3-Benzyl­sulfanyl-1H-1,2,4-triazol-5-amine

Zhang, S.; Liu, P.-J.; Ma, D.-S.; Hou, G.-F.

doi:10.1107/S1600536811052159

organic compounds

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Volume 68| Part 1| January 2012| Page o83

doi:10.1107/S1600536811052159

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3-Benzylsulfanyl-1H-1,2,4-triazol-5-amine

Shuai Zhang,^a Pei-Jiang Liu,^a Dong-Sheng Ma ^a ^* and Guang-Feng Hou ^a

^aCollege of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China
^*Correspondence e-mail: hgf1000@163.com

(Received 29 November 2011; accepted 3 December 2011; online 10 December 2011)

In the title molecule, C₉H₁₀N₄S, the dihedral angle between the benzene and triazole rings is 81.05 (5)°. In the crystal, N—H⋯N hydrogen bonds link the molecules into infinite zigzag chains along [010].

Related literature

For the biological properties of 1,2,4-triazoles derivatives, see: Paulvannan et al. (2001 ); El-Sagheer & Brown (2011 ).

Experimental

Crystal data

C₉H₁₀N₄S
M_r = 206.27
Monoclinic, P 2₁ /c
a = 9.870 (2) Å
b = 9.6370 (19) Å
c = 10.398 (2) Å
β = 90.18 (3)°
V = 989.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 293 K
0.38 × 0.26 × 0.11 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.897, T_max = 0.970
9367 measured reflections
2267 independent reflections
1372 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.111
S = 1.04
2267 reflections
136 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H41⋯N1ⁱ	0.89 (1)	2.20 (2)	3.044 (3)	158 (3)
N2—H21⋯N3ⁱⁱ	0.90 (1)	2.03 (2)	2.873 (2)	155 (2)
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalClear (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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811052159/cv5211sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811052159/cv5211Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811052159/cv5211Isup3.cml

checkCIF report

Comment top

We are paying attention to the synthesis and applications of substituted 1,2,4-triazoles due to their comprehensive biological activities such as antihypertensive, antifungal and antibacterial properties (Paulvannan et al., 2001; El-Sagheer et al., 2011). Herein, we report the synthesis and crystal structure of the title compound (I).

In (I) (Fig. 1), the benzene and triazole rings form a dihedral angle of 81.05 (5)°. In the crystal packing, the N—H···N hydrogen bonds (Table 1) link adjacent molecules into infinite zigzag chains along [010] (Fig. 2).

Related literature top

For the biological properties of 1,2,4-triazoles derivatives, see: Paulvannan et al. (2001); El-Sagheer & Brown (2011).

Experimental top

In aqueous (10 mL) solution of NaOH (0.40 g, 0.010 mol) and 5-amino-1H-1,2,4-triazole-3-thiol (1.16 g, 0.010 mol, commercial product) was added an ethanol (20 mL) solution of benzyl chloride (1.52 g, 0.012 mol) with stirring. After stirring for 10 min, the solution evaporated. Then the resulting precipitate was filtered off, diluted with water and purified to give the title compound. Colourless prismatic crystal suitable for X-ray analysis were obtained by recrystallization in chloroform solution.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (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).

Figures top

	Fig. 1. The molecular structure of (I) showing the atomic numbering and 30% probabilty displacement ellipsoids.
	Fig. 2. A portion of the crystal packing showing hydrogen-bonded (dashed lines) chains. C-bound H atoms omitted for clarity.

3-Benzylsulfanyl-1H-1,2,4-triazol-5-amine top

Crystal data top

C₉H₁₀N₄S	F(000) = 432
M_r = 206.27	D_x = 1.385 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6282 reflections
a = 9.870 (2) Å	θ = 3.5–27.5°
b = 9.6370 (19) Å	µ = 0.29 mm⁻¹
c = 10.398 (2) Å	T = 293 K
β = 90.18 (3)°	Block, colorless
V = 989.0 (3) Å³	0.38 × 0.26 × 0.11 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	2267 independent reflections
Radiation source: fine-focus sealed tube	1372 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
ω scan	θ_max = 27.5°, θ_min = 3.5°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −12→12
T_min = 0.897, T_max = 0.970	k = −12→12
9367 measured reflections	l = −13→13

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0455P)² + 0.1013P] where P = (F_o² + 2F_c²)/3
2267 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.26 e Å⁻³
3 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₉H₁₀N₄S	V = 989.0 (3) Å³
M_r = 206.27	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.870 (2) Å	µ = 0.29 mm⁻¹
b = 9.6370 (19) Å	T = 293 K
c = 10.398 (2) Å	0.38 × 0.26 × 0.11 mm
β = 90.18 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2267 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1372 reflections with I > 2σ(I)
T_min = 0.897, T_max = 0.970	R_int = 0.059
9367 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	3 restraints
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.26 e Å⁻³
2267 reflections	Δρ_min = −0.25 e Å⁻³
136 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	0.9298 (2)	0.2955 (2)	0.45864 (19)	0.0424 (5)
C2	1.0473 (2)	0.2171 (2)	0.4593 (2)	0.0510 (6)
H2	1.0536	0.1402	0.5131	0.061*
C3	1.1549 (3)	0.2511 (3)	0.3816 (2)	0.0598 (7)
H3	1.2329	0.1969	0.3823	0.072*
C4	1.1468 (3)	0.3657 (3)	0.3029 (2)	0.0606 (7)
H4	1.2198	0.3896	0.2510	0.073*
C5	1.0312 (3)	0.4446 (3)	0.3008 (2)	0.0564 (6)
H5	1.0256	0.5214	0.2469	0.068*
C6	0.9232 (2)	0.4102 (2)	0.3784 (2)	0.0501 (6)
H6	0.8453	0.4644	0.3769	0.060*
C7	0.8148 (2)	0.2577 (3)	0.5473 (2)	0.0541 (6)
H7A	0.7510	0.3341	0.5495	0.065*
H7B	0.8506	0.2456	0.6335	0.065*
C8	0.6212 (2)	0.1615 (2)	0.3776 (2)	0.0442 (5)
C9	0.4869 (2)	0.1511 (2)	0.2191 (2)	0.0462 (6)
N1	0.5965 (2)	0.29303 (18)	0.3524 (2)	0.0541 (5)
N2	0.5088 (2)	0.28358 (17)	0.2498 (2)	0.0539 (5)
H21	0.473 (3)	0.3613 (18)	0.216 (2)	0.081*
N3	0.55663 (18)	0.06938 (16)	0.29881 (19)	0.0460 (5)
N4	0.4055 (2)	0.1079 (2)	0.1236 (2)	0.0665 (6)
H41	0.404 (3)	0.0173 (12)	0.107 (3)	0.100*
H42	0.368 (3)	0.167 (3)	0.068 (2)	0.100*
S1	0.72492 (7)	0.10082 (6)	0.50093 (7)	0.0582 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0478 (13)	0.0408 (11)	0.0385 (11)	−0.0047 (9)	−0.0002 (10)	−0.0064 (10)
C2	0.0548 (15)	0.0433 (13)	0.0548 (14)	0.0000 (10)	−0.0025 (12)	0.0058 (11)
C3	0.0481 (15)	0.0580 (15)	0.0735 (16)	0.0027 (12)	0.0074 (13)	0.0032 (13)
C4	0.0516 (16)	0.0676 (17)	0.0625 (15)	−0.0123 (13)	0.0078 (12)	0.0057 (14)
C5	0.0657 (18)	0.0511 (14)	0.0522 (14)	−0.0083 (12)	−0.0014 (13)	0.0119 (12)
C6	0.0508 (14)	0.0453 (12)	0.0543 (13)	0.0016 (10)	−0.0055 (11)	0.0007 (11)
C7	0.0587 (16)	0.0511 (13)	0.0525 (13)	−0.0024 (11)	0.0059 (12)	−0.0027 (11)
C8	0.0382 (12)	0.0273 (10)	0.0672 (14)	0.0003 (9)	0.0137 (11)	0.0022 (10)
C9	0.0393 (12)	0.0266 (10)	0.0728 (15)	−0.0016 (9)	0.0111 (11)	0.0016 (11)
N1	0.0525 (13)	0.0264 (9)	0.0834 (14)	0.0016 (8)	−0.0020 (11)	−0.0027 (9)
N2	0.0495 (12)	0.0245 (9)	0.0876 (15)	0.0002 (8)	−0.0015 (11)	0.0035 (9)
N3	0.0400 (10)	0.0226 (8)	0.0753 (13)	−0.0012 (7)	0.0092 (9)	0.0002 (9)
N4	0.0709 (16)	0.0374 (11)	0.0912 (17)	−0.0030 (10)	−0.0166 (13)	0.0004 (12)
S1	0.0576 (4)	0.0398 (3)	0.0774 (5)	−0.0023 (3)	0.0053 (3)	0.0130 (3)

Geometric parameters (Å, º) top

C1—C2	1.384 (3)	C7—H7A	0.9700
C1—C6	1.386 (3)	C7—H7B	0.9700
C1—C7	1.509 (3)	C8—N1	1.317 (3)
C2—C3	1.377 (3)	C8—N3	1.365 (3)
C2—H2	0.9300	C8—S1	1.740 (2)
C3—C4	1.376 (3)	C9—N3	1.333 (3)
C3—H3	0.9300	C9—N2	1.334 (3)
C4—C5	1.371 (4)	C9—N4	1.342 (3)
C4—H4	0.9300	N1—N2	1.375 (3)
C5—C6	1.380 (3)	N2—H21	0.900 (10)
C5—H5	0.9300	N4—H42	0.892 (10)
C6—H6	0.9300	N4—H41	0.889 (10)
C7—S1	1.817 (2)	N4—H42	0.892 (10)

C2—C1—C6	118.5 (2)	C1—C7—H7B	108.8
C2—C1—C7	119.8 (2)	S1—C7—H7B	108.8
C6—C1—C7	121.7 (2)	H7A—C7—H7B	107.6
C3—C2—C1	121.0 (2)	N1—C8—N3	114.9 (2)
C3—C2—H2	119.5	N1—C8—S1	125.35 (18)
C1—C2—H2	119.5	N3—C8—S1	119.75 (15)
C4—C3—C2	119.8 (2)	N3—C9—N2	109.5 (2)
C4—C3—H3	120.1	N3—C9—N4	125.7 (2)
C2—C3—H3	120.1	N2—C9—N4	124.8 (2)
C5—C4—C3	120.0 (2)	C8—N1—N2	101.91 (18)
C5—C4—H4	120.0	C9—N2—N1	110.48 (19)
C3—C4—H4	120.0	C9—N2—H21	129.8 (18)
C4—C5—C6	120.1 (2)	N1—N2—H21	119.7 (17)
C4—C5—H5	119.9	C9—N3—C8	103.18 (17)
C6—C5—H5	119.9	H42—N4—C9	122 (2)
C5—C6—C1	120.6 (2)	H42—N4—H41	120 (3)
C5—C6—H6	119.7	C9—N4—H41	117 (2)
C1—C6—H6	119.7	H42—N4—H42	0 (2)
C1—C7—S1	113.99 (16)	C9—N4—H42	122 (2)
C1—C7—H7A	108.8	H41—N4—H42	120 (3)
S1—C7—H7A	108.8	C8—S1—C7	101.62 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H41···N1ⁱ	0.89 (1)	2.20 (2)	3.044 (3)	158 (3)
N2—H21···N3ⁱⁱ	0.90 (1)	2.03 (2)	2.873 (2)	155 (2)

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

Experimental details

Crystal data
Chemical formula	C₉H₁₀N₄S
M_r	206.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	9.870 (2), 9.6370 (19), 10.398 (2)
β (°)	90.18 (3)
V (Å³)	989.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.38 × 0.26 × 0.11

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.897, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	9367, 2267, 1372
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.111, 1.04
No. of reflections	2267
No. of parameters	136
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.25

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalClear (Rigaku/MSC, 2002), 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—H41···N1ⁱ	0.889 (10)	2.202 (15)	3.044 (3)	158 (3)
N2—H21···N3ⁱⁱ	0.900 (10)	2.032 (15)	2.873 (2)	155 (2)

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

Acknowledgements

The authors thank Heilongjiang University for supporting this work.

References

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