5-(2,3,4,5,6-Penta­fluoro­phen­yl)-1,3,4-thia­diazol-2-amine

Wang, P.; Wan, R.; Zhang, J.; Yu, P.; He, Q.

doi:10.1107/S1600536810039723

organic compounds

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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o2765

https://doi.org/10.1107/S1600536810039723

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5-(2,3,4,5,6-Pentafluorophenyl)-1,3,4-thiadiazol-2-amine

Peng Wang,^a Rong Wan,^a ^* Jianqiang Zhang,^a Peng Yu ^a and Qiu He ^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 6 August 2010; accepted 5 October 2010; online 9 October 2010)

The title compound, C₈H₂F₅N₃S, was synthesized by the reaction of perfluorobenzoic acid and thiosemicarbazide. The dihedral angle between the thiadiazole and perfluorophenyl ring is 35.41 (6)°. In the crystal, intermolecular N—H⋯N hydrogen bonds link the molecules, forming a three-dimensional network.

Related literature

For the fungicidal and herbicidal activity of thiadiazole derivatives, see: Chen et al. (2000 ); Kidwai et al. (2000 ); Vicentini et al. (1998 ) and for their insecticidal activity, see: Arun et al. (1999 ); Wasfy et al. (1996 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₈H₂F₅N₃S
M_r = 267.19
Monoclinic, P 2₁ /c
a = 11.897 (2) Å
b = 7.0680 (14) Å
c = 11.553 (2) Å
β = 104.66 (3)°
V = 939.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.889, T_max = 0.961
3428 measured reflections
1709 independent reflections
1283 reflections with I > 2σ(I)
R_int = 0.064
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.128
S = 1.00
1709 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N2ⁱ	0.86	2.18	3.001 (4)	160
N1—H1B⋯N3ⁱⁱ	0.86	2.19	3.013 (3)	161
Symmetry codes: (i) -x+2, -y+1, -z; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); 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: https://doi.org/10.1107/S1600536810039723/er2081sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810039723/er2081Isup2.hkl

checkCIF report

Comment top

Thiadiazole derivatives containing the thiazolidinone unit are of great interest because of their chemical and pharmaceutical properties. Some derivatives have fungicidal and herbicidal activities (Chen et al., 2000; Kidwai et al., 2000; Vicentini et al., 1998); some show insecticidal activities (Arun et al., 1999; Wasfy et al., 1996).

We report here the crystal structure of the title compound,(I). The molecular structure of (I) is shown in Fig.1, in which the bond lengths (Allen et al., 1987) and angles are generally within normal ranges. Ring(C1/S/C2/N3/N2) is planar, and the mean deviation from plane is 0.0012 Angstroms. The dihedral angle between the thiadiazole and perfluorophenyl ring is 35.41 (6)°. In the crystal structure, intermolecular N—H···N hydrogen bonds (Table 1) link the molecules to form a three-dimensional network (Fig. 2), in which they may be effective in the stabilization of the structure.

Related literature top

For the fungicidal and herbicidal activity of thiadiazole derivatives, see: Chen et al. (2000); Kidwai et al. (2000); Vicentini et al. (1998) and for their insecticidal activity, see: Arun et al. (1999); Wasfy et al. (1996). For bond-length data, see: Allen et al. (1987).

Experimental top

Perfluorobenzoic 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) (m.p. 523–525 K). Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of an acetone solution.

Structure description top

For the fungicidal and herbicidal activity of thiadiazole derivatives, see: Chen et al. (2000); Kidwai et al. (2000); Vicentini et al. (1998) and for their insecticidal activity, see: Arun et al. (1999); Wasfy et al. (1996). For bond-length data, see: Allen et al. (1987).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); 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. Partial packing view showing the hydrogen-bonded network. Dashed lines indicate intermolecular N—H···N hydrogen bonds.

5-(2,3,4,5,6-Pentafluorophenyl)-1,3,4-thiadiazol-2-amine top

Crystal data top

C₈H₂F₅N₃S	F(000) = 528
M_r = 267.19	D_x = 1.888 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 523–525 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 11.897 (2) Å	Cell parameters from 25 reflections
b = 7.0680 (14) Å	θ = 9–13°
c = 11.553 (2) Å	µ = 0.40 mm⁻¹
β = 104.66 (3)°	T = 293 K
V = 939.8 (3) Å³	Block, colorless
Z = 4	0.30 × 0.20 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1283 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.064
Graphite monochromator	θ_max = 25.3°, θ_min = 1.8°
ω/2θ scans	h = −14→0
Absorption correction: ψ scan (North et al., 1968)	k = −8→8
T_min = 0.889, T_max = 0.961	l = −13→13
3428 measured reflections	3 standard reflections every 200 reflections
1709 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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.080P)²] where P = (F_o² + 2F_c²)/3
1709 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₈H₂F₅N₃S	V = 939.8 (3) Å³
M_r = 267.19	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.897 (2) Å	µ = 0.40 mm⁻¹
b = 7.0680 (14) Å	T = 293 K
c = 11.553 (2) Å	0.30 × 0.20 × 0.10 mm
β = 104.66 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1283 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.064
T_min = 0.889, T_max = 0.961	3 standard reflections every 200 reflections
3428 measured reflections	intensity decay: 1%
1709 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 1.00	Δρ_max = 0.27 e Å⁻³
1709 reflections	Δρ_min = −0.29 e Å⁻³
154 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	0.82940 (7)	0.06662 (10)	0.05893 (6)	0.0461 (3)
F1	0.78775 (15)	−0.3360 (2)	−0.00245 (14)	0.0569 (5)
C1	0.9155 (2)	0.2602 (4)	0.0479 (2)	0.0404 (6)
N1	0.9659 (2)	0.3683 (4)	0.1416 (2)	0.0524 (6)
H1A	1.0105	0.4601	0.1330	0.063*
H1B	0.9537	0.3459	0.2106	0.063*
C2	0.8165 (2)	0.0294 (4)	−0.0925 (2)	0.0389 (6)
F2	0.65099 (17)	−0.6042 (2)	−0.12921 (18)	0.0685 (6)
N2	0.9298 (2)	0.2855 (4)	−0.06011 (19)	0.0472 (6)
F3	0.53266 (17)	−0.5342 (3)	−0.35867 (18)	0.0747 (6)
N3	0.8725 (2)	0.1519 (3)	−0.13946 (19)	0.0451 (6)
C3	0.7437 (2)	−0.1198 (4)	−0.1630 (2)	0.0387 (6)
F4	0.55308 (16)	−0.1942 (3)	−0.45890 (14)	0.0689 (6)
C4	0.7312 (2)	−0.2972 (4)	−0.1154 (2)	0.0429 (6)
F5	0.68393 (17)	0.0780 (2)	−0.33282 (15)	0.0609 (5)
C5	0.6609 (3)	−0.4358 (4)	−0.1800 (3)	0.0489 (7)
C6	0.6009 (2)	−0.4016 (4)	−0.2954 (3)	0.0502 (7)
C7	0.6116 (2)	−0.2282 (4)	−0.3459 (2)	0.0482 (7)
C8	0.6812 (2)	−0.0900 (4)	−0.2800 (2)	0.0453 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S	0.0633 (5)	0.0429 (4)	0.0347 (4)	−0.0129 (3)	0.0171 (3)	−0.0005 (3)
F1	0.0665 (10)	0.0469 (10)	0.0521 (10)	−0.0049 (8)	0.0052 (8)	0.0130 (8)
C1	0.0472 (14)	0.0406 (15)	0.0352 (13)	−0.0044 (12)	0.0139 (12)	−0.0027 (11)
N1	0.0725 (16)	0.0530 (15)	0.0339 (12)	−0.0221 (13)	0.0176 (11)	−0.0081 (10)
C2	0.0477 (14)	0.0358 (14)	0.0354 (13)	−0.0023 (11)	0.0147 (12)	−0.0012 (11)
F2	0.0801 (13)	0.0418 (10)	0.0824 (14)	−0.0148 (9)	0.0184 (11)	0.0058 (9)
N2	0.0600 (14)	0.0494 (14)	0.0368 (12)	−0.0185 (11)	0.0206 (11)	−0.0092 (10)
F3	0.0815 (13)	0.0659 (13)	0.0740 (13)	−0.0330 (10)	0.0145 (11)	−0.0233 (10)
N3	0.0586 (14)	0.0442 (13)	0.0362 (12)	−0.0136 (11)	0.0191 (11)	−0.0087 (10)
C3	0.0450 (14)	0.0351 (14)	0.0378 (13)	−0.0027 (11)	0.0139 (11)	−0.0040 (11)
F4	0.0762 (12)	0.0821 (14)	0.0411 (9)	−0.0162 (11)	0.0012 (8)	−0.0056 (9)
C4	0.0458 (15)	0.0405 (15)	0.0426 (15)	−0.0010 (12)	0.0114 (12)	0.0025 (12)
F5	0.0840 (12)	0.0443 (10)	0.0477 (10)	−0.0082 (9)	0.0041 (9)	0.0086 (7)
C5	0.0553 (16)	0.0349 (15)	0.0603 (18)	−0.0060 (13)	0.0217 (14)	−0.0005 (13)
C6	0.0508 (16)	0.0486 (17)	0.0531 (17)	−0.0159 (14)	0.0165 (14)	−0.0172 (13)
C7	0.0492 (16)	0.0547 (18)	0.0406 (15)	−0.0051 (13)	0.0108 (13)	−0.0087 (13)
C8	0.0542 (16)	0.0404 (15)	0.0429 (15)	−0.0015 (12)	0.0155 (13)	−0.0008 (11)

Geometric parameters (Å, º) top

S—C1	1.733 (3)	N2—N3	1.372 (3)
S—C2	1.737 (3)	F3—C6	1.331 (3)
F1—C4	1.336 (3)	C3—C8	1.383 (4)
C1—N2	1.313 (3)	C3—C4	1.392 (4)
C1—N1	1.337 (3)	F4—C7	1.336 (3)
N1—H1A	0.8600	C4—C5	1.379 (4)
N1—H1B	0.8600	F5—C8	1.339 (3)
C2—N3	1.292 (3)	C5—C6	1.365 (5)
C2—C3	1.473 (4)	C6—C7	1.377 (4)
F2—C5	1.345 (3)	C7—C8	1.379 (4)

C1—S—C2	87.05 (12)	F1—C4—C5	118.0 (3)
N2—C1—N1	123.5 (2)	F1—C4—C3	119.5 (2)
N2—C1—S	113.5 (2)	C5—C4—C3	122.4 (3)
N1—C1—S	122.92 (19)	F2—C5—C6	120.1 (3)
C1—N1—H1A	120.0	F2—C5—C4	120.0 (3)
C1—N1—H1B	120.0	C6—C5—C4	119.9 (3)
H1A—N1—H1B	120.0	F3—C6—C5	120.5 (3)
N3—C2—C3	122.8 (2)	F3—C6—C7	120.2 (3)
N3—C2—S	113.4 (2)	C5—C6—C7	119.3 (2)
C3—C2—S	123.72 (19)	F4—C7—C6	119.5 (2)
C1—N2—N3	112.3 (2)	F4—C7—C8	120.3 (3)
C2—N3—N2	113.8 (2)	C6—C7—C8	120.2 (3)
C8—C3—C4	116.0 (2)	F5—C8—C7	117.2 (2)
C8—C3—C2	121.8 (2)	F5—C8—C3	120.8 (2)
C4—C3—C2	122.2 (2)	C7—C8—C3	122.1 (3)

C2—S—C1—N2	−0.2 (2)	F1—C4—C5—C6	179.5 (3)
C2—S—C1—N1	−177.7 (3)	C3—C4—C5—C6	0.3 (4)
C1—S—C2—N3	0.2 (2)	F2—C5—C6—F3	−0.4 (4)
C1—S—C2—C3	−176.3 (2)	C4—C5—C6—F3	−179.9 (3)
N1—C1—N2—N3	177.7 (3)	F2—C5—C6—C7	179.7 (2)
S—C1—N2—N3	0.2 (3)	C4—C5—C6—C7	0.2 (4)
C3—C2—N3—N2	176.4 (2)	F3—C6—C7—F4	0.0 (4)
S—C2—N3—N2	−0.2 (3)	C5—C6—C7—F4	179.9 (3)
C1—N2—N3—C2	0.0 (4)	F3—C6—C7—C8	179.3 (3)
N3—C2—C3—C8	−34.3 (4)	C5—C6—C7—C8	−0.8 (4)
S—C2—C3—C8	141.9 (2)	F4—C7—C8—F5	2.1 (4)
N3—C2—C3—C4	147.3 (3)	C6—C7—C8—F5	−177.2 (3)
S—C2—C3—C4	−36.4 (4)	F4—C7—C8—C3	−179.6 (2)
C8—C3—C4—F1	−179.2 (2)	C6—C7—C8—C3	1.1 (4)
C2—C3—C4—F1	−0.8 (4)	C4—C3—C8—F5	177.6 (2)
C8—C3—C4—C5	0.0 (4)	C2—C3—C8—F5	−0.8 (4)
C2—C3—C4—C5	178.4 (3)	C4—C3—C8—C7	−0.6 (4)
F1—C4—C5—F2	−0.1 (4)	C2—C3—C8—C7	−179.1 (3)
C3—C4—C5—F2	−179.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2ⁱ	0.86	2.18	3.001 (4)	160
N1—H1B···N3ⁱⁱ	0.86	2.19	3.013 (3)	161

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

Experimental details

Crystal data
Chemical formula	C₈H₂F₅N₃S
M_r	267.19
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.897 (2), 7.0680 (14), 11.553 (2)
β (°)	104.66 (3)
V (Å³)	939.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.40
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.889, 0.961
No. of measured, independent and observed [I > 2σ(I)] reflections	3428, 1709, 1283
R_int	0.064
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.128, 1.00
No. of reflections	1709
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.29

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), 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
N1—H1A···N2ⁱ	0.86	2.18	3.001 (4)	160
N1—H1B···N3ⁱⁱ	0.86	2.19	3.013 (3)	161

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

Acknowledgements

The authors would like to thank Professor Hua-qin Wang of the Analysis Centre, Nanjing University, for carrying out the X-ray crystallographic analysis.

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. CSD CrossRef Web of Science Google Scholar
Arun, K. P., Nag, V. L. & Panda, C. S. (1999). Indian J. Chem. Sect. B, 38, 998–1001. Google Scholar
Chen, H. S., Li, Z. M. & Han, Y. F. (2000). J. Agric. Food Chem. 48, 5312–5315. Web of Science CrossRef PubMed CAS Google Scholar
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Kidwai, M., Negi, N. & Misra, P. (2000). J. Indian Chem. Soc. 77, 46–48. 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
Vicentini, C. B., Manfrini, M., Veronese, A. C. & Guarneri, M. (1998). J. Heterocycl. Chem. 35, 29–36. CrossRef CAS Google Scholar
Wasfy, A. A., Nassar, S. A. & Eissa, A. M. (1996). Indian J. Chem. Sect B, 35, 1218–1220. Google Scholar