5-(4-Meth­ylphenyl)-1,3,4-thia­diazol-2-amine

Guan, J.-N.; Wan, R.; Wang, Y.; Han, F.; Xu, C.-Z.

doi:10.1107/S1600536809012434

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o976

doi:10.1107/S1600536809012434

Open

access

5-(4-Methylphenyl)-1,3,4-thiadiazol-2-amine

Jian-Ning Guan,^a Rong Wan,^a ^* Yao Wang,^a Feng Han ^a and Cheng-Zhen Xu ^a

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, No.5 Xinmofan Road, Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: rwan@njut.edu.cn

(Received 31 March 2009; accepted 2 April 2009; online 8 April 2009)

The title compound, C₉H₉N₃S, was synthesized by the reaction of 4-methyl-benzoic acid and thiosemicarbazide. The thiadiazol ring adopts a planar conformation and makes a dihedral angle of 31.19 (18)° with the phenyl ring. In the crystal, molecules are linked by N—H⋯N hydrogen bonds.

Related literature

For applications of thiadiazole ligands, see: Nakagawa et al. (1996 ); Wang et al. (1999 ); Han et al. (2007 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₉H₉N₃S
M_r = 191.25
Monoclinic, P 2₁ /c
a = 12.284 (3) Å
b = 7.3730 (15) Å
c = 11.263 (2) Å
β = 109.09 (3)°
V = 964.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 293 K
0.30 × 0.10 × 0.10 mm

Data collection

Nonius CAD4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.918, T_max = 0.972
1963 measured reflections
1875 independent reflections
1351 reflections with I > 2σ(I)
R_int = 0.067
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.181
S = 1.01
1875 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N2ⁱ	0.86	2.13	2.970 (5)	166
N3—H3B⋯N1ⁱⁱ	0.86	2.18	3.025 (4)	166
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo,1995 ); 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 global, I. DOI: 10.1107/S1600536809012434/at2758sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809012434/at2758Isup2.hkl

checkCIF report

Comment top

1,3,4-Thiadiazole derivatives represent an interesting class of compounds possessing broad spectrum biological activities (Nakagawa et al., 1996; Wang et al., 1999). These compounds are known to exhibit diverse biological effects, such as insecticidal, fungicidal activities (Wang et al., 1999). We are focusing our synthetic and structural studies on thiadiazole derivatives and we have recently published the structure of 5-m-tolyl-[1,3,4]thiadiazol-2-ylamine (Han et al., 2007). We report here the crystal structure of the title compound, (I).

In (I) (Fig. 1), the bond lengths and angles are within normal ranges (Allen et al., 1987). The thiadiazole and the phenyl ring make a dihedral angle of 31.19 (18)°. The molecules link by N—H···N hydrogen bonds to stabilize the crystal structure (Fig. 2).

Related literature top

For applications of thiadiazole ligands, see: Nakagawa et al. (1996); Wang et al. (1999); Han et al. (2007). For bond-length data, see: Allen et al. (1987).

Experimental top

4-Methyl-benzoic acid (5 mmol) and thiosemicarbazide (5 mmol) were added in toluene (50 ml), which is heated under reflux for 4 h. The reaction mixture was left to cool to room temperature, poured into ice water, filtered, and the filter cake was crystallized from acetone to give pure compound (I). Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of an acetone solution.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo,1995); 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. A view of the molecular structure of (I). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. View of the N—H···N hydrogen bonds (dashed lines) in the unit cell. Dashed lines indicate hydrogen bonds.

5-(4-methylphenyl)-1,3,4-thiadiazol-2-amine top

Crystal data top

C₉H₉N₃S	F(000) = 400
M_r = 191.25	D_x = 1.318 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 476–478 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 12.284 (3) Å	Cell parameters from 25 reflections
b = 7.3730 (15) Å	θ = 9–13°
c = 11.263 (2) Å	µ = 0.29 mm⁻¹
β = 109.09 (3)°	T = 293 K
V = 964.0 (3) Å³	Block, colourless
Z = 4	0.30 × 0.10 × 0.10 mm

Data collection top

Nonius CAD4 diffractometer	1351 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.067
Graphite monochromator	θ_max = 26.0°, θ_min = 1.8°
ω/2θ scans	h = −15→0
Absorption correction: ψ scan (North et al., 1968)	k = 0→9
T_min = 0.918, T_max = 0.972	l = −13→13
1963 measured reflections	3 standard reflections every 200 reflections
1875 independent reflections	intensity decay: 1%

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.181	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.1P)² + 0.5P] where P = (F_o² + 2F_c²)/3
1875 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

C₉H₉N₃S	V = 964.0 (3) Å³
M_r = 191.25	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.284 (3) Å	µ = 0.29 mm⁻¹
b = 7.3730 (15) Å	T = 293 K
c = 11.263 (2) Å	0.30 × 0.10 × 0.10 mm
β = 109.09 (3)°

Data collection top

Nonius CAD4 diffractometer	1351 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.067
T_min = 0.918, T_max = 0.972	3 standard reflections every 200 reflections
1963 measured reflections	intensity decay: 1%
1875 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.181	H-atom parameters constrained
S = 1.01	Δρ_max = 0.26 e Å⁻³
1875 reflections	Δρ_min = −0.43 e Å⁻³
118 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
S	0.34151 (8)	0.08993 (12)	0.57346 (7)	0.0494 (3)
N1	0.3802 (2)	0.1397 (4)	0.3670 (2)	0.0477 (7)
N2	0.4336 (3)	0.2834 (4)	0.4424 (2)	0.0504 (8)
N3	0.4638 (3)	0.3988 (5)	0.6437 (3)	0.0662 (10)
H3A	0.5027	0.4894	0.6309	0.079*
H3B	0.4527	0.3872	0.7149	0.079*
C1	0.0739 (4)	−0.6083 (7)	0.1831 (5)	0.0932 (17)
H1B	0.0401	−0.5868	0.0945	0.140*
H1C	0.0143	−0.6328	0.2186	0.140*
H1D	0.1250	−0.7105	0.1966	0.140*
C2	0.1409 (3)	−0.4424 (6)	0.2453 (4)	0.0623 (11)
C3	0.1475 (3)	−0.2912 (6)	0.1764 (4)	0.0673 (11)
H3C	0.1101	−0.2917	0.0900	0.081*
C4	0.2085 (3)	−0.1380 (6)	0.2323 (3)	0.0583 (10)
H4A	0.2112	−0.0376	0.1834	0.070*
C5	0.2653 (3)	−0.1341 (5)	0.3606 (3)	0.0449 (8)
C6	0.2590 (3)	−0.2873 (5)	0.4300 (4)	0.0568 (9)
H6A	0.2967	−0.2886	0.5164	0.068*
C7	0.1975 (4)	−0.4375 (5)	0.3720 (4)	0.0640 (11)
H7A	0.1943	−0.5384	0.4203	0.077*
C8	0.3296 (3)	0.0279 (4)	0.4202 (3)	0.0414 (7)
C9	0.4208 (3)	0.2763 (5)	0.5533 (3)	0.0451 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S	0.0640 (6)	0.0540 (6)	0.0378 (5)	−0.0091 (4)	0.0267 (4)	0.0006 (4)
N1	0.0611 (17)	0.0532 (17)	0.0353 (14)	−0.0070 (14)	0.0249 (13)	−0.0057 (12)
N2	0.0683 (18)	0.0538 (18)	0.0387 (15)	−0.0117 (15)	0.0305 (14)	−0.0064 (13)
N3	0.097 (3)	0.070 (2)	0.0441 (17)	−0.0336 (19)	0.0401 (17)	−0.0159 (15)
C1	0.095 (3)	0.086 (4)	0.108 (4)	−0.041 (3)	0.046 (3)	−0.035 (3)
C2	0.063 (2)	0.058 (2)	0.076 (3)	−0.0128 (19)	0.037 (2)	−0.019 (2)
C3	0.072 (3)	0.080 (3)	0.053 (2)	−0.016 (2)	0.024 (2)	−0.015 (2)
C4	0.072 (2)	0.059 (2)	0.046 (2)	−0.011 (2)	0.0240 (18)	−0.0032 (17)
C5	0.0524 (19)	0.0435 (18)	0.0451 (18)	0.0001 (15)	0.0247 (16)	−0.0016 (14)
C6	0.064 (2)	0.051 (2)	0.055 (2)	−0.0024 (18)	0.0193 (18)	0.0026 (18)
C7	0.070 (2)	0.045 (2)	0.084 (3)	−0.0041 (19)	0.034 (2)	0.005 (2)
C8	0.0544 (19)	0.0384 (17)	0.0370 (16)	0.0016 (15)	0.0224 (15)	−0.0011 (13)
C9	0.0540 (19)	0.0482 (19)	0.0380 (17)	−0.0039 (16)	0.0218 (15)	0.0008 (14)

Geometric parameters (Å, º) top

S—C9	1.742 (3)	C2—C7	1.368 (6)
S—C8	1.745 (3)	C2—C3	1.376 (6)
N1—C8	1.292 (4)	C3—C4	1.387 (6)
N1—N2	1.382 (4)	C3—H3C	0.9300
N2—C9	1.309 (4)	C4—C5	1.385 (5)
N3—C9	1.335 (4)	C4—H4A	0.9300
N3—H3A	0.8600	C5—C6	1.390 (5)
N3—H3B	0.8600	C5—C8	1.468 (5)
C1—C2	1.512 (6)	C6—C7	1.380 (5)
C1—H1B	0.9600	C6—H6A	0.9300
C1—H1C	0.9600	C7—H7A	0.9300
C1—H1D	0.9600

C9—S—C8	86.96 (15)	C5—C4—C3	120.3 (4)
C8—N1—N2	114.0 (3)	C5—C4—H4A	119.9
C9—N2—N1	112.0 (3)	C3—C4—H4A	119.9
C9—N3—H3A	120.0	C4—C5—C6	117.9 (3)
C9—N3—H3B	120.0	C4—C5—C8	120.4 (3)
H3A—N3—H3B	120.0	C6—C5—C8	121.6 (3)
C2—C1—H1B	109.5	C7—C6—C5	120.6 (4)
C2—C1—H1C	109.5	C7—C6—H6A	119.7
H1B—C1—H1C	109.5	C5—C6—H6A	119.7
C2—C1—H1D	109.5	C2—C7—C6	121.9 (4)
H1B—C1—H1D	109.5	C2—C7—H7A	119.1
H1C—C1—H1D	109.5	C6—C7—H7A	119.1
C7—C2—C3	117.6 (4)	N1—C8—C5	125.2 (3)
C7—C2—C1	121.2 (4)	N1—C8—S	113.2 (2)
C3—C2—C1	121.2 (4)	C5—C8—S	121.6 (2)
C2—C3—C4	121.8 (4)	N2—C9—N3	124.1 (3)
C2—C3—H3C	119.1	N2—C9—S	113.8 (3)
C4—C3—H3C	119.1	N3—C9—S	122.2 (2)

C8—N1—N2—C9	−0.4 (4)	N2—N1—C8—S	0.5 (4)
C7—C2—C3—C4	−0.4 (6)	C4—C5—C8—N1	−30.4 (5)
C1—C2—C3—C4	179.9 (4)	C6—C5—C8—N1	149.7 (4)
C2—C3—C4—C5	0.3 (6)	C4—C5—C8—S	148.1 (3)
C3—C4—C5—C6	0.1 (6)	C6—C5—C8—S	−31.8 (4)
C3—C4—C5—C8	−179.8 (3)	C9—S—C8—N1	−0.3 (3)
C4—C5—C6—C7	−0.3 (5)	C9—S—C8—C5	−179.0 (3)
C8—C5—C6—C7	179.6 (3)	N1—N2—C9—N3	−179.9 (3)
C3—C2—C7—C6	0.2 (6)	N1—N2—C9—S	0.1 (4)
C1—C2—C7—C6	179.9 (4)	C8—S—C9—N2	0.1 (3)
C5—C6—C7—C2	0.2 (6)	C8—S—C9—N3	−179.9 (3)
N2—N1—C8—C5	179.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N2ⁱ	0.86	2.13	2.970 (5)	166
N3—H3B···N1ⁱⁱ	0.86	2.18	3.025 (4)	166

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

Experimental details

Crystal data
Chemical formula	C₉H₉N₃S
M_r	191.25
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	12.284 (3), 7.3730 (15), 11.263 (2)
β (°)	109.09 (3)
V (Å³)	964.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.30 × 0.10 × 0.10

Data collection
Diffractometer	Nonius CAD4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.918, 0.972
No. of measured, independent and observed [I > 2σ(I)] reflections	1963, 1875, 1351
R_int	0.067
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.181, 1.01
No. of reflections	1875
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.43

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo,1995), 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
N3—H3A···N2ⁱ	0.86	2.13	2.970 (5)	166
N3—H3B···N1ⁱⁱ	0.86	2.18	3.025 (4)	166

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

Acknowledgements

The authors thank Professor Hua-Qin Wang of the Analysis Centre, Nanjing University, for collecting the crystallographic data.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Han, F., Wan, R., Wu, W.-Y., Zhang, J.-J. & Wang, J.-T. (2007). Acta Cryst. E63, o717–o718. Web of Science CSD CrossRef IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Nakagawa, Y., Nishimura, K., Izumi, K., Kinoshita, K., Kimura, T. & Kurihara, N. (1996). J. Pestic. Sci. 21, 195-201. CrossRef CAS Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, Y. G., Cao, L., Yan, J., Ye, W. F., Zhou, Q. C. & Lu, B. X. (1999). Chem. J. Chin. Univ. 20, 1903–1905. CAS Google Scholar