,5-triazin-2-amine

Wu, Y.-P.; Tang, L.; Fu, F.; Liu, Q.-R.

doi:10.1107/S1600536811013171

organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1143

doi:10.1107/S1600536811013171

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4-Methylsulfanyl-6-(4-pyridyl)-1,3,5-triazin-2-amine

Ya-Pan Wu,^a Long Tang,^a Feng Fu ^a ^* and Qi-Rui Liu ^a

^aDepartment of Chemistry and Chemical Engineering, Shaanxi Key Laboratory of Chemical Reaction Engineering, Yan'an University, Yan'an, Shaanxi, 716000, People's Republic of China
^*Correspondence e-mail: yadxgncl@126.com

(Received 11 March 2011; accepted 8 April 2011; online 16 April 2011)

In the title compound, C₉H₉N₅S, the pyridyl and triazine rings make a dihedral angle of 4.8 (2)°. In the crystal, adjacent molecules are bridged by an N—H⋯N hydrogen bond, forming a helical chain running along the b axis.

Related literature

For the use of N-heterocycles in the synthesis of solid-state architectures, see: Janczak et al. (2003 ). For silmilar triazine derivatives, see: Ma & Che (2003 ).

Experimental

Crystal data

C₉H₉N₅S
M_r = 219.27
Orthorhombic, P 2₁ 2₁ 2₁
a = 3.9002 (11) Å
b = 10.111 (3) Å
c = 25.143 (7) Å
V = 991.4 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 298 K
0.29 × 0.08 × 0.06 mm

Data collection

Bruker SMART diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.919, T_max = 0.982
5053 measured reflections
1083 independent reflections
877 reflections with I > 2σ(I)
R_int = 0.055

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.096
S = 1.06
1083 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯N5ⁱ	0.86	2.10	2.956 (4)	172
Symmetry code: (i) x, y+1, z.

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); 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/S1600536811013171/ng5131sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811013171/ng5131Isup2.hkl

checkCIF report

Comment top

The title compound (I), (Fig. 1), crystallizes in space group P2(1)2(1)2(1) with one crystallographically independent molecule per asymmetric unit.Strong intermolecular N—H···N hydrogen bonds link the subunit into the one-dimensional linear structure (Fig. 2).

Related literature top

For the use of N-heterocycles in the synthesis of solid-state architectures, see: Janczak et al. (2003). For silmilar triazine derivatives, see: Ma & Che (2003).

Experimental top

The title compound was crystallized by hydrothermal method. A mixture of Cu(Ac)₂.H₂O (0.20 mmol), 2-amino-4-methylthio-6-(4-pyridyl)- 1,3,5-triazine (ampt, 0.20 mmol), 3-(4-carboxyphenyl)propionic acid (H₂cppa 0.20 mmol) 0.2M NaOH (0.1 mL) and water (10 ml) was stirred for 20 min. The mixture was then transferred to a 23 ml Teflon-lined autoclave and kept at 413 K for 72 h under autogenous pressure. Then the mixture was cooled to room temperature slowly. The targeted ternary Cu(II) coordination polymer was not synthesized. Accidentally,the compound ampt was returned unchangedly and crystallized in the hydrothermal reaction.Finally, Colorless single crystals of the title compound suitable for X-ray analysis were obtained from the reaction mixture.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker,1997); data reduction: SAINT (Bruker,1997); 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 molecular structure and labeling of (I). Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The one-dimensional linear structre (I), viewed along the b axis via N—H···N hydrogen bonding interaction. Dashed lines denote hydrogen bonds.

4-Methylsulfanyl-6-(4-pyridyl)-1,3,5-triazin-2-amine top

Crystal data top

C₉H₉N₅S	F(000) = 456
M_r = 219.27	D_x = 1.469 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	θ = 1.6–25.0°
a = 3.9002 (11) Å	µ = 0.30 mm⁻¹
b = 10.111 (3) Å	T = 298 K
c = 25.143 (7) Å	Prism, colorless
V = 991.4 (5) Å³	0.29 × 0.08 × 0.06 mm
Z = 4

Data collection top

Bruker SMART diffractometer	1083 independent reflections
Radiation source: fine-focus sealed tube	877 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.055
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −4→4
T_min = 0.919, T_max = 0.982	k = −10→12
5053 measured reflections	l = −29→29

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0478P)² + 0.2208P] where P = (F_o² + 2F_c²)/3
1083 reflections	(Δ/σ)_max = 0.001
136 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₉H₉N₅S	V = 991.4 (5) Å³
M_r = 219.27	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 3.9002 (11) Å	µ = 0.30 mm⁻¹
b = 10.111 (3) Å	T = 298 K
c = 25.143 (7) Å	0.29 × 0.08 × 0.06 mm

Data collection top

Bruker SMART diffractometer	1083 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	877 reflections with I > 2σ(I)
T_min = 0.919, T_max = 0.982	R_int = 0.055
5053 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 1.06	Δρ_max = 0.24 e Å⁻³
1083 reflections	Δρ_min = −0.24 e Å⁻³
136 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
N1	1.1007 (9)	0.9098 (3)	0.16248 (11)	0.0339 (8)
N2	1.0449 (9)	1.1369 (3)	0.13727 (11)	0.0343 (9)
N3	0.8318 (10)	0.9659 (3)	0.08066 (11)	0.0351 (8)
N4	0.7949 (11)	1.1828 (3)	0.05641 (13)	0.0478 (11)
H4A	0.8298	1.2657	0.0620	0.057*
H4B	0.6971	1.1574	0.0275	0.057*
N5	0.8411 (12)	0.4703 (3)	0.07660 (13)	0.0495 (10)
S1	1.3341 (3)	1.07833 (10)	0.23066 (4)	0.0426 (3)
C1	1.1382 (10)	1.0410 (4)	0.17022 (13)	0.0329 (9)
C2	0.8925 (11)	1.0938 (4)	0.09250 (14)	0.0339 (10)
C3	0.9465 (10)	0.8803 (3)	0.11698 (14)	0.0311 (10)
C4	1.3782 (12)	1.2539 (4)	0.22817 (16)	0.0508 (12)
H4C	1.4850	1.2846	0.2603	0.076*
H4D	1.1559	1.2938	0.2247	0.076*
H4E	1.5175	1.2779	0.1982	0.076*
C5	0.9850 (14)	0.5082 (4)	0.12212 (17)	0.0489 (13)
H5	1.0671	0.4430	0.1449	0.059*
C6	1.0198 (13)	0.6385 (4)	0.13752 (15)	0.0432 (12)
H6	1.1208	0.6594	0.1699	0.052*
C7	0.9028 (10)	0.7375 (3)	0.10425 (13)	0.0309 (9)
C8	0.7467 (11)	0.6986 (4)	0.05768 (15)	0.0377 (11)
H8	0.6563	0.7616	0.0346	0.045*
C9	0.7248 (12)	0.5655 (4)	0.04524 (16)	0.0460 (12)
H9	0.6230	0.5417	0.0132	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.040 (2)	0.0343 (19)	0.0279 (17)	−0.0042 (17)	−0.0046 (16)	−0.0005 (13)
N2	0.041 (2)	0.0336 (17)	0.0289 (18)	−0.0003 (17)	0.0012 (17)	−0.0010 (14)
N3	0.049 (2)	0.0304 (17)	0.0264 (17)	0.0020 (18)	−0.0011 (18)	0.0006 (13)
N4	0.076 (3)	0.0345 (17)	0.0325 (19)	−0.003 (2)	−0.011 (2)	0.0013 (15)
N5	0.066 (3)	0.0368 (18)	0.046 (2)	−0.004 (2)	−0.010 (2)	0.0011 (16)
S1	0.0492 (6)	0.0466 (6)	0.0318 (5)	−0.0024 (6)	−0.0092 (5)	−0.0037 (4)
C1	0.027 (2)	0.043 (2)	0.028 (2)	−0.002 (2)	0.001 (2)	−0.0035 (17)
C2	0.040 (3)	0.038 (2)	0.0235 (19)	−0.001 (2)	0.0020 (19)	0.0013 (18)
C3	0.035 (2)	0.034 (2)	0.025 (2)	−0.0040 (19)	0.0058 (19)	−0.0016 (16)
C4	0.056 (3)	0.053 (3)	0.044 (2)	−0.002 (3)	−0.010 (3)	−0.015 (2)
C5	0.059 (3)	0.042 (3)	0.046 (3)	0.002 (2)	−0.009 (3)	0.0127 (19)
C6	0.055 (3)	0.038 (2)	0.036 (2)	−0.005 (2)	−0.013 (2)	0.0021 (19)
C7	0.031 (2)	0.037 (2)	0.0238 (19)	−0.002 (2)	0.0028 (19)	0.0000 (17)
C8	0.044 (3)	0.037 (2)	0.032 (2)	0.000 (2)	−0.002 (2)	0.0039 (16)
C9	0.060 (3)	0.041 (2)	0.037 (2)	−0.009 (3)	−0.005 (2)	−0.0029 (19)

Geometric parameters (Å, º) top

N1—C3	1.327 (5)	C3—C7	1.488 (5)
N1—C1	1.349 (4)	C4—H4C	0.9600
N2—C1	1.326 (4)	C4—H4D	0.9600
N2—C2	1.345 (4)	C4—H4E	0.9600
N3—C3	1.336 (5)	C5—C6	1.379 (5)
N3—C2	1.348 (4)	C5—H5	0.9300
N4—C2	1.333 (5)	C6—C7	1.383 (5)
N4—H4A	0.8600	C6—H6	0.9300
N4—H4B	0.8600	C7—C8	1.377 (5)
N5—C9	1.325 (5)	C8—C9	1.384 (5)
N5—C5	1.331 (5)	C8—H8	0.9300
S1—C1	1.742 (4)	C9—H9	0.9300
S1—C4	1.785 (4)

C3—N1—C1	113.3 (3)	H4C—C4—H4D	109.5
C1—N2—C2	114.1 (3)	S1—C4—H4E	109.5
C3—N3—C2	114.4 (3)	H4C—C4—H4E	109.5
C2—N4—H4A	120.0	H4D—C4—H4E	109.5
C2—N4—H4B	120.0	N5—C5—C6	123.9 (4)
H4A—N4—H4B	120.0	N5—C5—H5	118.0
C9—N5—C5	116.5 (3)	C6—C5—H5	118.0
C1—S1—C4	103.12 (19)	C5—C6—C7	119.3 (4)
N2—C1—N1	126.8 (3)	C5—C6—H6	120.3
N2—C1—S1	120.5 (3)	C7—C6—H6	120.3
N1—C1—S1	112.7 (3)	C8—C7—C6	117.0 (4)
N4—C2—N2	118.5 (3)	C8—C7—C3	120.7 (3)
N4—C2—N3	116.6 (3)	C6—C7—C3	122.3 (3)
N2—C2—N3	124.9 (3)	C7—C8—C9	119.8 (4)
N1—C3—N3	126.5 (3)	C7—C8—H8	120.1
N1—C3—C7	117.1 (3)	C9—C8—H8	120.1
N3—C3—C7	116.3 (3)	N5—C9—C8	123.4 (4)
S1—C4—H4C	109.5	N5—C9—H9	118.3
S1—C4—H4D	109.5	C8—C9—H9	118.3

C2—N2—C1—N1	1.3 (6)	C2—N3—C3—C7	−176.7 (4)
C2—N2—C1—S1	−179.1 (3)	C9—N5—C5—C6	−0.5 (8)
C3—N1—C1—N2	−1.5 (6)	N5—C5—C6—C7	−0.5 (8)
C3—N1—C1—S1	178.9 (3)	C5—C6—C7—C8	1.9 (7)
C4—S1—C1—N2	−3.7 (4)	C5—C6—C7—C3	−177.0 (4)
C4—S1—C1—N1	176.0 (3)	N1—C3—C7—C8	−179.7 (4)
C1—N2—C2—N4	−178.8 (4)	N3—C3—C7—C8	−1.0 (6)
C1—N2—C2—N3	0.6 (6)	N1—C3—C7—C6	−0.8 (6)
C3—N3—C2—N4	177.4 (4)	N3—C3—C7—C6	177.9 (4)
C3—N3—C2—N2	−2.0 (6)	C6—C7—C8—C9	−2.4 (6)
C1—N1—C3—N3	−0.3 (6)	C3—C7—C8—C9	176.6 (4)
C1—N1—C3—C7	178.3 (3)	C5—N5—C9—C8	0.0 (7)
C2—N3—C3—N1	1.9 (6)	C7—C8—C9—N5	1.5 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N5ⁱ	0.86	2.10	2.956 (4)	172

Symmetry code: (i) x, y+1, z.

Experimental details

Crystal data
Chemical formula	C₉H₉N₅S
M_r	219.27
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	3.9002 (11), 10.111 (3), 25.143 (7)
V (Å³)	991.4 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.29 × 0.08 × 0.06

Data collection
Diffractometer	Bruker SMART diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.919, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	5053, 1083, 877
R_int	0.055
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.096, 1.06
No. of reflections	1083
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.24

Computer programs: SMART (Bruker, 1997), SAINT (Bruker,1997), 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···N5ⁱ	0.86	2.10	2.956 (4)	172

Symmetry code: (i) x, y+1, z.

Acknowledgements

This project was supported by the Natural Scientific Research Foundation of the Shaanxi Provincial Education Office of China (2010 J K903, 2010 J K905).

References

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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar