organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

1,3-Benzo­thia­zol-2-amine

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[Goubitz, K., Sonneveld, E. J. & Schenk, H. (2001). Z. Kristallogr. 216, 176-181.]). For related structures containing the title compound, see: Martínez-Martínez et al. (2003[Martínez-Martínez, F. J., García-Báez, E. V., Höpfl, H. & Padilla-Martínez, I. I. (2003). Acta Cryst. E59, o1628-o1630.]); Padilla-Martínez et al. (2003[Padilla-Martínez, I. I., García-Báez, E. V., Höpfl, H. & Martínez-Martínez, F. J. I. (2003). Acta Cryst. C59, o544-o546.]); Wang et al. (2008[Wang, Y.-Y., Hu, R.-D. & Wang, Y.-J. (2008). Acta Cryst. E64, o1442.]). For a description of the Cambridge Structural Database, see: Allen (2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]).

[Scheme 1]

Experimental

Crystal data
  • C7H6N2S

  • Mr = 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)

  • Rint = 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

  • Δρmax = 0.38 e Å−3

  • Δρmin = −0.31 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Stoe & Cie (2006). X-AREA and X-RED32. Stoe & Cie, Darmstadt, Germany.]); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2006[Stoe & Cie (2006). X-AREA and X-RED32. Stoe & Cie, Darmstadt, Germany.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]) and Mercury (Macrae et al., 2006[Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453-457.]); software used to prepare material for publication: SHELXL97.

Supporting information


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 Rf 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.

Refinement top

All the H-atoms could be located in difference electron-density maps. The amino H-atoms were refined isotropically with distance restraints: N—H = 0.82 (2) Å. The aromatic H-atoms were included in calculated postitions and treated as riding atoms: C—H = 0.95 Å with Uiso(H) = 1.2Ueq(parent C-atom).

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
[Figure 1] Fig. 1. A view of the molecular structure of the title compound, with the displacement ellipsoids drawn at the 50% probability level.
[Figure 2] 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
C7H6N2SF(000) = 312
Mr = 150.20Dx = 1.482 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 42133 reflections
a = 14.606 (4) Åθ = 3.5–25.6°
b = 3.997 (1) ŵ = 0.39 mm1
c = 11.565 (4) ÅT = 173 K
β = 94.47 (2)°Block, colourless
V = 673.1 (3) Å30.50 × 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 tubeRint = 0.086
Graphite monochromatorθmax = 25.2°, θmin = 3.5°
ϕ and ω scansh = 1715
2783 measured reflectionsk = 44
1181 independent reflectionsl = 1313
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.143H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.1031P)2 + 0.0494P]
where P = (Fo2 + 2Fc2)/3
1181 reflections(Δ/σ)max < 0.001
99 parametersΔρmax = 0.38 e Å3
2 restraintsΔρmin = 0.31 e Å3
Crystal data top
C7H6N2SV = 673.1 (3) Å3
Mr = 150.20Z = 4
Monoclinic, P21/cMo Kα radiation
a = 14.606 (4) ŵ = 0.39 mm1
b = 3.997 (1) ÅT = 173 K
c = 11.565 (4) Å0.50 × 0.50 × 0.50 mm
β = 94.47 (2)°
Data collection top
Stoe IPDS-2
diffractometer
1061 reflections with I > 2σ(I)
2783 measured reflectionsRint = 0.086
1181 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0522 restraints
wR(F2) = 0.143H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.38 e Å3
1181 reflectionsΔρmin = 0.31 e Å3
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
xyzUiso*/Ueq
S10.17155 (4)0.19806 (15)0.24812 (4)0.0406 (3)
N10.12810 (12)0.4914 (5)0.04966 (13)0.0373 (5)
N20.00290 (14)0.2707 (6)0.14135 (17)0.0427 (7)
C10.25983 (15)0.3777 (6)0.17558 (17)0.0391 (7)
C20.35252 (17)0.3886 (7)0.2091 (2)0.0481 (8)
C30.40994 (17)0.5406 (7)0.1364 (2)0.0523 (8)
C40.37475 (18)0.6870 (6)0.0321 (2)0.0492 (8)
C50.28136 (17)0.6797 (6)0.0011 (2)0.0435 (7)
C60.22260 (15)0.5222 (5)0.07108 (17)0.0381 (6)
C70.09342 (15)0.3274 (5)0.13327 (18)0.0367 (7)
H20.376100.293400.280600.0580*
H2A0.009 (2)0.116 (6)0.182 (2)0.062 (9)*
H2B0.0377 (18)0.328 (7)0.091 (2)0.063 (9)*
H30.474200.546400.157100.0630*
H40.415500.793000.016600.0590*
H50.257900.780200.071700.0520*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0458 (5)0.0516 (5)0.0240 (4)0.0062 (2)0.0010 (3)0.0025 (2)
N10.0421 (10)0.0481 (10)0.0218 (8)0.0010 (8)0.0038 (7)0.0002 (7)
N20.0419 (11)0.0582 (12)0.0282 (11)0.0013 (9)0.0048 (8)0.0087 (8)
C10.0429 (12)0.0467 (11)0.0278 (11)0.0062 (9)0.0038 (9)0.0062 (8)
C20.0472 (13)0.0581 (14)0.0376 (12)0.0064 (11)0.0050 (10)0.0080 (10)
C30.0391 (12)0.0645 (16)0.0526 (15)0.0011 (11)0.0001 (11)0.0144 (12)
C40.0458 (14)0.0573 (15)0.0456 (14)0.0084 (10)0.0103 (11)0.0114 (10)
C50.0454 (13)0.0546 (14)0.0310 (11)0.0034 (10)0.0067 (9)0.0056 (9)
C60.0443 (12)0.0456 (11)0.0242 (10)0.0010 (9)0.0023 (8)0.0057 (8)
C70.0425 (12)0.0459 (13)0.0215 (10)0.0039 (9)0.0017 (9)0.0031 (8)
Geometric parameters (Å, º) top
S1—C11.747 (2)C2—C31.375 (4)
S1—C71.760 (2)C3—C41.402 (3)
N1—C61.389 (3)C4—C51.388 (4)
N1—C71.303 (3)C5—C61.393 (3)
N2—C71.352 (3)C2—H20.9500
N2—H2B0.83 (2)C3—H30.9500
N2—H2A0.80 (2)C4—H40.9500
C1—C61.410 (3)C5—H50.9500
C1—C21.380 (3)
C1—S1—C788.64 (10)N1—C6—C1115.36 (18)
C6—N1—C7110.53 (17)N1—C6—C5125.68 (19)
H2A—N2—H2B117 (3)S1—C7—N1116.18 (16)
C7—N2—H2B123.7 (18)S1—C7—N2118.60 (16)
C7—N2—H2A115 (2)N1—C7—N2125.1 (2)
C2—C1—C6122.2 (2)C1—C2—H2121.00
S1—C1—C6109.29 (16)C3—C2—H2121.00
S1—C1—C2128.54 (17)C2—C3—H3120.00
C1—C2—C3118.3 (2)C4—C3—H3120.00
C2—C3—C4120.7 (2)C3—C4—H4119.00
C3—C4—C5121.0 (2)C5—C4—H4120.00
C4—C5—C6118.8 (2)C4—C5—H5121.00
C1—C6—C5119.0 (2)C6—C5—H5121.00
C7—S1—C1—C2179.8 (2)S1—C1—C6—N10.0 (2)
C7—S1—C1—C60.41 (17)S1—C1—C6—C5179.83 (17)
C1—S1—C7—N10.79 (18)C2—C1—C6—N1179.8 (2)
C1—S1—C7—N2176.53 (19)C2—C1—C6—C50.4 (3)
C7—N1—C6—C10.6 (3)C1—C2—C3—C41.4 (4)
C7—N1—C6—C5179.2 (2)C2—C3—C4—C50.6 (4)
C6—N1—C7—S10.9 (2)C3—C4—C5—C60.3 (4)
C6—N1—C7—N2176.3 (2)C4—C5—C6—N1179.4 (2)
S1—C1—C2—C3179.0 (2)C4—C5—C6—C10.4 (3)
C6—C1—C2—C31.2 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···N1i0.83 (2)2.14 (2)2.964 (3)172 (2)
N2—H2A···N2ii0.80 (2)2.46 (2)3.217 (3)157 (2)
Symmetry codes: (i) x, y+1, z; (ii) x, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC7H6N2S
Mr150.20
Crystal system, space groupMonoclinic, P21/c
Temperature (K)173
a, b, c (Å)14.606 (4), 3.997 (1), 11.565 (4)
β (°) 94.47 (2)
V3)673.1 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.39
Crystal size (mm)0.50 × 0.50 × 0.50
Data collection
DiffractometerStoe IPDS2
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
2783, 1181, 1061
Rint0.086
(sin θ/λ)max1)0.598
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.052, 0.143, 1.06
No. of reflections1181
No. of parameters99
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N2—H2B···N1i0.83 (2)2.14 (2)2.964 (3)172 (2)
N2—H2A···N2ii0.80 (2)2.46 (2)3.217 (3)157 (2)
Symmetry codes: (i) x, y+1, z; (ii) x, y1/2, z+1/2.
 

Acknowledgements

This work was supported by the Swiss National Science Foundation.

References

First citationAllen, F. H. (2002). Acta Cryst. B58, 380–388.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationGoubitz, K., Sonneveld, E. J. & Schenk, H. (2001). Z. Kristallogr. 216, 176–181.  Web of Science CSD CrossRef CAS Google Scholar
First citationMacrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationMartínez-Martínez, F. J., García-Báez, E. V., Höpfl, H. & Padilla-Martínez, I. I. (2003). Acta Cryst. E59, o1628–o1630.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationPadilla-Martínez, I. I., García-Báez, E. V., Höpfl, H. & Martínez-Martínez, F. J. I. (2003). Acta Cryst. C59, o544–o546.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationStoe & Cie (2006). X-AREA and X-RED32. Stoe & Cie, Darmstadt, Germany.  Google Scholar
First citationWang, Y.-Y., Hu, R.-D. & Wang, Y.-J. (2008). Acta Cryst. E64, o1442.  Web of Science CSD CrossRef IUCr Journals Google Scholar

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COMMUNICATIONS
ISSN: 2056-9890
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