5-(2-Fluoro-4-nitro­phen­yl)-1,3,4-thia­diazole-2-amine

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

doi:10.1107/S1600536809016614

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1250

doi:10.1107/S1600536809016614

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5-(2-Fluoro-4-nitrophenyl)-1,3,4-thiadiazole-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, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: rwan@njut.edu.cn

(Received 30 April 2009; accepted 4 May 2009; online 14 May 2009)

The title compound, C₈H₅FN₄O₂S, was synthesized by the reaction of 2-fluoro-4-nitrobenzoic acid and thiosemicarbazide. The dihedral angle between the thiadiazole and benzene rings is 27.1 (2)°. In the crystal, intermolecular N—H⋯N and C—H⋯O hydrogen bonds link the molecules.

Related literature

For general background to the biological activity of 1,3,4-thiadiazole derivatives, see: Nakagawa et al. (1996 ); Wang et al. (1999 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₈H₅FN₄O₂S
M_r = 240.22
Monoclinic, P 2₁ /c
a = 9.1780 (18) Å
b = 9.3720 (19) Å
c = 11.413 (2) Å
β = 102.55 (3)°
V = 958.2 (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
1832 measured reflections
1720 independent reflections
1301 reflections with I > 2σ(I)
R_int = 0.047
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.194
S = 1.01
1720 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯N3ⁱ	0.86	2.16	3.000 (5)	167
C3—H3B⋯O1ⁱⁱ	0.93	2.54	3.182 (7)	126
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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/S1600536809016614/at2775sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809016614/at2775Isup2.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).

The structure of the title compound, (I), is shown in Fig. 1, in which the bond lengths and angles are generally within normal ranges (Allen et al., 1987). The dihedral angle between the thiadiazole and benzene ring is 27.1 (2)°. There are intermolecular N—H···N and C—H···O hydrogen bonds, linking the molecules, forming chains along the b axis (Fig. 2),.

Related literature top

For general background to the biological activity of 1,3,4-thiadiazole derivatives, see: Nakagawa et al. (1996); Wang et al. (1999). For bond-length data, see: Allen et al. (1987).

Experimental top

2-Fluoro-4-nitrobenzoic 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. Partial packing view showing the hydrogen-bonded network. Dashed lines indicate intermolecular N—H···N and C—H···O hydrogen bonds.

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

Crystal data top

C₈H₅FN₄O₂S	F(000) = 488
M_r = 240.22	D_x = 1.665 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 476 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 9.1780 (18) Å	Cell parameters from 25 reflections
b = 9.3720 (19) Å	θ = 9–12°
c = 11.413 (2) Å	µ = 0.34 mm⁻¹
β = 102.55 (3)°	T = 293 K
V = 958.2 (3) Å³	Block, colourless
Z = 4	0.20 × 0.10 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1301 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.047
Graphite monochromator	θ_max = 25.2°, θ_min = 2.3°
ω/2θ scans	h = 0→11
Absorption correction: ψ scan (North et al., 1968)	k = 0→11
T_min = 0.935, T_max = 0.967	l = −13→13
1832 measured reflections	3 standard reflections every 200 reflections
1720 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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.194	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.1P)² + 2.P] where P = (F_o² + 2F_c²)/3
1720 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.47 e Å⁻³

Crystal data top

C₈H₅FN₄O₂S	V = 958.2 (3) Å³
M_r = 240.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.1780 (18) Å	µ = 0.34 mm⁻¹
b = 9.3720 (19) Å	T = 293 K
c = 11.413 (2) Å	0.20 × 0.10 × 0.10 mm
β = 102.55 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1301 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.047
T_min = 0.935, T_max = 0.967	3 standard reflections every 200 reflections
1832 measured reflections	intensity decay: 1%
1720 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.194	H-atom parameters constrained
S = 1.01	Δρ_max = 0.43 e Å⁻³
1720 reflections	Δρ_min = −0.47 e Å⁻³
145 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	0.65883 (14)	0.15613 (12)	0.66472 (10)	0.0442 (4)
F	0.6863 (3)	−0.1515 (3)	0.6466 (2)	0.0539 (8)
N1	0.9259 (5)	−0.4021 (5)	0.3718 (4)	0.0537 (11)
C1	0.8706 (5)	−0.2697 (4)	0.4162 (4)	0.0404 (10)
O1	1.0171 (6)	−0.3935 (5)	0.3093 (4)	0.0892 (15)
O2	0.8765 (4)	−0.5153 (4)	0.4009 (4)	0.0656 (11)
N2	0.6452 (5)	0.2128 (4)	0.4420 (3)	0.0449 (9)
C2	0.8888 (5)	−0.1427 (5)	0.3565 (4)	0.0448 (11)
H2B	0.9387	−0.1415	0.2938	0.054*
N3	0.5854 (5)	0.3311 (4)	0.4867 (3)	0.0475 (10)
C3	0.8298 (5)	−0.0180 (5)	0.3938 (4)	0.0412 (10)
H3B	0.8386	0.0674	0.3544	0.049*
N4	0.5320 (5)	0.4162 (4)	0.6663 (3)	0.0535 (11)
H4A	0.4951	0.4943	0.6329	0.064*
H4B	0.5347	0.4016	0.7412	0.064*
C4	0.7568 (5)	−0.0197 (4)	0.4903 (4)	0.0358 (10)
C5	0.7505 (5)	−0.1484 (5)	0.5495 (4)	0.0388 (10)
C6	0.8026 (5)	−0.2754 (5)	0.5131 (4)	0.0421 (10)
H6A	0.7925	−0.3609	0.5519	0.050*
C7	0.6885 (5)	0.1134 (4)	0.5224 (4)	0.0367 (10)
C8	0.5851 (5)	0.3175 (4)	0.6019 (4)	0.0378 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S	0.0663 (8)	0.0343 (6)	0.0343 (6)	0.0124 (5)	0.0166 (5)	0.0053 (4)
F	0.0753 (19)	0.0440 (16)	0.0517 (16)	0.0078 (13)	0.0340 (14)	0.0074 (12)
N1	0.069 (3)	0.038 (2)	0.054 (2)	0.013 (2)	0.012 (2)	−0.0076 (19)
C1	0.047 (2)	0.031 (2)	0.042 (2)	0.0064 (19)	0.0066 (19)	−0.0057 (19)
O1	0.125 (4)	0.067 (3)	0.096 (3)	0.032 (3)	0.068 (3)	−0.003 (2)
O2	0.075 (3)	0.041 (2)	0.075 (3)	0.0038 (18)	0.003 (2)	−0.0161 (19)
N2	0.068 (3)	0.0328 (19)	0.0379 (19)	0.0120 (18)	0.0200 (18)	0.0030 (16)
C2	0.053 (3)	0.040 (3)	0.045 (2)	0.006 (2)	0.019 (2)	−0.005 (2)
N3	0.073 (3)	0.0292 (19)	0.045 (2)	0.0150 (18)	0.0237 (19)	0.0044 (16)
C3	0.055 (3)	0.032 (2)	0.038 (2)	0.0018 (19)	0.014 (2)	0.0020 (18)
N4	0.084 (3)	0.040 (2)	0.039 (2)	0.020 (2)	0.018 (2)	0.0030 (17)
C4	0.040 (2)	0.032 (2)	0.034 (2)	0.0034 (18)	0.0068 (18)	−0.0020 (17)
C5	0.043 (2)	0.037 (2)	0.038 (2)	0.0015 (19)	0.0131 (18)	−0.0014 (18)
C6	0.056 (3)	0.030 (2)	0.041 (2)	0.003 (2)	0.012 (2)	0.0016 (18)
C7	0.042 (2)	0.031 (2)	0.038 (2)	0.0026 (18)	0.0120 (19)	0.0016 (18)
C8	0.048 (2)	0.032 (2)	0.035 (2)	0.0058 (18)	0.0101 (19)	0.0053 (17)

Geometric parameters (Å, º) top

S—C8	1.746 (4)	C2—H2B	0.9300
S—C7	1.750 (4)	N3—C8	1.321 (6)
F—C5	1.363 (5)	C3—C4	1.409 (6)
N1—O1	1.214 (6)	C3—H3B	0.9300
N1—O2	1.227 (5)	N4—C8	1.338 (6)
N1—C1	1.472 (6)	N4—H4A	0.8600
C1—C6	1.384 (6)	N4—H4B	0.8600
C1—C2	1.400 (6)	C4—C5	1.389 (6)
N2—C7	1.308 (5)	C4—C7	1.478 (6)
N2—N3	1.382 (5)	C5—C6	1.381 (6)
C2—C3	1.392 (6)	C6—H6A	0.9300

C8—S—C7	86.65 (19)	H4A—N4—H4B	120.0
O1—N1—O2	124.0 (4)	C5—C4—C3	117.9 (4)
O1—N1—C1	118.6 (4)	C5—C4—C7	123.2 (4)
O2—N1—C1	117.4 (4)	C3—C4—C7	118.9 (4)
C6—C1—C2	123.0 (4)	F—C5—C6	117.7 (4)
C6—C1—N1	119.4 (4)	F—C5—C4	119.0 (4)
C2—C1—N1	117.6 (4)	C6—C5—C4	123.3 (4)
C7—N2—N3	113.4 (3)	C5—C6—C1	116.9 (4)
C3—C2—C1	118.0 (4)	C5—C6—H6A	121.5
C3—C2—H2B	121.0	C1—C6—H6A	121.5
C1—C2—H2B	121.0	N2—C7—C4	120.6 (4)
C8—N3—N2	112.1 (3)	N2—C7—S	113.8 (3)
C2—C3—C4	120.8 (4)	C4—C7—S	125.7 (3)
C2—C3—H3B	119.6	N3—C8—N4	124.0 (4)
C4—C3—H3B	119.6	N3—C8—S	114.1 (3)
C8—N4—H4A	120.0	N4—C8—S	121.9 (3)
C8—N4—H4B	120.0

O1—N1—C1—C6	−161.4 (5)	C4—C5—C6—C1	3.3 (7)
O2—N1—C1—C6	18.5 (6)	C2—C1—C6—C5	0.5 (7)
O1—N1—C1—C2	19.2 (7)	N1—C1—C6—C5	−178.9 (4)
O2—N1—C1—C2	−161.0 (5)	N3—N2—C7—C4	−179.2 (4)
C6—C1—C2—C3	−2.8 (7)	N3—N2—C7—S	0.2 (5)
N1—C1—C2—C3	176.7 (4)	C5—C4—C7—N2	−153.1 (4)
C7—N2—N3—C8	0.0 (6)	C3—C4—C7—N2	25.6 (6)
C1—C2—C3—C4	1.3 (7)	C5—C4—C7—S	27.5 (6)
C2—C3—C4—C5	2.2 (7)	C3—C4—C7—S	−153.7 (4)
C2—C3—C4—C7	−176.6 (4)	C8—S—C7—N2	−0.2 (4)
C3—C4—C5—F	177.2 (4)	C8—S—C7—C4	179.2 (4)
C7—C4—C5—F	−4.0 (7)	N2—N3—C8—N4	−179.3 (4)
C3—C4—C5—C6	−4.7 (7)	N2—N3—C8—S	−0.2 (5)
C7—C4—C5—C6	174.1 (4)	C7—S—C8—N3	0.2 (4)
F—C5—C6—C1	−178.5 (4)	C7—S—C8—N4	179.4 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N3ⁱ	0.86	2.16	3.000 (5)	167
C3—H3B···O1ⁱⁱ	0.93	2.54	3.182 (7)	126

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

Experimental details

Crystal data
Chemical formula	C₈H₅FN₄O₂S
M_r	240.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	9.1780 (18), 9.3720 (19), 11.413 (2)
β (°)	102.55 (3)
V (Å³)	958.2 (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	1832, 1720, 1301
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.194, 1.01
No. of reflections	1720
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.47

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
N4—H4A···N3ⁱ	0.8600	2.1600	3.000 (5)	167.00
C3—H3B···O1ⁱⁱ	0.9300	2.5400	3.182 (7)	126.00

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

Acknowledgements

The authors thank Professor Hua-qin Wang of the Analysis Centre, Nanjing University, for providing the Enraf–Nonius CAD-4 diffractometer for this research project.

References

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