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

Yin, L.-H.; Wan, R.; Wang, Y.; Han, F.; Wang, J.-T.

doi:10.1107/S1600536808027827

organic compounds

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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Page o1884

doi:10.1107/S1600536808027827

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

Li-He Yin,^a Rong Wan,^a ^* Yao Wang,^a Feng Han ^a and Jin-Tang 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 29 August 2008; accepted 30 August 2008; online 6 September 2008)

In the title compound, C₈H₆BrN₃S, the thiadiazole ring is oriented at a dihedral angle of 48.35 (3)° with respect to the bromophenyl ring. In the crystal structure, intermolecular N—H⋯N hydrogen bonds link the molecules.

Related literature

For related literature, see: Nakagawa et al. (1996 ); Omar et al. (1986 ); Wang et al. (1999 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₈H₆BrN₃S
M_r = 256.13
Monoclinic, P 2₁ /c
a = 14.869 (3) Å
b = 8.0250 (16) Å
c = 7.9480 (16) Å
β = 97.43 (3)°
V = 940.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 4.54 mm⁻¹
T = 298 (2) K
0.30 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.343, T_max = 0.659
1832 measured reflections
1694 independent reflections
972 reflections with I > 2σ(I)
R_int = 0.034
3 standard reflections frequency: 120 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.153
S = 0.97
1694 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N1ⁱ	0.86	2.27	3.092 (7)	160
N3—H3A⋯N2ⁱ	0.86	2.61	3.221 (7)	129
N3—H3B⋯N2ⁱⁱ	0.86	2.06	2.896 (7)	163
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x, -y+{\script{5\over 2}}, z+{\script{1\over 2}}]$ .

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: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808027827/hk2522sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808027827/hk2522Isup2.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 and fungicidal activities (Wang et al., 1999). It can also be widely used in the field of medicine, such as anti-cancer drugs (Omar et al., 1986).

In the molecule of the title compound, (Fig. 1), the bond lengths (Allen et al., 1987) and angles are generally within normal ranges. Rings A (C1–C6) and B (S/N1/N2/C7/C8) are, of course, planar, and they are oriented at a dihedral angle of 48.35 (3)°.

In the crystal structure, intermolecular N—H···N hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure.

Related literature top

For related literature, see: Nakagawa et al. (1996); Omar et al. (1986); Wang et al. (1999). For bond-length data, see: Allen et al. (1987).

Experimental top

For the preparation of the title compound, 2-bromobenzoic 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 title compound (m.p. 486–487 K). Crystals suitable for X-ray analysis 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

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

Crystal data top

C₈H₆BrN₃S	F(000) = 504
M_r = 256.13	D_x = 1.809 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 486–487 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 14.869 (3) Å	Cell parameters from 25 reflections
b = 8.0250 (16) Å	θ = 10–14°
c = 7.9480 (16) Å	µ = 4.55 mm⁻¹
β = 97.43 (3)°	T = 298 K
V = 940.4 (3) Å³	Block, colorless
Z = 4	0.30 × 0.10 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	972 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.034
Graphite monochromator	θ_max = 25.2°, θ_min = 1.4°
ω/2θ scans	h = −17→17
Absorption correction: ψ scan (North et al., 1968)	k = 0→9
T_min = 0.343, T_max = 0.659	l = 0→9
1832 measured reflections	3 standard reflections every 120 min
1694 independent reflections	intensity decay: none

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.153	H-atom parameters constrained
S = 0.97	w = 1/[σ²(F_o²) + (0.0838P)²] where P = (F_o² + 2F_c²)/3
1694 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.57 e Å⁻³

Crystal data top

C₈H₆BrN₃S	V = 940.4 (3) Å³
M_r = 256.13	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.869 (3) Å	µ = 4.55 mm⁻¹
b = 8.0250 (16) Å	T = 298 K
c = 7.9480 (16) Å	0.30 × 0.10 × 0.10 mm
β = 97.43 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	972 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.034
T_min = 0.343, T_max = 0.659	3 standard reflections every 120 min
1832 measured reflections	intensity decay: none
1694 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.153	H-atom parameters constrained
S = 0.97	Δρ_max = 0.41 e Å⁻³
1694 reflections	Δρ_min = −0.57 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
Br	0.88329 (5)	1.09232 (10)	1.09121 (14)	0.0845 (5)
S	0.65602 (11)	1.1146 (2)	1.0932 (2)	0.0458 (5)
N1	0.6259 (3)	0.9573 (7)	0.8134 (6)	0.0424 (13)
N2	0.5587 (3)	1.0773 (6)	0.8048 (6)	0.0430 (13)
N3	0.5081 (3)	1.2909 (6)	0.9666 (6)	0.0480 (14)
H3A	0.4635	1.3143	0.8901	0.058*
H3B	0.5158	1.3467	1.0597	0.058*
C1	0.7308 (5)	0.6693 (8)	0.9656 (9)	0.0512 (18)
H1	0.6722	0.6431	0.9176	0.061*
C2	0.7921 (5)	0.5423 (8)	1.0064 (10)	0.0591 (19)
H2	0.7750	0.4319	0.9866	0.071*
C3	0.8787 (5)	0.5816 (10)	1.0769 (10)	0.068 (2)
H3	0.9204	0.4968	1.1067	0.081*
C4	0.9041 (4)	0.7438 (10)	1.1036 (9)	0.059 (2)
H4	0.9630	0.7698	1.1506	0.071*
C5	0.8416 (4)	0.8692 (8)	1.0602 (9)	0.0493 (17)
C6	0.7542 (4)	0.8348 (7)	0.9941 (8)	0.0378 (14)
C7	0.6811 (4)	0.9618 (8)	0.9507 (7)	0.0363 (14)
C8	0.5647 (4)	1.1688 (7)	0.9412 (7)	0.0332 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br	0.0417 (5)	0.0576 (5)	0.1483 (10)	−0.0105 (4)	−0.0096 (5)	−0.0066 (6)
S	0.0396 (9)	0.0538 (10)	0.0394 (9)	0.0102 (8)	−0.0131 (7)	−0.0097 (8)
N1	0.042 (3)	0.046 (3)	0.037 (3)	0.000 (3)	−0.001 (3)	−0.003 (3)
N2	0.045 (3)	0.043 (3)	0.037 (3)	0.008 (3)	−0.008 (2)	−0.005 (3)
N3	0.049 (3)	0.056 (4)	0.036 (3)	0.015 (3)	−0.008 (2)	−0.007 (3)
C1	0.046 (4)	0.049 (4)	0.057 (5)	−0.003 (3)	0.005 (3)	0.001 (4)
C2	0.057 (4)	0.035 (4)	0.086 (5)	0.004 (3)	0.013 (4)	0.004 (4)
C3	0.050 (4)	0.068 (6)	0.083 (6)	0.021 (4)	0.005 (4)	0.012 (5)
C4	0.037 (4)	0.064 (5)	0.073 (5)	0.009 (4)	−0.003 (4)	0.009 (4)
C5	0.031 (3)	0.049 (4)	0.065 (4)	−0.004 (3)	−0.004 (3)	0.006 (3)
C6	0.038 (3)	0.040 (3)	0.036 (3)	−0.002 (3)	0.006 (3)	−0.004 (3)
C7	0.029 (3)	0.042 (3)	0.037 (3)	−0.006 (3)	0.001 (3)	0.001 (3)
C8	0.029 (3)	0.035 (3)	0.034 (4)	0.000 (3)	−0.003 (3)	0.004 (3)

Geometric parameters (Å, º) top

Br—C5	1.901 (7)	C3—H3	0.9300
N1—N2	1.383 (7)	C4—C5	1.383 (9)
N3—H3A	0.8600	C4—H4	0.9300
N3—H3B	0.8600	C5—C6	1.365 (8)
C1—C2	1.377 (9)	C6—C7	1.498 (8)
C1—C6	1.384 (8)	C7—N1	1.278 (7)
C1—H1	0.9300	C7—S	1.742 (6)
C2—C3	1.373 (10)	C8—N2	1.302 (7)
C2—H2	0.9300	C8—N3	1.325 (7)
C3—C4	1.365 (11)	C8—S	1.752 (6)

C2—C1—C6	121.8 (7)	C5—C6—C1	117.6 (6)
C2—C1—H1	119.1	C5—C6—C7	125.3 (6)
C6—C1—H1	119.1	C1—C6—C7	117.1 (6)
C3—C2—C1	118.9 (7)	N1—C7—C6	123.0 (6)
C3—C2—H2	120.5	N1—C7—S	114.0 (5)
C1—C2—H2	120.5	C6—C7—S	122.6 (4)
C4—C3—C2	120.6 (7)	N2—C8—N3	124.6 (5)
C4—C3—H3	119.7	N2—C8—S	113.4 (4)
C2—C3—H3	119.7	N3—C8—S	122.0 (5)
C3—C4—C5	119.4 (6)	C7—N1—N2	113.7 (5)
C3—C4—H4	120.3	C8—N2—N1	112.4 (5)
C5—C4—H4	120.3	C8—N3—H3A	120.0
C6—C5—C4	121.6 (6)	C8—N3—H3B	120.0
C6—C5—Br	121.2 (5)	H3A—N3—H3B	120.0
C4—C5—Br	117.1 (5)	C7—S—C8	86.4 (3)

C6—C1—C2—C3	−0.2 (11)	C1—C6—C7—N1	−44.3 (9)
C1—C2—C3—C4	−1.0 (12)	C5—C6—C7—S	−51.2 (8)
C2—C3—C4—C5	0.5 (12)	C1—C6—C7—S	128.4 (6)
C3—C4—C5—C6	1.3 (11)	C6—C7—N1—N2	174.6 (5)
C3—C4—C5—Br	−177.2 (6)	S—C7—N1—N2	1.3 (7)
C4—C5—C6—C1	−2.5 (11)	N3—C8—N2—N1	−179.0 (6)
Br—C5—C6—C1	176.0 (5)	S—C8—N2—N1	0.6 (6)
C4—C5—C6—C7	177.2 (6)	C7—N1—N2—C8	−1.2 (7)
Br—C5—C6—C7	−4.4 (9)	N1—C7—S—C8	−0.8 (5)
C2—C1—C6—C5	1.9 (11)	C6—C7—S—C8	−174.1 (5)
C2—C1—C6—C7	−177.8 (6)	N2—C8—S—C7	0.1 (5)
C5—C6—C7—N1	136.1 (7)	N3—C8—S—C7	179.6 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N1ⁱ	0.86	2.27	3.092 (7)	160
N3—H3A···N2ⁱ	0.86	2.61	3.221 (7)	129
N3—H3B···N2ⁱⁱ	0.86	2.06	2.896 (7)	163

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x, −y+5/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₈H₆BrN₃S
M_r	256.13
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	14.869 (3), 8.0250 (16), 7.9480 (16)
β (°)	97.43 (3)
V (Å³)	940.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.55
Crystal size (mm)	0.30 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.343, 0.659
No. of measured, independent and observed [I > 2σ(I)] reflections	1832, 1694, 972
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.598

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.153, 0.97
No. of reflections	1694
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.57

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···N1ⁱ	0.86	2.27	3.092 (7)	160.3
N3—H3A···N2ⁱ	0.86	2.61	3.221 (7)	128.5
N3—H3B···N2ⁱⁱ	0.86	2.06	2.896 (7)	163.2

Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x, −y+5/2, z+1/2.

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

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