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ISSN: 2056-9890

6-Nitro-1,3-benzo­thia­zole-2(3H)-thione

aDepartment of Chemistry, Capital Normal University, Beijing 100048, People's Republic of China, and bKey Laboratory of Terahertz Optoelectronics, Ministry of Education, Department of Physics, Capital Normal University, Beijing 100048, People's Republic of China
*Correspondence e-mail: jinqh204@163.com

(Received 20 November 2012; accepted 4 December 2012; online 4 January 2013)

In the title mol­ecule, C7H4N2O2S2, the nitro group is twisted by 5.5 (1)° from the plane of the attached benzene ring. In the crystal, N—H⋯S hydrogen bonds link pairs of mol­ecules into inversion dimers, which are linked by weak C—H⋯O inter­actions into sheets parallel to (101). The crystal packing exhibits short inter­molecular S⋯O contacts of 3.054 (4) Å and ππ inter­actions of 3.588 (5) Å between the centroids of the five- and six-membered rings of neighbouring mol­ecules.

Related literature

For coordination compounds based on 2-mercapto-6-nitro­benzothia­zole ligands, see: Ma et al. (2003a[Ma, C. L., Jiang, Q. & Zhang, R. F. (2003a). Can. J. Chem. 81, 825-831.],b[Ma, C. L., Jiang, Q. & Zhang, R. F. (2003b). Appl. Organomet. Chem. 17, 623-630.], 2004[Ma, C. L., Jiang, Q. & Zhang, R. F. (2004). Polyhedron, 23, 779-786.]). For the structure of the related compound 2-mercapto-benzothia­zole, see: Chesick & Donohue (1971[Chesick, J. P. & Donohue, J. (1971). Acta Cryst. B27, 1441-1444.]).

[Scheme 1]

Experimental

Crystal data
  • C7H4N2O2S2

  • Mr = 212.24

  • Monoclinic, P 21 /n

  • a = 3.8645 (2) Å

  • b = 26.345 (2) Å

  • c = 7.8961 (4) Å

  • β = 92.509 (1)°

  • V = 803.14 (9) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.62 mm−1

  • T = 298 K

  • 0.40 × 0.35 × 0.27 mm

Data collection
  • Bruker SMART CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2007[Bruker (2007). SMART, SAINT-Plus and SADABS. Bruker AXS Inc., Wisconsin, USA.]) Tmin = 0.789, Tmax = 0.850

  • 4092 measured reflections

  • 1425 independent reflections

  • 1104 reflections with I > 2σ(I)

  • Rint = 0.109

Refinement
  • R[F2 > 2σ(F2)] = 0.063

  • wR(F2) = 0.165

  • S = 1.04

  • 1425 reflections

  • 118 parameters

  • H-atom parameters constrained

  • Δρmax = 0.45 e Å−3

  • Δρmin = −0.42 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1⋯S2i 0.86 2.45 3.271 (3) 160
C4—H4⋯O1ii 0.93 2.60 3.285 (6) 131
Symmetry codes: (i) -x, -y, -z+1; (ii) [x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}].

Data collection: SMART (Bruker, 2007[Bruker (2007). SMART, SAINT-Plus and SADABS. Bruker AXS Inc., Wisconsin, USA.]); cell refinement: SAINT-Plus (Bruker, 2007[Bruker (2007). SMART, SAINT-Plus and SADABS. Bruker AXS Inc., Wisconsin, USA.]); data reduction: SAINT-Plus; 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: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

Metal-organic supramolecular compounds have received much attention due to their structural diversities and potential applications as new materials. The ligand 2-mercapto-6-nitrobenzothiazole (MNBT) is excellent in building supramolecular structures. However, to our best knowledge, only a few Ag(I)-MNBT (MNBT = 2-mercapto-6-nitrobenzothiazole) framework structures have been reported (Ma et al., 2003a,b; 2004). The title compound, (I), was unexpectedly obtained when we tried to synthesize Ag(I)-MNBT complexes containing bis(diphenylphosphino)methane.

In (I) (Fig.1), the nitro group is twisted at 5.5 (1)° from the plane of the attached benzene ring. Intermolecular N—H···S hydrogen bonds (Table 1) link two molecules into centrosymmetric dimer, and weak C—H···O interactions (Table 1) link further these dimers into sheets parallel to (101). The hydrogen bond N—H···S is similar to that reported for 2-mercapto-benzothiazole (Chesick & Donohue, 1971). The crystal packing (Fig. 2) exhibits short intermolecular S···O contacts of 3.054 (4) Å and ππ interactions proved by short distance of 3.588 (5) Å between the centroids of the five- and six-membered rings from the neighbouring molecules.

Related literature top

For coordination compounds based on 2-mercapto-6-nitrobenzothiazole ligands, see: Ma et al. (2003a,b, 2004). For the structure of the related compound 2-mercapto-benzothiazole, see: Chesick & Donohue (1971).

Experimental top

A mixture of AgCl (0.2 mmol) and bis(diphenylphosphino)methane (0.2 mmol) in MeOH and CH2Cl2 (10 mL, v/v = 1:1) was stirred for 3 h. The insoluble residues were removed by filtration. The filtrate was then evaporated slowly at room temperature for a week to yield colourless crystalline product.

The title compound was prepared by dissolving 0.0587 g colourless product mentioned above in MeOH and CH2Cl2 (10 mL, v/v = 3:7), adding 2-mercapto-6-nitrobenzothiazole (0.2 mmol) into the solution, stirring for 4 h. Subsequent slow evaporation of the yellow filtrate resulted in the formation of yellow crystals.

Refinement top

All H atoms were geometrically positioned [C—H 0.93 Å; N—H 0.86 Å], and included in the final refinement in the riding model approximation, with Uiso(H) = 1.2 Ueq of the parent atom.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); 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
[Figure 1] Fig. 1. The molecular structure of (I) showing the atomic numbering scheme and displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. A portion of the crystal packing viewed approximately along the a axis. Dashed lines indicate short N···S and O···S contacts. H atoms omitted for clarity.
6-Nitro-1,3-benzothiazole-2(3H)-thione top
Crystal data top
C7H4N2O2S2F(000) = 432
Mr = 212.24Dx = 1.755 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1148 reflections
a = 3.8645 (2) Åθ = 2.7–23.7°
b = 26.345 (2) ŵ = 0.62 mm1
c = 7.8961 (4) ÅT = 298 K
β = 92.509 (1)°Block, colourless
V = 803.14 (9) Å30.40 × 0.35 × 0.27 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
1425 independent reflections
Radiation source: fine-focus sealed tube1104 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.109
phi and ω scansθmax = 25.0°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
h = 44
Tmin = 0.789, Tmax = 0.850k = 3031
4092 measured reflectionsl = 96
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)] = 0.063Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.165H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0915P)2]
where P = (Fo2 + 2Fc2)/3
1425 reflections(Δ/σ)max < 0.001
118 parametersΔρmax = 0.45 e Å3
0 restraintsΔρmin = 0.42 e Å3
Crystal data top
C7H4N2O2S2V = 803.14 (9) Å3
Mr = 212.24Z = 4
Monoclinic, P21/nMo Kα radiation
a = 3.8645 (2) ŵ = 0.62 mm1
b = 26.345 (2) ÅT = 298 K
c = 7.8961 (4) Å0.40 × 0.35 × 0.27 mm
β = 92.509 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
1425 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
1104 reflections with I > 2σ(I)
Tmin = 0.789, Tmax = 0.850Rint = 0.109
4092 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0630 restraints
wR(F2) = 0.165H-atom parameters constrained
S = 1.04Δρmax = 0.45 e Å3
1425 reflectionsΔρmin = 0.42 e Å3
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
xyzUiso*/Ueq
N10.2970 (8)0.05823 (12)0.4296 (4)0.0383 (8)
H10.24340.02780.39850.046*
N20.8798 (11)0.20738 (15)0.0513 (6)0.0559 (10)
O10.9284 (13)0.24753 (15)0.1198 (5)0.1031 (17)
O20.9722 (12)0.19831 (14)0.0880 (5)0.0844 (13)
S10.3759 (3)0.13687 (4)0.60511 (13)0.0414 (4)
S20.0806 (3)0.04194 (4)0.73917 (14)0.0450 (4)
C10.2447 (10)0.07491 (14)0.5857 (5)0.0360 (9)
C20.4399 (10)0.09190 (14)0.3216 (5)0.0350 (9)
C30.5018 (10)0.13824 (14)0.3978 (5)0.0350 (9)
C40.6477 (10)0.17709 (15)0.3110 (5)0.0403 (10)
H40.69360.20850.36100.048*
C50.7219 (11)0.16726 (15)0.1476 (5)0.0410 (10)
C60.6620 (11)0.12160 (16)0.0691 (6)0.0444 (10)
H60.72120.11680.04260.053*
C70.5160 (11)0.08351 (16)0.1556 (5)0.0429 (10)
H70.46840.05240.10410.052*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.043 (2)0.0305 (17)0.0407 (19)0.0046 (14)0.0031 (16)0.0022 (15)
N20.066 (3)0.043 (2)0.060 (3)0.0034 (18)0.013 (2)0.010 (2)
O10.182 (5)0.045 (2)0.088 (3)0.028 (2)0.066 (3)0.007 (2)
O20.129 (4)0.067 (2)0.060 (2)0.016 (2)0.038 (2)0.008 (2)
S10.0487 (7)0.0354 (6)0.0401 (6)0.0059 (4)0.0029 (5)0.0051 (4)
S20.0497 (7)0.0425 (6)0.0427 (6)0.0076 (5)0.0023 (5)0.0004 (4)
C10.028 (2)0.035 (2)0.043 (2)0.0026 (16)0.0063 (17)0.0030 (17)
C20.029 (2)0.033 (2)0.042 (2)0.0016 (16)0.0089 (17)0.0010 (17)
C30.031 (2)0.032 (2)0.041 (2)0.0034 (15)0.0022 (17)0.0017 (16)
C40.042 (2)0.033 (2)0.045 (2)0.0029 (17)0.0004 (19)0.0005 (17)
C50.040 (2)0.037 (2)0.047 (2)0.0041 (17)0.0051 (19)0.0043 (19)
C60.050 (3)0.047 (2)0.035 (2)0.005 (2)0.0008 (19)0.0003 (19)
C70.049 (3)0.041 (2)0.038 (2)0.0025 (18)0.0031 (19)0.0065 (19)
Geometric parameters (Å, º) top
N1—C11.332 (5)C2—C71.373 (5)
N1—C21.364 (5)C2—C31.378 (5)
N1—H10.8600C3—C41.367 (5)
N2—O21.196 (5)C4—C51.359 (5)
N2—O11.199 (5)C4—H40.9300
N2—C51.452 (5)C5—C61.368 (6)
S1—C11.714 (4)C6—C71.351 (6)
S1—C31.728 (4)C6—H60.9300
S2—C11.641 (4)C7—H70.9300
C1—N1—C2116.5 (3)C4—C3—S1129.0 (3)
C1—N1—H1121.8C2—C3—S1110.2 (3)
C2—N1—H1121.8C5—C4—C3116.3 (4)
O2—N2—O1123.0 (4)C5—C4—H4121.9
O2—N2—C5119.1 (4)C3—C4—H4121.9
O1—N2—C5117.9 (4)C4—C5—C6124.0 (4)
C1—S1—C391.69 (18)C4—C5—N2118.0 (4)
N1—C1—S2126.0 (3)C6—C5—N2118.0 (4)
N1—C1—S1109.9 (3)C7—C6—C5119.4 (4)
S2—C1—S1124.1 (2)C7—C6—H6120.3
N1—C2—C7127.0 (4)C5—C6—H6120.3
N1—C2—C3111.7 (3)C6—C7—C2118.3 (4)
C7—C2—C3121.3 (4)C6—C7—H7120.8
C4—C3—C2120.8 (4)C2—C7—H7120.8
C2—N1—C1—S2179.4 (3)S1—C3—C4—C5179.8 (3)
C2—N1—C1—S10.5 (4)C3—C4—C5—C60.6 (6)
C3—S1—C1—N10.3 (3)C3—C4—C5—N2179.5 (4)
C3—S1—C1—S2179.6 (3)O2—N2—C5—C4174.2 (4)
C1—N1—C2—C7179.7 (4)O1—N2—C5—C41.9 (7)
C1—N1—C2—C30.4 (5)O2—N2—C5—C64.8 (7)
N1—C2—C3—C4179.4 (4)O1—N2—C5—C6179.2 (5)
C7—C2—C3—C41.3 (6)C4—C5—C6—C71.0 (7)
N1—C2—C3—S10.2 (4)N2—C5—C6—C7179.8 (4)
C7—C2—C3—S1179.5 (3)C5—C6—C7—C21.4 (6)
C1—S1—C3—C4179.1 (4)N1—C2—C7—C6179.2 (4)
C1—S1—C3—C20.1 (3)C3—C2—C7—C61.6 (6)
C2—C3—C4—C50.7 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···S2i0.862.453.271 (3)160
C4—H4···O1ii0.932.603.285 (6)131
Symmetry codes: (i) x, y, z+1; (ii) x1/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC7H4N2O2S2
Mr212.24
Crystal system, space groupMonoclinic, P21/n
Temperature (K)298
a, b, c (Å)3.8645 (2), 26.345 (2), 7.8961 (4)
β (°) 92.509 (1)
V3)803.14 (9)
Z4
Radiation typeMo Kα
µ (mm1)0.62
Crystal size (mm)0.40 × 0.35 × 0.27
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2007)
Tmin, Tmax0.789, 0.850
No. of measured, independent and
observed [I > 2σ(I)] reflections
4092, 1425, 1104
Rint0.109
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.063, 0.165, 1.04
No. of reflections1425
No. of parameters118
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.45, 0.42

Computer programs: SMART (Bruker, 2007), SAINT-Plus (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···S2i0.862.453.271 (3)160
C4—H4···O1ii0.932.603.285 (6)131
Symmetry codes: (i) x, y, z+1; (ii) x1/2, y+1/2, z+1/2.
 

Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant No. 21171119), the National High Technology Research and Development Program 863 of China (grant No. 2012 A A063201), Beijing Personnel Bureau, the National Keystone Basic Research Program (973 Program) under grant Nos. 2007CB310408 and 2006CB302901, and the Committee of Education of the Beijing Foundation of China (grant No. KM201210028020).

References

First citationBruker (2007). SMART, SAINT-Plus and SADABS. Bruker AXS Inc., Wisconsin, USA.
First citationChesick, J. P. & Donohue, J. (1971). Acta Cryst. B27, 1441–1444.  CSD CrossRef CAS IUCr Journals Web of Science
First citationMa, C. L., Jiang, Q. & Zhang, R. F. (2003a). Can. J. Chem. 81, 825–831.  Web of Science CSD CrossRef CAS
First citationMa, C. L., Jiang, Q. & Zhang, R. F. (2003b). Appl. Organomet. Chem. 17, 623–630.  Web of Science CSD CrossRef CAS
First citationMa, C. L., Jiang, Q. & Zhang, R. F. (2004). Polyhedron, 23, 779–786.  Web of Science CSD CrossRef CAS
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals

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ISSN: 2056-9890
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