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

Abstract

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,

• a = 3.9002 (11) Å

• b = 10.111 (3) Å

• c = 25.143 (7) Å

• V = 991.4 (5) ų

• 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[F ² > 2σ(F ²)] = 0.046

• wR(F ²) = 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

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.

Supplementary Material

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

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) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

The C-bound H atoms were geometrically placed (C—H = 0.93 Å) and refined as riding with U_iso(H) =1.2U_eq(C). The NH H atoms were found from a difference Fourier map and restrained to 0.86 Å, and refined with U_iso(H) =1.2U_eq(N). Friedel equivalents have been merged.

Figures

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.

Crystal data

C9H9N5S	F(000) = 456
Mr = 219.27	Dx = 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

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

Refinement

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(Fo2) + (0.0478P)2 + 0.2208P] where P = (Fo2 + 2Fc2)/3
1083 reflections	(Δ/σ)max = 0.001
136 parameters	Δρmax = 0.24 e Å−3
0 restraints	Δρmin = −0.24 e Å−3

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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

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