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

Wang, Y.; Wan, R.; Han, F.; Wang, P.

doi:10.1107/S1600536809019333

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1425

doi:10.1107/S1600536809019333

Open

access

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

Yao Wang,^a Rong Wan,^a ^* Feng Han ^a and Peng Wang ^a

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

(Received 14 May 2009; accepted 21 May 2009; online 29 May 2009)

The title compound, C₈H₆FN₃S, was synthesized by the reaction of 3-fluorobenzoic acid and thiosemicarbazide. The dihedral angle between the planes of the thiadiazole and benzene rings is 37.3 (2)°. In the structure, two crystallographically independent molecules form a centrosymmetric dimer, in which two intermolecular N—H⋯N hydrogen bonds generate an R₂²(8) motif.

Related literature

For the biological activity of 1,3,4-thiadiazole derivatives, see: Nakagawa et al. (1996 ); Wang et al. (1999 ). For a similar structure, see: Wan et al. (2006 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₈H₆FN₃S
M_r = 195.23
Monoclinic, P 2₁ /c
a = 11.345 (2) Å
b = 7.3130 (15) Å
c = 11.269 (2) Å
β = 111.64 (3)°
V = 869.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 293 K
0.20 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.935, T_max = 0.967
1667 measured reflections
1584 independent reflections
1177 reflections with I > 2σ(I)
R_int = 0.021
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.124
S = 1.01
1584 reflections
118 parameters
13 restraints
H-atom parameters constrained
Δρ_max = 0.37 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
N3—H3A⋯N2ⁱ	0.86	2.14	2.981 (5)	165
Symmetry code: (i) -x+2, -y+1, -z+1.

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; 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/S1600536809019333/at2787sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809019333/at2787Isup2.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). 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 have published the structure of 5-(4-fluoro-phenyl)-[1,3,4]thiadiazol-2-ylamine (Wan et al., 2006). Here we report the crystal structure, (I).

In the title molecule (I), (Fig. 1), the dihedral angle between the thiadiazole and benzene ring is 37.3 (2)°, which is bigger than the angle in the structure of 5-(4-fluoro-phenyl)-[1,3,4]thiadiazol-2-ylamine (Wan et al., 2006), which is 30.1 (2)°. In the structure, two crystallographically independent molecules form a dimer structure, in which two intermolecular N—H···N hydrogen bonds generate a motif R₂²(8) (Fig. 2).

Related literature top

For general background, see: Nakagawa et al. (1996); Wang et al. (1999). For a similar structure, see: Wan et al. (2006). For bond-length data, see: Allen et al. (1987).

Experimental top

3-Fluoro-benzoic acid (2 mmol) and thiosemicarbazide (5 mmol) were mixed in a 25 ml flask, and kept in the oil bath at 363 K for 6 h. After cooling, the crude product (I) precipitated and was filted. Pure compound (I) was obtained by crystallization from ethanol (20 ml). Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of an acetone solution.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (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. A view of a dimer structure, in which two intermolecular N—H···N hydrogen bonds generate a motif R₂²(8).

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

Crystal data top

C₈H₆FN₃S	F(000) = 400
M_r = 195.23	D_x = 1.492 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 515 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 11.345 (2) Å	Cell parameters from 25 reflections
b = 7.3130 (15) Å	θ = 10–13°
c = 11.269 (2) Å	µ = 0.34 mm⁻¹
β = 111.64 (3)°	T = 293 K
V = 869.0 (3) Å³	Block, colourless
Z = 4	0.20 × 0.10 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1177 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.021
Graphite monochromator	θ_max = 25.3°, θ_min = 1.9°
ω/2θ scans	h = −13→0
Absorption correction: ψ scan (North et al., 1968)	k = 0→8
T_min = 0.935, T_max = 0.967	l = −12→13
1667 measured reflections	3 standard reflections every 200 reflections
1584 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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.124	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.06P)²] where P = (F_o² + 2F_c²)/3
1584 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.37 e Å⁻³
13 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₈H₆FN₃S	V = 869.0 (3) Å³
M_r = 195.23	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.345 (2) Å	µ = 0.34 mm⁻¹
b = 7.3130 (15) Å	T = 293 K
c = 11.269 (2) Å	0.20 × 0.10 × 0.10 mm
β = 111.64 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1177 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.021
T_min = 0.935, T_max = 0.967	3 standard reflections every 200 reflections
1667 measured reflections	intensity decay: 1%
1584 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	13 restraints
wR(F²) = 0.124	H-atom parameters constrained
S = 1.01	Δρ_max = 0.37 e Å⁻³
1584 reflections	Δρ_min = −0.25 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	0.82144 (7)	0.08639 (11)	0.55908 (6)	0.0548 (3)
F	0.5162 (3)	−0.2428 (3)	0.0198 (2)	0.1125 (9)
N1	0.8658 (2)	0.1443 (3)	0.3566 (2)	0.0523 (6)
C1	0.7322 (3)	−0.2918 (5)	0.3984 (3)	0.0713 (9)
H1B	0.7804	−0.3036	0.4850	0.086*
N2	0.9262 (2)	0.2841 (3)	0.4381 (2)	0.0551 (6)
C2	0.6592 (4)	−0.4354 (5)	0.3322 (4)	0.0817 (11)
H2B	0.6585	−0.5443	0.3746	0.098*
N3	0.9606 (3)	0.3931 (4)	0.6429 (2)	0.0733 (9)
H3A	1.0043	0.4846	0.6340	0.088*
H3B	0.9481	0.3787	0.7131	0.088*
C3	0.5871 (4)	−0.4202 (5)	0.2040 (4)	0.0822 (12)
H3C	0.5378	−0.5175	0.1592	0.099*
C4	0.5898 (3)	−0.2597 (6)	0.1447 (3)	0.0741 (10)
C5	0.6637 (3)	−0.1132 (4)	0.2071 (3)	0.0639 (9)
H5A	0.6658	−0.0066	0.1628	0.077*
C6	0.7338 (3)	−0.1272 (4)	0.3350 (3)	0.0516 (7)
C7	0.8082 (3)	0.0307 (4)	0.4039 (2)	0.0475 (7)
C8	0.9121 (3)	0.2733 (4)	0.5476 (2)	0.0499 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S	0.0686 (5)	0.0626 (5)	0.0402 (4)	−0.0130 (4)	0.0282 (3)	0.0002 (3)
F	0.1200 (19)	0.122 (2)	0.0888 (16)	−0.0253 (16)	0.0307 (14)	−0.0193 (15)
N1	0.0646 (15)	0.0583 (14)	0.0421 (12)	−0.0113 (12)	0.0293 (11)	−0.0079 (11)
C1	0.070 (2)	0.068 (2)	0.073 (2)	−0.0121 (18)	0.0235 (17)	0.0023 (18)
N2	0.0753 (16)	0.0580 (15)	0.0433 (12)	−0.0172 (13)	0.0353 (12)	−0.0097 (11)
C2	0.074 (2)	0.060 (2)	0.112 (3)	−0.0081 (19)	0.035 (2)	0.001 (2)
N3	0.110 (2)	0.0800 (19)	0.0452 (14)	−0.0379 (17)	0.0462 (15)	−0.0191 (13)
C3	0.074 (2)	0.079 (3)	0.104 (3)	−0.020 (2)	0.045 (2)	−0.040 (2)
C4	0.075 (2)	0.091 (3)	0.062 (2)	−0.024 (2)	0.0319 (18)	−0.0344 (19)
C5	0.075 (2)	0.068 (2)	0.0514 (17)	−0.0144 (17)	0.0271 (16)	−0.0140 (16)
C6	0.0557 (17)	0.0533 (17)	0.0519 (16)	0.0000 (13)	0.0270 (14)	−0.0051 (13)
C7	0.0541 (16)	0.0513 (16)	0.0421 (14)	0.0000 (13)	0.0236 (13)	−0.0013 (12)
C8	0.0634 (18)	0.0556 (17)	0.0374 (13)	−0.0068 (14)	0.0265 (13)	−0.0025 (13)

Geometric parameters (Å, º) top

S—C8	1.744 (3)	C2—H2B	0.9300
S—C7	1.747 (3)	N3—C8	1.338 (3)
F—C4	1.351 (4)	N3—H3A	0.8600
N1—C7	1.288 (3)	N3—H3B	0.8600
N1—N2	1.377 (3)	C3—C4	1.357 (5)
C1—C2	1.375 (5)	C3—H3C	0.9300
C1—C6	1.403 (4)	C4—C5	1.382 (4)
C1—H1B	0.9300	C5—C6	1.369 (4)
N2—C8	1.303 (3)	C5—H5A	0.9300
C2—C3	1.378 (5)	C6—C7	1.472 (4)

C8—S—C7	86.76 (13)	F—C4—C3	118.3 (3)
C7—N1—N2	114.0 (2)	F—C4—C5	119.0 (4)
C2—C1—C6	119.8 (3)	C3—C4—C5	122.7 (3)
C2—C1—H1B	120.1	C6—C5—C4	119.0 (3)
C6—C1—H1B	120.1	C6—C5—H5A	120.5
C8—N2—N1	112.5 (2)	C4—C5—H5A	120.5
C1—C2—C3	120.9 (4)	C5—C6—C1	119.3 (3)
C1—C2—H2B	119.6	C5—C6—C7	119.6 (3)
C3—C2—H2B	119.6	C1—C6—C7	121.1 (3)
C8—N3—H3A	120.0	N1—C7—C6	124.6 (2)
C8—N3—H3B	120.0	N1—C7—S	113.2 (2)
H3A—N3—H3B	120.0	C6—C7—S	122.1 (2)
C4—C3—C2	118.3 (3)	N2—C8—N3	124.3 (3)
C4—C3—H3C	120.9	N2—C8—S	113.5 (2)
C2—C3—H3C	120.9	N3—C8—S	122.19 (19)

C7—N1—N2—C8	−0.2 (4)	N2—N1—C7—S	0.5 (3)
C6—C1—C2—C3	−0.1 (5)	C5—C6—C7—N1	−36.0 (4)
C1—C2—C3—C4	−0.1 (6)	C1—C6—C7—N1	144.6 (3)
C2—C3—C4—F	−178.1 (3)	C5—C6—C7—S	141.4 (3)
C2—C3—C4—C5	1.3 (6)	C1—C6—C7—S	−37.9 (4)
F—C4—C5—C6	177.0 (3)	C8—S—C7—N1	−0.4 (2)
C3—C4—C5—C6	−2.4 (5)	C8—S—C7—C6	−178.2 (2)
C4—C5—C6—C1	2.2 (5)	N1—N2—C8—N3	−179.5 (3)
C4—C5—C6—C7	−177.2 (3)	N1—N2—C8—S	−0.1 (3)
C2—C1—C6—C5	−1.0 (5)	C7—S—C8—N2	0.3 (2)
C2—C1—C6—C7	178.4 (3)	C7—S—C8—N3	179.7 (3)
N2—N1—C7—C6	178.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N2ⁱ	0.86	2.14	2.981 (5)	165

Symmetry code: (i) −x+2, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₈H₆FN₃S
M_r	195.23
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.345 (2), 7.3130 (15), 11.269 (2)
β (°)	111.64 (3)
V (Å³)	869.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.935, 0.967
No. of measured, independent and observed [I > 2σ(I)] reflections	1667, 1584, 1177
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.124, 1.01
No. of reflections	1584
No. of parameters	118
No. of restraints	13
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.25

Computer programs: CAD-4 Software (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	0.8600	2.1400	2.981 (5)	165.00

Symmetry code: (i) −x+2, −y+1, −z+1.

Acknowledgements

The authors gratefully acknowledge Professor Hua-Qin Wang of the Analysis Center, Nanjing University, for providing the Enraf–Nonius CAD-4 diffractometer for this research project.

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
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
Wan, R., Han, F., Wu, F., Zhang, J.-J. & Wang, J.-T. (2006). Acta Cryst. E62, o5547–o5548. Web of Science CSD 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