3-Methyl­sulfanyl-5-phenyl-4H-1,2,4-triazol-4-amine–water (6/1)

Wu, D.-Z.; Liu, M.-C.; Wu, H.-Y.; Huang, X.-B.; Li, J.-J.

doi:10.1107/S1600536808041056

organic compounds

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Volume 65| Part 4| April 2009| Page o676

doi:10.1107/S1600536808041056

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3-Methylsulfanyl-5-phenyl-4H-1,2,4-triazol-4-amine–water (6/1)

Deng-Ze Wu,^a Miao-Chang Liu,^a Hua-Yue Wu,^a Xiao-Bo Huang ^a and Jian-Jun Li ^b ^*

^aSchool of Chemistry and Materials Science, Wenzhou University, Zhejiang Wenzhou 325027, People's Republic of China, and ^bZhejiang Key Laboratory of Pharmaceutical Engineering, College of Pharmaceutical Sciences, Zhejiang University of Technology, Zhejiang Hangzhou 310014, People's Republic of China
^*Correspondence e-mail: lijianjun@zjut.edu.cn

(Received 30 October 2008; accepted 5 December 2008; online 6 March 2009)

In the title compound, 6C₉H₁₀N₄S·H₂O, the dihedral angle between the five-membered triazole ring and the phenyl ring is 44.33 (16)°. The solvent water molecule is disordered about a special position with $[\overline3]$ symmetry and its occupancy cannot be greater than 0.1667. The crystal structure is stabilized by intermolecular N—H⋯N and C–H⋯N hydrogen bonds.

Related literature

For general background to 1,2,4-triazoles, see: Feng et al. (1992 ); Hui et al. (2000 ); Prasad et al. (1989 ); Mohan et al. (1987 ) For related structures, see: Xiang et al. (2004 ); Jin et al. (2004 )

Experimental

Crystal data

6C₉H₁₀N₄S·H₂O
M_r = 1255.73
Hexagonal, $[R \overline 3]$
a = 23.0266 (15) Å
c = 10.5190 (9) Å
V = 4830.2 (6) Å³
Z = 3
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 298 K
0.32 × 0.23 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.918, T_max = 0.960
8946 measured reflections
2011 independent reflections
1647 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.073
wR(F²) = 0.204
S = 0.99
2011 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯N1ⁱ	0.86	2.30	3.127 (4)	162
N4—H4B⋯N2ⁱⁱ	0.86	2.21	3.060 (4)	172
C5—H5⋯N1ⁱ	0.93	2.60	3.507 (6)	167
Symmetry codes: (i) y, -x+y+1, -z+1; (ii) $[-y+{\script{5\over 3}}, x-y+{\script{1\over 3}}, z+{\script{1\over 3}}]$ .

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); 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/S1600536808041056/sj2552sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808041056/sj2552Isup2.hkl

checkCIF report

Comment top

A literature survey reveals that 1,2,4-triazoles are good intermediates in the synthesis of some fused heterocycles which exhibit various biological properties, including antimicrobial (Feng et al., 1992), antibacterial and antifungal (Hui et al., 2000), anti-inflammatory (Prasad et al., 1989) and diuretic (Mohan & Anjaneyulu, 1987) activities.

The molecule of (I), Fig. 1, contains a five-membered triazole ring A(N1,N2,C3,N3,C2) with a benzene ring substituent B(C1—C6). The two rings are each essentially planar, with average deviations from planarity of 0.003 (1) and 0.004 (1) Å, respectively. The dihedral angle between the thiadiazole ring and the benzene ring is 44.33 (16)°.

The water molecule is disordered about a threefold inversion axis such that the asymmetric unit comprises one C₉H₁₀N₄S molecule and a water molecule with occupancy ca 0.167

The C—N bond lengths in the molecule lie in the range 1.302 (5)–1.364 (4) Å. These are longer than a typical double C=N bond [ca 1.269 (2) Å] (Xiang et al., 2004), but shorter than a C—N single bond [ca 1.443 (4) Å] (Jin et al., 2004), indicating a degree of electron delocalization in the triazole ring.

The crystal packing in (I), Fig. 2, is stabilized by intermolecular and intramolecular N—H···N and C–H···N hydrogen bonds, Table 1.

Related literature top

For general background to 1,2,4-triazoles, see: Feng et al. (1992); Hui et al. (2000); Prasad et al. (1989); Mohan et al. (1987) For related structures, see: Xiang et al. (2004); Jin et al. (2004)

Experimental top

4-Amino-5-phenyl-2,4-dihydro[1,2,4]triazole-3-thione(0.96 g 5.0 mmol), methyl iodide(1.07 g 7.5 mmol) and sodium hydroxide(0.28 g 7.0 mmol) were dissolved in stirred dichloromethane (30 ml)and left for 2 h at room temperature. The resulting solid was filtered off and recrystallized from ethanol to give the title compound in 73% yield. Crystals suitable for X-ray analysis were obtained by slow evaporation of a ethanol solution at room temperature (m.p. 425–426 K).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The formula unit of (I) with atom numbering, showing displacement ellipsoids at the 50% probability level.
	Fig. 2. Part of the crystal structure, showing the infinite hydrogen-bonding network of (I) running along the a axis. Hydrogen bonds are indicated by dashed lines.

3-Methylsulfanyl-5-phenyl-4H-1,2,4-triazol-4-amine–water (6/1) top

Crystal data top

6C₉H₁₀N₄S·H₂O	D_x = 1.314 Mg m⁻³
M_r = 1255.73	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, R3	Cell parameters from 2375 reflections
Hall symbol: -R 3	θ = 2.2–23.0°
a = 23.0266 (15) Å	µ = 0.27 mm⁻¹
c = 10.5190 (9) Å	T = 298 K
V = 4830.2 (6) Å³	Prism, colorless
Z = 3	0.32 × 0.23 × 0.15 mm
F(000) = 2004

Data collection top

Bruker SMART CCD area-detector diffractometer	2011 independent reflections
Radiation source: fine-focus sealed tube	1647 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
ϕ and ω scans	θ_max = 25.5°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −27→27
T_min = 0.918, T_max = 0.960	k = −27→20
8946 measured reflections	l = −10→12

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)] = 0.073	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.204	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.1049P)² + 19.9182P] where P = (F_o² + 2F_c²)/3
2011 reflections	(Δ/σ)_max < 0.001
137 parameters	Δρ_max = 0.70 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

6C₉H₁₀N₄S·H₂O	Z = 3
M_r = 1255.73	Mo Kα radiation
Hexagonal, R3	µ = 0.27 mm⁻¹
a = 23.0266 (15) Å	T = 298 K
c = 10.5190 (9) Å	0.32 × 0.23 × 0.15 mm
V = 4830.2 (6) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	2011 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1647 reflections with I > 2σ(I)
T_min = 0.918, T_max = 0.960	R_int = 0.047
8946 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.073	0 restraints
wR(F²) = 0.204	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.1049P)² + 19.9182P] where P = (F_o² + 2F_c²)/3
2011 reflections	Δρ_max = 0.70 e Å⁻³
137 parameters	Δρ_min = −0.27 e Å⁻³

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	Occ. (<1)
S1	1.03285 (6)	0.89151 (5)	0.71331 (11)	0.0608 (4)
O1W	0.645 (2)	0.348 (3)	0.356 (2)	0.095 (12)	0.166667
H1W	0.6667	0.3333	0.3967	0.142*	0.50
H2W	0.6439	0.3779	0.3102	0.142*	0.166667
N1	1.08197 (15)	0.83742 (16)	0.5409 (3)	0.0520 (8)
N2	1.05881 (15)	0.77523 (16)	0.4828 (3)	0.0501 (8)
N3	0.98055 (13)	0.76822 (14)	0.6086 (3)	0.0381 (7)
N4	0.92266 (14)	0.74747 (15)	0.6827 (3)	0.0457 (8)
H4A	0.8918	0.7438	0.6318	0.055*
H4B	0.9136	0.7090	0.7124	0.055*
C1	1.1062 (3)	0.9644 (2)	0.6516 (5)	0.0809 (15)
H1A	1.1442	0.9579	0.6578	0.121*
H1B	1.1146	1.0031	0.7001	0.121*
H1C	1.0989	0.9709	0.5642	0.121*
C2	1.03399 (18)	0.83096 (18)	0.6157 (3)	0.0433 (9)
C3	0.99830 (17)	0.73476 (18)	0.5243 (3)	0.0410 (8)
C4	0.95704 (18)	0.66410 (18)	0.4868 (3)	0.0427 (8)
C5	0.8903 (2)	0.6366 (2)	0.4557 (4)	0.0555 (10)
H5	0.8695	0.6622	0.4626	0.067*
C6	0.8543 (2)	0.5711 (2)	0.4142 (5)	0.0726 (13)
H6	0.8092	0.5526	0.3935	0.087*
C7	0.8845 (3)	0.5333 (2)	0.4034 (5)	0.0783 (14)
H7	0.8600	0.4892	0.3746	0.094*
C8	0.9510 (3)	0.5600 (2)	0.4349 (5)	0.0689 (13)
H8	0.9714	0.5341	0.4276	0.083*
C9	0.9874 (2)	0.6252 (2)	0.4773 (4)	0.0524 (10)
H9	1.0322	0.6431	0.4996	0.063*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0603 (7)	0.0493 (6)	0.0676 (7)	0.0236 (5)	0.0099 (5)	−0.0071 (5)
O1W	0.050 (15)	0.09 (3)	0.100 (18)	0.001 (10)	0.041 (12)	−0.015 (14)
N1	0.0389 (17)	0.0496 (19)	0.060 (2)	0.0166 (15)	0.0097 (15)	0.0029 (15)
N2	0.0428 (18)	0.0512 (19)	0.0565 (19)	0.0236 (15)	0.0112 (14)	0.0018 (15)
N3	0.0322 (14)	0.0406 (16)	0.0436 (16)	0.0197 (13)	0.0060 (12)	0.0054 (12)
N4	0.0378 (16)	0.0474 (17)	0.0534 (19)	0.0225 (14)	0.0097 (13)	0.0090 (14)
C1	0.079 (3)	0.044 (2)	0.095 (4)	0.012 (2)	0.013 (3)	−0.005 (2)
C2	0.0404 (19)	0.0412 (19)	0.048 (2)	0.0203 (16)	0.0030 (16)	0.0040 (15)
C3	0.0404 (19)	0.045 (2)	0.0417 (19)	0.0245 (16)	0.0027 (15)	0.0037 (15)
C4	0.048 (2)	0.045 (2)	0.0392 (19)	0.0258 (17)	0.0067 (15)	0.0056 (15)
C5	0.050 (2)	0.053 (2)	0.069 (3)	0.029 (2)	−0.0036 (19)	−0.005 (2)
C6	0.056 (3)	0.057 (3)	0.100 (4)	0.025 (2)	−0.012 (2)	−0.012 (3)
C7	0.080 (3)	0.048 (3)	0.102 (4)	0.028 (2)	0.000 (3)	−0.014 (2)
C8	0.081 (3)	0.060 (3)	0.081 (3)	0.047 (3)	0.010 (3)	0.001 (2)
C9	0.055 (2)	0.056 (2)	0.054 (2)	0.033 (2)	0.0063 (18)	0.0038 (18)

Geometric parameters (Å, º) top

S1—C2	1.743 (4)	N4—H4B	0.8600
S1—C1	1.804 (5)	C1—H1A	0.9600
O1W—O1Wⁱ	0.88 (3)	C1—H1B	0.9600
O1W—O1Wⁱⁱ	0.88 (3)	C1—H1C	0.9600
O1W—O1Wⁱⁱⁱ	1.28 (4)	C3—C4	1.470 (5)
O1W—O1W^iv	1.28 (4)	C4—C5	1.378 (5)
O1W—O1W^v	1.55 (4)	C4—C9	1.388 (5)
O1W—H1W	0.8501	C5—C6	1.379 (6)
O1W—H2W	0.8500	C5—H5	0.9300
N1—C2	1.302 (5)	C6—C7	1.365 (7)
N1—N2	1.395 (5)	C6—H6	0.9300
N2—C3	1.305 (5)	C7—C8	1.375 (7)
N3—C2	1.352 (5)	C7—H7	0.9300
N3—C3	1.364 (4)	C8—C9	1.377 (6)
N3—N4	1.406 (4)	C8—H8	0.9300
N4—H4A	0.8601	C9—H9	0.9300

C2—S1—C1	98.7 (2)	S1—C1—H1C	109.5
O1Wⁱ—O1W—O1Wⁱⁱ	93 (4)	H1A—C1—H1C	109.5
O1Wⁱ—O1W—O1Wⁱⁱⁱ	89.994 (4)	H1B—C1—H1C	109.5
O1Wⁱⁱ—O1W—O1W^iv	89.995 (9)	N1—C2—N3	110.8 (3)
O1Wⁱⁱⁱ—O1W—O1W^iv	60.000 (8)	N1—C2—S1	128.0 (3)
O1Wⁱ—O1W—O1W^v	55.4 (9)	N3—C2—S1	121.2 (3)
O1Wⁱⁱ—O1W—O1W^v	55.4 (9)	N2—C3—N3	109.2 (3)
O1Wⁱ—O1W—H1W	85.0	N2—C3—C4	124.7 (3)
O1Wⁱⁱ—O1W—H1W	85.0	N3—C3—C4	126.1 (3)
O1W^v—O1W—H1W	48.2	C5—C4—C9	119.5 (4)
O1Wⁱ—O1W—H2W	67.8	C5—C4—C3	121.8 (3)
O1Wⁱⁱ—O1W—H2W	108.1	C9—C4—C3	118.6 (3)
O1Wⁱⁱⁱ—O1W—H2W	144.8	C4—C5—C6	119.9 (4)
O1W^iv—O1W—H2W	110.0	C4—C5—H5	120.0
O1W^v—O1W—H2W	117.3	C6—C5—H5	120.0
H1W—O1W—H2W	149.9	C7—C6—C5	120.4 (4)
C2—N1—N2	106.3 (3)	C7—C6—H6	119.8
C3—N2—N1	108.1 (3)	C5—C6—H6	119.8
C2—N3—C3	105.6 (3)	C6—C7—C8	120.1 (4)
C2—N3—N4	122.3 (3)	C6—C7—H7	119.9
C3—N3—N4	132.0 (3)	C8—C7—H7	119.9
N3—N4—H4A	106.6	C7—C8—C9	120.1 (4)
N3—N4—H4B	104.5	C7—C8—H8	120.0
H4A—N4—H4B	111.3	C9—C8—H8	120.0
S1—C1—H1A	109.5	C8—C9—C4	119.9 (4)
S1—C1—H1B	109.5	C8—C9—H9	120.1
H1A—C1—H1B	109.5	C4—C9—H9	120.1

C2—N1—N2—C3	0.4 (4)	N4—N3—C3—C4	1.5 (6)
N2—N1—C2—N3	−0.6 (4)	N2—C3—C4—C5	−135.3 (4)
N2—N1—C2—S1	−179.7 (3)	N3—C3—C4—C5	45.9 (5)
C3—N3—C2—N1	0.6 (4)	N2—C3—C4—C9	41.9 (5)
N4—N3—C2—N1	178.1 (3)	N3—C3—C4—C9	−137.0 (4)
C3—N3—C2—S1	179.7 (2)	C9—C4—C5—C6	−0.7 (6)
N4—N3—C2—S1	−2.7 (5)	C3—C4—C5—C6	176.4 (4)
C1—S1—C2—N1	11.9 (4)	C4—C5—C6—C7	−0.2 (7)
C1—S1—C2—N3	−167.1 (3)	C5—C6—C7—C8	0.6 (8)
N1—N2—C3—N3	−0.1 (4)	C6—C7—C8—C9	−0.1 (8)
N1—N2—C3—C4	−179.1 (3)	C7—C8—C9—C4	−0.8 (7)
C2—N3—C3—N2	−0.3 (4)	C5—C4—C9—C8	1.2 (6)
N4—N3—C3—N2	−177.5 (3)	C3—C4—C9—C8	−176.0 (4)
C2—N3—C3—C4	178.7 (3)

Symmetry codes: (i) y+1/3, −x+y+2/3, −z+2/3; (ii) x−y+1/3, x−1/3, −z+2/3; (iii) −y+1, x−y, z; (iv) −x+y+1, −x+1, z; (v) −x+4/3, −y+2/3, −z+2/3.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N1^vi	0.86	2.30	3.127 (4)	162
N4—H4B···N2^vii	0.86	2.21	3.060 (4)	172
C5—H5···N1^vi	0.93	2.60	3.507 (6)	167

Symmetry codes: (vi) y, −x+y+1, −z+1; (vii) −y+5/3, x−y+1/3, z+1/3.

Experimental details

Crystal data
Chemical formula	6C₉H₁₀N₄S·H₂O
M_r	1255.73
Crystal system, space group	Hexagonal, R3
Temperature (K)	298
a, c (Å)	23.0266 (15), 10.5190 (9)
V (Å³)	4830.2 (6)
Z	3
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
Crystal size (mm)	0.32 × 0.23 × 0.15

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.918, 0.960
No. of measured, independent and observed [I > 2σ(I)] reflections	8946, 2011, 1647
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.605

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.073, 0.204, 0.99
No. of reflections	2011
No. of parameters	137
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.1049P)² + 19.9182P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.70, −0.27

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 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—H4A···N1ⁱ	0.86	2.30	3.127 (4)	162.4
N4—H4B···N2ⁱⁱ	0.86	2.21	3.060 (4)	171.6
C5—H5···N1ⁱ	0.93	2.60	3.507 (6)	166.6

Symmetry codes: (i) y, −x+y+1, −z+1; (ii) −y+5/3, x−y+1/3, z+1/3.

Acknowledgements

The authors thank the Opening Foundation of Zhejiang Provincial Top-Key Pharmaceutical Discipline (grant Nos. 20050603, 20050610 and 20080602) for financial support.

References

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