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

Zhang, J.; He, Q.; Jiang, Q.; Mu, H.; Wan, R.

doi:10.1107/S1600536811030868

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2255

doi:10.1107/S1600536811030868

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

Jian-qiang Zhang,^a Qiu He,^a Qianghua Jiang,^a Haipin Mu ^a and Rong Wan ^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 12 July 2011; accepted 1 August 2011; online 6 August 2011)

The title compound, C₈H₅BrN₄O₂S, was synthesized by the reaction of 4-bromo-2-nitrobenzoic acid with thiosemicarbazide. The dihedral angle between the thiadiazole and benzene rings is 40.5 (2)°. In the crystal, the strongest N—H⋯N intermolecular hydrogen bond, between the amine group and one thiadiazole N atom, forms centrosymmetric dimers. The other amine H atom extends the supramolecular network, forming an N—H⋯N contact with the other thiadiazole N atom.

Related literature

For the biological activity of 1,3,4-thiadiazole derivatives, see: Nakagawa et al. (1996 ); Wang et al. (1999 ).

Experimental

Crystal data

C₈H₅BrN₄O₂S
M_r = 301.13
Monoclinic, P 2₁ /c
a = 11.231 (2) Å
b = 9.2580 (19) Å
c = 10.868 (2) Å
β = 113.08 (3)°
V = 1039.6 (4) Å³
Z = 4
Mo Kα radiation
μ = 4.14 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 = 0.491, T_max = 0.682
3909 measured reflections
1920 independent reflections
1409 reflections with I > 2σ(I)
R_int = 0.116
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.104
S = 1.01
1920 reflections
152 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.97 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4B⋯N3ⁱ	0.79 (7)	2.25 (7)	3.014 (6)	165 (7)
N4—H4C⋯N2ⁱⁱ	0.80 (6)	2.34 (6)	3.103 (6)	161 (6)
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

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/S1600536811030868/bh2371sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811030868/bh2371Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811030868/bh2371Isup3.cml

checkCIF report

Comment top

1,3,4-Thiadiazole derivatives represent an interesting class of compounds possessing a broad spectrum of biological activities (Nakagawa et al., 1996). These compounds are known to exhibit diverse biological activities, such as insecticidal and fungicidal activities (Wang et al., 1999). Here we report the crystal structure of the title compound, a new thiadiazole. In the molecular structure (Fig. 1) the bond lengths and angles are within normal ranges. Thiadiazole ring C8/S/C7/N2/N3 is planar, and the mean deviation from the plane is 0.0046 Å. The dihedral angle between the thiadiazole and benzene rings is 40.5 (2)°. In the crystal structure, the strongest N—H···N intermolecular contact (first entry in the hydrogen bonds Table) forms centrosymmetric dimers in the crystal (top molecules in Fig. 2). This pattern is the primary supramolecular structure for this compound. The other hydrogen bond (entry 2) is comparatively weak, and extends the primary pattern to a three-dimensional network, which may be effective in the stabilization of the crystal structure.

Related literature top

For the biological activity of 1,3,4-thiadiazole derivatives, see: Nakagawa et al. (1996); Wang et al. (1999).

Experimental top

4-Bromo-2-nitrobenzoic acid (2 mmol) and thiosemicarbazide (5 mmol) were mixed in a 25 ml flask, and kept in the oil bath at 90 °C for 6 h. After cooling, the crude product precipitated and was filtered. Pure compound was obtained by crystallization from ethanol (20 ml). Single crystals 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 the title compound, with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Partial packing view showing the hydrogen bonds network. Dashed lines indicate intermolecular N—H···N hydrogen bonds.

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

Crystal data top

C₈H₅BrN₄O₂S	F(000) = 592
M_r = 301.13	D_x = 1.924 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 506 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 11.231 (2) Å	Cell parameters from 25 reflections
b = 9.2580 (19) Å	θ = 10–13°
c = 10.868 (2) Å	µ = 4.14 mm⁻¹
β = 113.08 (3)°	T = 293 K
V = 1039.6 (4) Å³	Block, yellow
Z = 4	0.20 × 0.10 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1409 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.116
Graphite monochromator	θ_max = 25.4°, θ_min = 2.0°
ω/2θ scans	h = −13→12
Absorption correction: ψ scan (North et al., 1968)	k = −11→11
T_min = 0.491, T_max = 0.682	l = 0→13
3909 measured reflections	3 standard reflections every 200 reflections
1920 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.049	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.104	w = 1/[σ²(F_o²) + (0.025P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
1920 reflections	Δρ_max = 0.55 e Å⁻³
152 parameters	Δρ_min = −0.97 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 constraints	Extinction coefficient: 0.0114 (8)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₈H₅BrN₄O₂S	V = 1039.6 (4) Å³
M_r = 301.13	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.231 (2) Å	µ = 4.14 mm⁻¹
b = 9.2580 (19) Å	T = 293 K
c = 10.868 (2) Å	0.20 × 0.10 × 0.10 mm
β = 113.08 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1409 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.116
T_min = 0.491, T_max = 0.682	3 standard reflections every 200 reflections
3909 measured reflections	intensity decay: 1%
1920 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.55 e Å⁻³
1920 reflections	Δρ_min = −0.97 e Å⁻³
152 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br	0.11486 (5)	0.01063 (5)	0.19612 (6)	0.0512 (2)
S	0.34305 (13)	0.66328 (12)	0.58298 (11)	0.0389 (3)
C1	0.2933 (5)	0.3456 (5)	0.4493 (4)	0.0398 (11)
H1A	0.3437	0.3551	0.5402	0.048*
N1	0.1367 (4)	0.5710 (4)	0.1441 (4)	0.0370 (9)
O1	0.1374 (4)	0.5588 (4)	0.0330 (3)	0.0585 (10)
O2	0.0937 (3)	0.6740 (3)	0.1818 (3)	0.0517 (10)
N2	0.3728 (4)	0.6948 (4)	0.3620 (3)	0.0357 (9)
C2	0.2492 (5)	0.2112 (5)	0.3991 (5)	0.0418 (12)
H2B	0.2717	0.1308	0.4549	0.050*
N3	0.4262 (4)	0.8176 (4)	0.4373 (3)	0.0339 (9)
C3	0.1724 (4)	0.1958 (4)	0.2670 (5)	0.0360 (10)
C4	0.1413 (5)	0.3137 (5)	0.1816 (4)	0.0339 (11)
H4A	0.0920	0.3029	0.0907	0.041*
N4	0.4674 (5)	0.9189 (5)	0.6472 (4)	0.0460 (12)
H4B	0.486 (6)	0.996 (7)	0.630 (6)	0.055*
H4C	0.446 (5)	0.910 (6)	0.709 (6)	0.055*
C5	0.1853 (4)	0.4459 (5)	0.2350 (4)	0.0331 (10)
C6	0.2654 (4)	0.4671 (4)	0.3696 (4)	0.0283 (9)
C7	0.3245 (4)	0.6062 (5)	0.4235 (4)	0.0303 (9)
C8	0.4186 (4)	0.8148 (4)	0.5534 (4)	0.0318 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br	0.0612 (3)	0.0292 (3)	0.0646 (4)	−0.0078 (3)	0.0262 (3)	−0.0142 (2)
S	0.0593 (7)	0.0333 (6)	0.0300 (5)	−0.0143 (6)	0.0240 (5)	−0.0042 (5)
C1	0.045 (3)	0.037 (2)	0.031 (2)	0.001 (2)	0.008 (2)	0.000 (2)
N1	0.037 (2)	0.036 (2)	0.031 (2)	0.001 (2)	0.0059 (17)	0.0040 (17)
O1	0.073 (2)	0.056 (2)	0.0359 (18)	−0.001 (2)	0.0100 (17)	0.0107 (18)
O2	0.060 (2)	0.0277 (16)	0.057 (2)	0.0082 (18)	0.0115 (19)	0.0035 (16)
N2	0.047 (2)	0.0326 (17)	0.0289 (18)	−0.010 (2)	0.0163 (17)	−0.0061 (16)
C2	0.046 (3)	0.026 (2)	0.044 (3)	−0.003 (2)	0.008 (2)	0.005 (2)
N3	0.045 (2)	0.0318 (18)	0.0267 (18)	−0.0118 (19)	0.0163 (17)	−0.0039 (15)
C3	0.034 (2)	0.0213 (18)	0.053 (3)	−0.005 (2)	0.017 (2)	−0.009 (2)
C4	0.039 (3)	0.031 (2)	0.028 (2)	−0.002 (2)	0.0086 (19)	−0.0053 (18)
N4	0.076 (3)	0.036 (2)	0.033 (2)	−0.023 (2)	0.028 (2)	−0.0124 (19)
C5	0.034 (2)	0.0246 (18)	0.035 (2)	−0.001 (2)	0.007 (2)	−0.0030 (19)
C6	0.034 (2)	0.0274 (19)	0.0261 (19)	−0.005 (2)	0.0140 (17)	−0.0026 (17)
C7	0.034 (2)	0.031 (2)	0.028 (2)	−0.004 (2)	0.0140 (19)	−0.0012 (18)
C8	0.035 (2)	0.027 (2)	0.031 (2)	−0.007 (2)	0.0109 (19)	−0.0013 (18)

Geometric parameters (Å, º) top

Br—C3	1.887 (4)	C2—C3	1.362 (7)
S—C8	1.734 (4)	C2—H2B	0.9300
S—C7	1.744 (4)	N3—C8	1.297 (5)
C1—C2	1.371 (6)	C3—C4	1.386 (6)
C1—C6	1.379 (6)	C4—C5	1.361 (6)
C1—H1A	0.9300	C4—H4A	0.9300
N1—O2	1.210 (5)	N4—C8	1.353 (6)
N1—O1	1.215 (5)	N4—H4B	0.79 (6)
N1—C5	1.481 (6)	N4—H4C	0.81 (6)
N2—C7	1.303 (5)	C5—C6	1.399 (6)
N2—N3	1.392 (4)	C6—C7	1.462 (6)

C8—S—C7	86.4 (2)	C3—C4—H4A	121.0
C2—C1—C6	122.2 (4)	C8—N4—H4B	122 (4)
C2—C1—H1A	118.9	C8—N4—H4C	113 (4)
C6—C1—H1A	118.9	H4B—N4—H4C	119 (6)
O2—N1—O1	124.7 (4)	C4—C5—C6	123.3 (4)
O2—N1—C5	118.8 (4)	C4—C5—N1	116.2 (3)
O1—N1—C5	116.4 (4)	C6—C5—N1	120.4 (4)
C7—N2—N3	112.4 (3)	C1—C6—C5	115.9 (4)
C3—C2—C1	119.7 (4)	C1—C6—C7	120.7 (3)
C3—C2—H2B	120.2	C5—C6—C7	123.2 (4)
C1—C2—H2B	120.2	N2—C7—C6	124.3 (4)
C8—N3—N2	112.3 (3)	N2—C7—S	114.1 (3)
C2—C3—C4	120.8 (4)	C6—C7—S	121.6 (3)
C2—C3—Br	119.9 (3)	N3—C8—N4	123.8 (4)
C4—C3—Br	119.1 (3)	N3—C8—S	114.8 (3)
C5—C4—C3	118.0 (4)	N4—C8—S	121.3 (3)
C5—C4—H4A	121.0

C6—C1—C2—C3	−1.8 (8)	N1—C5—C6—C1	172.8 (4)
C7—N2—N3—C8	1.5 (5)	C4—C5—C6—C7	172.7 (5)
C1—C2—C3—C4	2.1 (8)	N1—C5—C6—C7	−11.3 (7)
C1—C2—C3—Br	178.4 (4)	N3—N2—C7—C6	−178.4 (4)
C2—C3—C4—C5	−2.8 (7)	N3—N2—C7—S	−1.3 (5)
Br—C3—C4—C5	−179.2 (4)	C1—C6—C7—N2	135.9 (5)
C3—C4—C5—C6	3.5 (8)	C5—C6—C7—N2	−39.8 (7)
C3—C4—C5—N1	−172.6 (4)	C1—C6—C7—S	−40.9 (6)
O2—N1—C5—C4	130.8 (5)	C5—C6—C7—S	143.4 (4)
O1—N1—C5—C4	−45.7 (6)	C8—S—C7—N2	0.7 (4)
O2—N1—C5—C6	−45.5 (6)	C8—S—C7—C6	177.8 (4)
O1—N1—C5—C6	138.1 (5)	N2—N3—C8—N4	177.6 (4)
C2—C1—C6—C5	2.3 (7)	N2—N3—C8—S	−1.0 (5)
C2—C1—C6—C7	−173.7 (5)	C7—S—C8—N3	0.2 (4)
C4—C5—C6—C1	−3.1 (7)	C7—S—C8—N4	−178.4 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···N3ⁱ	0.79 (7)	2.25 (7)	3.014 (6)	165 (7)
N4—H4C···N2ⁱⁱ	0.80 (6)	2.34 (6)	3.103 (6)	161 (6)

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

Experimental details

Crystal data
Chemical formula	C₈H₅BrN₄O₂S
M_r	301.13
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.231 (2), 9.2580 (19), 10.868 (2)
β (°)	113.08 (3)
V (Å³)	1039.6 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.14
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	0.491, 0.682
No. of measured, independent and observed [I > 2σ(I)] reflections	3909, 1920, 1409
R_int	0.116
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.104, 1.01
No. of reflections	1920
No. of parameters	152
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.97

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
N4—H4B···N3ⁱ	0.79 (7)	2.25 (7)	3.014 (6)	165 (7)
N4—H4C···N2ⁱⁱ	0.80 (6)	2.34 (6)	3.103 (6)	161 (6)

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

Acknowledgements

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

References

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