6-Bromo-1,3-benzothia­zol-2-amine

Gao, X.-J.; Jin, S.-W.; Huang, Y.-F.; Zhou, Y.; Zhou, Y.-P.

doi:10.1107/S1600536812040123

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 10| October 2012| Page o3016

https://doi.org/10.1107/S1600536812040123

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6-Bromo-1,3-benzothiazol-2-amine

Xing-Jun Gao,^a Shou-Wen Jin,^b ^* Yan-Fei Huang,^b Yong Zhou ^b and Ying-Ping Zhou ^b

^aFaculty of Science, ZheJiang A & F University, Lin'An 311300, People's Republic of China, and ^bTianmu College of ZheJiang A & F University, Lin'An 311300, People's Republic of China
^*Correspondence e-mail: shouwenjin@yahoo.cn

(Received 7 September 2012; accepted 21 September 2012; online 26 September 2012)

The r.m.s. deviation from the mean plane for the non-H atoms in the title compound, C₇H₅BrN₂S, is 0.011 Å. In the crystal, the molecules are linked by N—H⋯N and N—H⋯Br hydrogen bonds to generate (010) sheets. Weak aromatic π–π stacking [centroid-to-centroid separation = 3.884 (10) Å] and possible C—H⋯Br interactions are also observed. The crystal studied was found to be an inversion twin.

Related literature

For a related structure and background to benzothiazole derivatives, see: Jin et al. (2012 ).

Experimental

Crystal data

C₇H₅BrN₂S
M_r = 229.10
Orthorhombic, P n a 2₁
a = 8.6268 (7) Å
b = 22.487 (2) Å
c = 4.0585 (3) Å
V = 787.30 (11) Å³
Z = 4
Mo Kα radiation
μ = 5.41 mm⁻¹
T = 298 K
0.31 × 0.25 × 0.16 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.215, T_max = 0.421
3645 measured reflections
1340 independent reflections
929 reflections with I > 2σ(I)
R_int = 0.087

Refinement

R[F² > 2σ(F²)] = 0.095
wR(F²) = 0.246
S = 1.07
1340 reflections
100 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 1.13 e Å⁻³
Δρ_min = −0.74 e Å⁻³
Absolute structure: Flack (1983 ), 539 Friedel pairs
Flack parameter: 0.42 (9)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯Br1ⁱ	0.86	3.04	3.864 (17)	160
N2—H2A⋯N1ⁱⁱ	0.86	2.26	2.94 (2)	136
C4—H4⋯Br1ⁱⁱⁱ	0.93	2.87	3.402 (17)	118
Symmetry codes: (i) x-1, y, z+1; (ii) $[-x+1, -y+1, z+{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ .

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; 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: https://doi.org/10.1107/S1600536812040123/hb6956sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812040123/hb6956Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812040123/hb6956Isup3.cml

checkCIF report

Comment top

As an extension of our study of 2-aminoheterocyclic compounds (Jin et al., 2012), herein we report the crystal structure of 6-bromobenzo[d]thiazol-2-amine.

The single crystals of the title compound (Fig.1) with the formula C₇H₅BrN₂S was obtained by slow evaporating its methanol solution.

The 6-bromobenzo[d]thiazol-2-amine molecules (Fig. 1) are linked together in head to tail fashion via the N—H···Br association to form one-dimensional chain running along the direction that made a dihedral angle of ca 30° with the a axis direction. Two neighboring chains were held together by the CH—Br interaction with C—Br distance of 3.402 Å generating one-dimensional double chain (Fig.2). The double chains were stacked along the direction that is perpendicular with its extending direction by the CH—Br interaction with C—Br distance of 3.402 Å to form two-dimensional sheet extending parallel to the ac plane. The sheets were further stacked along the b axis direction by the intersheet N—H···N hydrogen bonds to form three-dimensional ABAB layer network structure.

Related literature top

For a related structure and background to benzothiazole derivatives, see: Jin et al. (2012).

Experimental top

The 6-bromobenzo[d]thiazol-2-amine (22.9 mg, 0.1 mmol) was dissolved in a methanol solution (8 ml). The solution was filtered into a test tube. The solution was left standing at room temperature for a month, light-yellow blocks were isolated after slow evaporation of the methanol solution to ca 3 ml in air.

Structure description top

As an extension of our study of 2-aminoheterocyclic compounds (Jin et al., 2012), herein we report the crystal structure of 6-bromobenzo[d]thiazol-2-amine.

The single crystals of the title compound (Fig.1) with the formula C₇H₅BrN₂S was obtained by slow evaporating its methanol solution.

For a related structure and background to benzothiazole derivatives, see: Jin et al. (2012).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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 structure of the title compound, showing displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. One-dimensional double chain structure.

6-Bromo-1,3-benzothiazol-2-amine top

Crystal data top

C₇H₅BrN₂S	D_x = 1.933 Mg m⁻³
M_r = 229.10	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna2₁	Cell parameters from 868 reflections
a = 8.6268 (7) Å	θ = 3.6–21.4°
b = 22.487 (2) Å	µ = 5.41 mm⁻¹
c = 4.0585 (3) Å	T = 298 K
V = 787.30 (11) Å³	Block, colourless
Z = 4	0.31 × 0.25 × 0.16 mm
F(000) = 448

Data collection top

Bruker SMART CCD diffractometer	1340 independent reflections
Radiation source: fine-focus sealed tube	929 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.087
ω scans	θ_max = 25.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −6→10
T_min = 0.215, T_max = 0.421	k = −26→26
3645 measured reflections	l = −4→4

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)] = 0.095	H-atom parameters constrained
wR(F²) = 0.246	w = 1/[σ²(F_o²) + (0.067P)² + 14.6225P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
1340 reflections	Δρ_max = 1.13 e Å⁻³
100 parameters	Δρ_min = −0.74 e Å⁻³
1 restraint	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.42 (9)

Crystal data top

C₇H₅BrN₂S	V = 787.30 (11) Å³
M_r = 229.10	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 8.6268 (7) Å	µ = 5.41 mm⁻¹
b = 22.487 (2) Å	T = 298 K
c = 4.0585 (3) Å	0.31 × 0.25 × 0.16 mm

Data collection top

Bruker SMART CCD diffractometer	1340 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	929 reflections with I > 2σ(I)
T_min = 0.215, T_max = 0.421	R_int = 0.087
3645 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.095	H-atom parameters constrained
wR(F²) = 0.246	w = 1/[σ²(F_o²) + (0.067P)² + 14.6225P] where P = (F_o² + 2F_c²)/3
S = 1.07	Δρ_max = 1.13 e Å⁻³
1340 reflections	Δρ_min = −0.74 e Å⁻³
100 parameters	Absolute structure: Flack (1983), with how many Friedel pairs?
1 restraint	Absolute structure parameter: 0.42 (9)

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
Br1	1.2451 (2)	0.69710 (7)	0.3819 (16)	0.0745 (8)
S1	0.6334 (4)	0.65747 (14)	0.8676 (16)	0.0407 (9)
N2	0.4231 (13)	0.5675 (5)	0.884 (6)	0.051 (3)
H2A	0.3952	0.5318	0.8379	0.061*
H2B	0.3608	0.5908	0.9878	0.061*
C7	0.9282 (17)	0.5595 (6)	0.404 (6)	0.044 (4)
H7	0.9250	0.5204	0.3294	0.052*
C6	1.0594 (18)	0.5939 (6)	0.352 (6)	0.043 (4)
H6	1.1456	0.5786	0.2435	0.052*
N1	0.6666 (18)	0.5508 (6)	0.627 (4)	0.047 (4)
C1	0.5630 (19)	0.5869 (7)	0.795 (4)	0.046 (5)
C2	0.802 (2)	0.5836 (7)	0.568 (4)	0.042 (4)
C4	0.933 (2)	0.6779 (7)	0.634 (5)	0.046 (4)
H4	0.9364	0.7170	0.7084	0.055*
C3	0.804 (2)	0.6421 (8)	0.682 (4)	0.045 (4)
C5	1.057 (2)	0.6520 (7)	0.469 (4)	0.052 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0513 (10)	0.0510 (9)	0.1212 (18)	−0.0117 (8)	0.005 (2)	0.005 (2)
S1	0.0394 (18)	0.0344 (16)	0.048 (2)	−0.0010 (15)	0.006 (3)	0.015 (3)
N2	0.041 (7)	0.041 (6)	0.071 (10)	−0.005 (5)	−0.012 (15)	−0.004 (11)
C7	0.045 (8)	0.033 (7)	0.053 (11)	0.000 (6)	0.007 (13)	−0.012 (11)
C6	0.052 (9)	0.038 (7)	0.040 (10)	−0.002 (6)	0.014 (14)	−0.007 (11)
N1	0.054 (9)	0.040 (7)	0.047 (9)	−0.001 (7)	0.010 (8)	−0.006 (7)
C1	0.043 (9)	0.037 (8)	0.059 (15)	−0.007 (7)	0.000 (9)	−0.009 (8)
C2	0.047 (10)	0.038 (9)	0.041 (10)	−0.005 (8)	0.011 (8)	−0.004 (8)
C4	0.052 (11)	0.035 (8)	0.051 (11)	0.002 (8)	0.005 (9)	−0.008 (8)
C3	0.050 (11)	0.044 (9)	0.040 (10)	−0.004 (8)	0.005 (8)	−0.001 (8)
C5	0.051 (10)	0.044 (9)	0.060 (16)	−0.001 (8)	0.004 (9)	0.002 (8)

Geometric parameters (Å, º) top

Br1—C5	1.944 (18)	C6—C5	1.39 (2)
S1—C3	1.686 (19)	C6—H6	0.9300
S1—C1	1.725 (16)	N1—C1	1.39 (2)
N2—C1	1.33 (2)	N1—C2	1.40 (2)
N2—H2A	0.8600	C2—C3	1.39 (2)
N2—H2B	0.8600	C4—C3	1.39 (3)
C7—C6	1.39 (2)	C4—C5	1.39 (2)
C7—C2	1.39 (2)	C4—H4	0.9300
C7—H7	0.9300

C3—S1—C1	92.4 (9)	N1—C1—S1	113.3 (12)
C1—N2—H2A	120.0	C7—C2—C3	121.1 (16)
C1—N2—H2B	120.0	C7—C2—N1	122.0 (15)
H2A—N2—H2B	120.0	C3—C2—N1	116.9 (16)
C6—C7—C2	119.7 (14)	C3—C4—C5	116.3 (15)
C6—C7—H7	120.1	C3—C4—H4	121.8
C2—C7—H7	120.1	C5—C4—H4	121.8
C7—C6—C5	117.5 (15)	C4—C3—C2	120.7 (17)
C7—C6—H6	121.2	C4—C3—S1	130.0 (14)
C5—C6—H6	121.2	C2—C3—S1	109.2 (14)
C1—N1—C2	108.1 (14)	C6—C5—C4	124.6 (16)
N2—C1—N1	121.7 (14)	C6—C5—Br1	114.7 (13)
N2—C1—S1	125.0 (13)	C4—C5—Br1	120.7 (12)

C2—C7—C6—C5	0 (3)	C7—C2—C3—C4	0 (3)
C2—N1—C1—N2	179.8 (19)	N1—C2—C3—C4	−180.0 (17)
C2—N1—C1—S1	0.3 (18)	C7—C2—C3—S1	179.8 (17)
C3—S1—C1—N2	−179.9 (18)	N1—C2—C3—S1	0 (2)
C3—S1—C1—N1	−0.4 (15)	C1—S1—C3—C4	−180 (2)
C6—C7—C2—C3	0 (3)	C1—S1—C3—C2	0.4 (15)
C6—C7—C2—N1	−179.9 (19)	C7—C6—C5—C4	0 (3)
C1—N1—C2—C7	180 (2)	C7—C6—C5—Br1	−179.5 (15)
C1—N1—C2—C3	0 (2)	C3—C4—C5—C6	0 (3)
C5—C4—C3—C2	0 (3)	C3—C4—C5—Br1	179.6 (14)
C5—C4—C3—S1	−179.7 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···Br1ⁱ	0.86	3.04	3.864 (17)	160
N2—H2A···N1ⁱⁱ	0.86	2.26	2.94 (2)	136
C4—H4···Br1ⁱⁱⁱ	0.93	2.87	3.402 (17)	118

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

Experimental details

Crystal data
Chemical formula	C₇H₅BrN₂S
M_r	229.10
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	298
a, b, c (Å)	8.6268 (7), 22.487 (2), 4.0585 (3)
V (Å³)	787.30 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.41
Crystal size (mm)	0.31 × 0.25 × 0.16

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.215, 0.421
No. of measured, independent and observed [I > 2σ(I)] reflections	3645, 1340, 929
R_int	0.087
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.095, 0.246, 1.07
No. of reflections	1340
No. of parameters	100
No. of restraints	1
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.067P)² + 14.6225P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.13, −0.74
Absolute structure	Flack (1983), with how many Friedel pairs?
Absolute structure parameter	0.42 (9)

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), 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
N2—H2B···Br1ⁱ	0.86	3.04	3.864 (17)	160
N2—H2A···N1ⁱⁱ	0.86	2.26	2.94 (2)	136
C4—H4···Br1ⁱⁱⁱ	0.93	2.87	3.402 (17)	118

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

Acknowledgements

The authors gratefully acknowledge financial support from the Education Office Foundation of Zhejiang Province (project No. Y201017321) and from the Innovation Project of Zhejiang A & F University.

References

Bruker (2002). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
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