1,3-Benzothia­zol-2-amine

Altaf, M.; Stoeckli-Evans, H.

doi:10.1107/S1600536809027561

organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1894

doi:10.1107/S1600536809027561

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1,3-Benzothiazol-2-amine

Muhammad Altaf ^a and Helen Stoeckli-Evans ^a ^*

^aInstitute of Physics, University of Neuchâtel, rue Emile-Argand 11, CH-2009 Neuchâtel, Switzerland
^*Correspondence e-mail: helen.stoeckli-evans@unine.ch

(Received 7 July 2009; accepted 13 July 2009; online 18 July 2009)

In the crystal structure of the title compound, C₇H₆N₂S, molecules related by an inversion center are linked via N—H⋯N hydrogen bonds involving the amino groups, forming dimers. In turn, these dimers are linked via a second N—H⋯N hydrogen bond, forming an infinite two-dimensional network parallel to (011).

Related literature

For the original powder diffraction study of the title compound, see: Goubitz et al. (2001 ). For related structures containing the title compound, see: Martínez-Martínez et al. (2003 ); Padilla-Martínez et al. (2003 ); Wang et al. (2008 ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

C₇H₆N₂S
M_r = 150.20
Monoclinic, P 2₁ /c
a = 14.606 (4) Å
b = 3.997 (1) Å
c = 11.565 (4) Å
β = 94.47 (2)°
V = 673.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.39 mm⁻¹
T = 173 K
0.50 × 0.50 × 0.50 mm

Data collection

Stoe IPDS-2 diffractometer
Absorption correction: none
2783 measured reflections
1181 independent reflections
1061 reflections with I > 2σ(I)
R_int = 0.086

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.143
S = 1.06
1181 reflections
99 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯N1ⁱ	0.83 (2)	2.14 (2)	2.964 (3)	172 (2)
N2—H2A⋯N2ⁱⁱ	0.80 (2)	2.46 (2)	3.217 (3)	157 (2)
Symmetry codes: (i) -x, -y+1, -z; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: X-AREA (Stoe & Cie, 2006 ); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809027561/jh2090sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809027561/jh2090Isup2.hkl

checkCIF report

Comment top

The first reference to the crystal structure of the title compound appeared in a study by (Goubitz et al., 2001) on the crystal structure determination of a series of small organic molecules from powder diffraction data. The analysis, using Guinier photographic data, was successful but the final Reitveld refinement gave an R_f value of only 16.4%. Herein, we report on a single-crystal low temperature analysis (173 K) of the title compound.

A search of the Cambridge Structural Database (Allen, 2002; CSD version 5.30, last update May 2009) revealed the presence of the title compound in a number of co-crystals, for example, with rac-7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylic acid (Wang et al., 2008), and in some (1/1) donor-acceptor complexes, for example, with N-benzyl-2-oxo-2H-1-benzopyran-3-carboximade (Martínez-Martínez et al., 2003) and ethyl-coumarin-3-carboxylate (Padilla-Martínez et al., 2003).

The molecular structure of the title compound is illustrated in Fig. 1. The geometric parameters are available in the archived CIF and are similar to those in the above mentioned compounds.

In the crystal of the title compound molecules related by an inversion center are linked by N2—H2B··· N1ⁱ [symmetry operation: (i) -x, -y + 1, -z] hydrogen bonds to form centrosymmetric dimers (Table 1 and Fig. 2). These dimers are further linked via N2—H2A···N1ⁱⁱ [symmetry operation: (ii) -x, y - 1/2, -z + 1/2] interactions to form infinite two-dimensional networks lying parallel to the (011) plane, and stacking along the [100] direction.

Related literature top

For the original powder diffraction study of the title compound, see: Goubitz et al. (2001). For related structures containing the title compound, see: Martínez-Martínez et al. (2003); Padilla-Martínez et al. (2003); Wang et al. (2008). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

Single crystals of the title compound were obtained by recrystallization from methanol of a reagent grade sample.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2006); cell refinement: X-AREA (Stoe & Cie, 2006); data reduction: X-RED32 (Stoe & Cie, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2006); 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 the displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. A view along the a axis of the crystal packing of the title compound, illustrating the formation of the centrosymmetric hydrogen bonded dimers and the two-dimensional hydrogen bonded network (see Table 1 for details; the hydrogen bonds are shown a pale-blue dashed lines; H-atoms not involved in hydrogen bonding have been omitted for clarity).

1,3-Benzothiazol-2-amine top

Crystal data top

C₇H₆N₂S	F(000) = 312
M_r = 150.20	D_x = 1.482 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 42133 reflections
a = 14.606 (4) Å	θ = 3.5–25.6°
b = 3.997 (1) Å	µ = 0.39 mm⁻¹
c = 11.565 (4) Å	T = 173 K
β = 94.47 (2)°	Block, colourless
V = 673.1 (3) Å³	0.50 × 0.50 × 0.50 mm
Z = 4

Data collection top

Stoe IPDS-2 diffractometer	1061 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.086
Graphite monochromator	θ_max = 25.2°, θ_min = 3.5°
ϕ and ω scans	h = −17→15
2783 measured reflections	k = −4→4
1181 independent reflections	l = −13→13

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.143	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.1031P)² + 0.0494P] where P = (F_o² + 2F_c²)/3
1181 reflections	(Δ/σ)_max < 0.001
99 parameters	Δρ_max = 0.38 e Å⁻³
2 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₇H₆N₂S	V = 673.1 (3) Å³
M_r = 150.20	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.606 (4) Å	µ = 0.39 mm⁻¹
b = 3.997 (1) Å	T = 173 K
c = 11.565 (4) Å	0.50 × 0.50 × 0.50 mm
β = 94.47 (2)°

Data collection top

Stoe IPDS-2 diffractometer	1061 reflections with I > 2σ(I)
2783 measured reflections	R_int = 0.086
1181 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	2 restraints
wR(F²) = 0.143	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.38 e Å⁻³
1181 reflections	Δρ_min = −0.31 e Å⁻³
99 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
S1	0.17155 (4)	0.19806 (15)	0.24812 (4)	0.0406 (3)
N1	0.12810 (12)	0.4914 (5)	0.04966 (13)	0.0373 (5)
N2	0.00290 (14)	0.2707 (6)	0.14135 (17)	0.0427 (7)
C1	0.25983 (15)	0.3777 (6)	0.17558 (17)	0.0391 (7)
C2	0.35252 (17)	0.3886 (7)	0.2091 (2)	0.0481 (8)
C3	0.40994 (17)	0.5406 (7)	0.1364 (2)	0.0523 (8)
C4	0.37475 (18)	0.6870 (6)	0.0321 (2)	0.0492 (8)
C5	0.28136 (17)	0.6797 (6)	−0.0011 (2)	0.0435 (7)
C6	0.22260 (15)	0.5222 (5)	0.07108 (17)	0.0381 (6)
C7	0.09342 (15)	0.3274 (5)	0.13327 (18)	0.0367 (7)
H2	0.37610	0.29340	0.28060	0.0580*
H2A	−0.009 (2)	0.116 (6)	0.182 (2)	0.062 (9)*
H2B	−0.0377 (18)	0.328 (7)	0.091 (2)	0.063 (9)*
H3	0.47420	0.54640	0.15710	0.0630*
H4	0.41550	0.79300	−0.01660	0.0590*
H5	0.25790	0.78020	−0.07170	0.0520*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0458 (5)	0.0516 (5)	0.0240 (4)	0.0062 (2)	0.0010 (3)	0.0025 (2)
N1	0.0421 (10)	0.0481 (10)	0.0218 (8)	0.0010 (8)	0.0038 (7)	−0.0002 (7)
N2	0.0419 (11)	0.0582 (12)	0.0282 (11)	−0.0013 (9)	0.0048 (8)	0.0087 (8)
C1	0.0429 (12)	0.0467 (11)	0.0278 (11)	0.0062 (9)	0.0038 (9)	−0.0062 (8)
C2	0.0472 (13)	0.0581 (14)	0.0376 (12)	0.0064 (11)	−0.0050 (10)	−0.0080 (10)
C3	0.0391 (12)	0.0645 (16)	0.0526 (15)	0.0011 (11)	−0.0001 (11)	−0.0144 (12)
C4	0.0458 (14)	0.0573 (15)	0.0456 (14)	−0.0084 (10)	0.0103 (11)	−0.0114 (10)
C5	0.0454 (13)	0.0546 (14)	0.0310 (11)	−0.0034 (10)	0.0067 (9)	−0.0056 (9)
C6	0.0443 (12)	0.0456 (11)	0.0242 (10)	0.0010 (9)	0.0023 (8)	−0.0057 (8)
C7	0.0425 (12)	0.0459 (13)	0.0215 (10)	0.0039 (9)	0.0017 (9)	−0.0031 (8)

Geometric parameters (Å, º) top

S1—C1	1.747 (2)	C2—C3	1.375 (4)
S1—C7	1.760 (2)	C3—C4	1.402 (3)
N1—C6	1.389 (3)	C4—C5	1.388 (4)
N1—C7	1.303 (3)	C5—C6	1.393 (3)
N2—C7	1.352 (3)	C2—H2	0.9500
N2—H2B	0.83 (2)	C3—H3	0.9500
N2—H2A	0.80 (2)	C4—H4	0.9500
C1—C6	1.410 (3)	C5—H5	0.9500
C1—C2	1.380 (3)

C1—S1—C7	88.64 (10)	N1—C6—C1	115.36 (18)
C6—N1—C7	110.53 (17)	N1—C6—C5	125.68 (19)
H2A—N2—H2B	117 (3)	S1—C7—N1	116.18 (16)
C7—N2—H2B	123.7 (18)	S1—C7—N2	118.60 (16)
C7—N2—H2A	115 (2)	N1—C7—N2	125.1 (2)
C2—C1—C6	122.2 (2)	C1—C2—H2	121.00
S1—C1—C6	109.29 (16)	C3—C2—H2	121.00
S1—C1—C2	128.54 (17)	C2—C3—H3	120.00
C1—C2—C3	118.3 (2)	C4—C3—H3	120.00
C2—C3—C4	120.7 (2)	C3—C4—H4	119.00
C3—C4—C5	121.0 (2)	C5—C4—H4	120.00
C4—C5—C6	118.8 (2)	C4—C5—H5	121.00
C1—C6—C5	119.0 (2)	C6—C5—H5	121.00

C7—S1—C1—C2	−179.8 (2)	S1—C1—C6—N1	0.0 (2)
C7—S1—C1—C6	0.41 (17)	S1—C1—C6—C5	−179.83 (17)
C1—S1—C7—N1	−0.79 (18)	C2—C1—C6—N1	−179.8 (2)
C1—S1—C7—N2	−176.53 (19)	C2—C1—C6—C5	0.4 (3)
C7—N1—C6—C1	−0.6 (3)	C1—C2—C3—C4	1.4 (4)
C7—N1—C6—C5	179.2 (2)	C2—C3—C4—C5	−0.6 (4)
C6—N1—C7—S1	0.9 (2)	C3—C4—C5—C6	−0.3 (4)
C6—N1—C7—N2	176.3 (2)	C4—C5—C6—N1	−179.4 (2)
S1—C1—C2—C3	179.0 (2)	C4—C5—C6—C1	0.4 (3)
C6—C1—C2—C3	−1.2 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···N1ⁱ	0.83 (2)	2.14 (2)	2.964 (3)	172 (2)
N2—H2A···N2ⁱⁱ	0.80 (2)	2.46 (2)	3.217 (3)	157 (2)

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

Experimental details

Crystal data
Chemical formula	C₇H₆N₂S
M_r	150.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	14.606 (4), 3.997 (1), 11.565 (4)
β (°)	94.47 (2)
V (Å³)	673.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.39
Crystal size (mm)	0.50 × 0.50 × 0.50

Data collection
Diffractometer	Stoe IPDS2 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2783, 1181, 1061
R_int	0.086
(sin θ/λ)_max (Å⁻¹)	0.598

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.143, 1.06
No. of reflections	1181
No. of parameters	99
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.31

Computer programs: X-AREA (Stoe & Cie, 2006), X-RED32 (Stoe & Cie, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···N1ⁱ	0.83 (2)	2.14 (2)	2.964 (3)	172 (2)
N2—H2A···N2ⁱⁱ	0.80 (2)	2.46 (2)	3.217 (3)	157 (2)

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

Acknowledgements

This work was supported by the Swiss National Science Foundation.

References

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