5-(4-Bromo-2-nitro-phen-yl)-1,3,4-thia-diazol-2-amine.

The title compound, C(8)H(5)BrN(4)O(2)S, was synthesized by the reaction of 4-bromo-2-nitro-benzoic acid with thio-semi-carbazide. The dihedral angle between the thia-diazole and benzene rings is 40.5 (2)°. In the crystal, the strongest N-H⋯N inter-molecular hydrogen bond, between the amine group and one thia-diazole N atom, forms centrosymmetric dimers. The other amine H atom extends the supra-molecular network, forming an N-H⋯N contact with the other thia-diazole 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 = 301.13

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.104

S = 1.01

1920 reflections

152 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.55 e Å−3

Δρmin = −0.97 e Å−3

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.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811030868/bh2371sup1.cif

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

Supplementary material file. DOI: 10.1107/S1600536811030868/bh2371Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C8H5BrN4O2S	F(000) = 592
Mr = 301.13	Dx = 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

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

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(Fo2) + (0.025P)2] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max < 0.001
1920 reflections	Δρmax = 0.55 e Å−3
152 parameters	Δρmin = −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

	x	y	z	Uiso*/Ueq
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)

	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)

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)

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)

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) ; (ii) .