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

Qiu, Q.-M.; Cui, Y.-Z.; Zhao, Y.-H.; Jin, Q.-H.; Zhang, C.-L.

doi:10.1107/S1600536812049719

organic compounds

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ISSN: 2056-9890

Volume 69| Part 2| February 2013| Page o171

doi:10.1107/S1600536812049719

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

Qi-Ming Qiu,^a Yang-Zhe Cui,^a Yin-Hua Zhao,^a Qiong-Hua Jin ^a ^* and Cun-Lin Zhang ^b

^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 π–π 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 ,b , 2004 ). For the structure of the related compound 2-mercapto-benzothiazole, see: Chesick & Donohue (1971 ).

Experimental

Crystal data

C₇H₄N₂O₂S₂
M_r = 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 ) T_min = 0.789, T_max = 0.850
4092 measured reflections
1425 independent reflections
1104 reflections with I > 2σ(I)
R_int = 0.109

Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.165
S = 1.04
1425 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; 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/S1600536812049719/cv5367sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812049719/cv5367Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812049719/cv5367Isup3.cml

checkCIF report

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 π–π 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.

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

	Fig. 1. The molecular structure of (I) showing the atomic numbering scheme and displacement ellipsoids drawn at the 50% probability level.
	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

C₇H₄N₂O₂S₂	F(000) = 432
M_r = 212.24	D_x = 1.755 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1148 reflections
a = 3.8645 (2) Å	θ = 2.7–23.7°
b = 26.345 (2) Å	µ = 0.62 mm⁻¹
c = 7.8961 (4) Å	T = 298 K
β = 92.509 (1)°	Block, colourless
V = 803.14 (9) Å³	0.40 × 0.35 × 0.27 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1425 independent reflections
Radiation source: fine-focus sealed tube	1104 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.109
phi and ω scans	θ_max = 25.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −4→4
T_min = 0.789, T_max = 0.850	k = −30→31
4092 measured reflections	l = −9→6

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.165	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0915P)²] where P = (F_o² + 2F_c²)/3
1425 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

C₇H₄N₂O₂S₂	V = 803.14 (9) Å³
M_r = 212.24	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 3.8645 (2) Å	µ = 0.62 mm⁻¹
b = 26.345 (2) Å	T = 298 K
c = 7.8961 (4) Å	0.40 × 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)
T_min = 0.789, T_max = 0.850	R_int = 0.109
4092 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	0 restraints
wR(F²) = 0.165	H-atom parameters constrained
S = 1.04	Δρ_max = 0.45 e Å⁻³
1425 reflections	Δρ_min = −0.42 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
N1	0.2970 (8)	0.05823 (12)	0.4296 (4)	0.0383 (8)
H1	0.2434	0.0278	0.3985	0.046*
N2	0.8798 (11)	0.20738 (15)	0.0513 (6)	0.0559 (10)
O1	0.9284 (13)	0.24753 (15)	0.1198 (5)	0.1031 (17)
O2	0.9722 (12)	0.19831 (14)	−0.0880 (5)	0.0844 (13)
S1	0.3759 (3)	0.13687 (4)	0.60511 (13)	0.0414 (4)
S2	0.0806 (3)	0.04194 (4)	0.73917 (14)	0.0450 (4)
C1	0.2447 (10)	0.07491 (14)	0.5857 (5)	0.0360 (9)
C2	0.4399 (10)	0.09190 (14)	0.3216 (5)	0.0350 (9)
C3	0.5018 (10)	0.13824 (14)	0.3978 (5)	0.0350 (9)
C4	0.6477 (10)	0.17709 (15)	0.3110 (5)	0.0403 (10)
H4	0.6936	0.2085	0.3610	0.048*
C5	0.7219 (11)	0.16726 (15)	0.1476 (5)	0.0410 (10)
C6	0.6620 (11)	0.12160 (16)	0.0691 (6)	0.0444 (10)
H6	0.7212	0.1168	−0.0426	0.053*
C7	0.5160 (11)	0.08351 (16)	0.1556 (5)	0.0429 (10)
H7	0.4684	0.0524	0.1041	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.043 (2)	0.0305 (17)	0.0407 (19)	−0.0046 (14)	−0.0031 (16)	−0.0022 (15)
N2	0.066 (3)	0.043 (2)	0.060 (3)	0.0034 (18)	0.013 (2)	0.010 (2)
O1	0.182 (5)	0.045 (2)	0.088 (3)	−0.028 (2)	0.066 (3)	−0.007 (2)
O2	0.129 (4)	0.067 (2)	0.060 (2)	−0.016 (2)	0.038 (2)	0.008 (2)
S1	0.0487 (7)	0.0354 (6)	0.0401 (6)	−0.0059 (4)	0.0029 (5)	−0.0051 (4)
S2	0.0497 (7)	0.0425 (6)	0.0427 (6)	−0.0076 (5)	0.0023 (5)	0.0004 (4)
C1	0.028 (2)	0.035 (2)	0.043 (2)	0.0026 (16)	−0.0063 (17)	−0.0030 (17)
C2	0.029 (2)	0.033 (2)	0.042 (2)	0.0016 (16)	−0.0089 (17)	−0.0010 (17)
C3	0.031 (2)	0.032 (2)	0.041 (2)	0.0034 (15)	−0.0022 (17)	−0.0017 (16)
C4	0.042 (2)	0.033 (2)	0.045 (2)	0.0029 (17)	0.0004 (19)	−0.0005 (17)
C5	0.040 (2)	0.037 (2)	0.047 (2)	0.0041 (17)	0.0051 (19)	0.0043 (19)
C6	0.050 (3)	0.047 (2)	0.035 (2)	0.005 (2)	0.0008 (19)	−0.0003 (19)
C7	0.049 (3)	0.041 (2)	0.038 (2)	0.0025 (18)	−0.0031 (19)	−0.0065 (19)

Geometric parameters (Å, º) top

N1—C1	1.332 (5)	C2—C7	1.373 (5)
N1—C2	1.364 (5)	C2—C3	1.378 (5)
N1—H1	0.8600	C3—C4	1.367 (5)
N2—O2	1.196 (5)	C4—C5	1.359 (5)
N2—O1	1.199 (5)	C4—H4	0.9300
N2—C5	1.452 (5)	C5—C6	1.368 (6)
S1—C1	1.714 (4)	C6—C7	1.351 (6)
S1—C3	1.728 (4)	C6—H6	0.9300
S2—C1	1.641 (4)	C7—H7	0.9300

C1—N1—C2	116.5 (3)	C4—C3—S1	129.0 (3)
C1—N1—H1	121.8	C2—C3—S1	110.2 (3)
C2—N1—H1	121.8	C5—C4—C3	116.3 (4)
O2—N2—O1	123.0 (4)	C5—C4—H4	121.9
O2—N2—C5	119.1 (4)	C3—C4—H4	121.9
O1—N2—C5	117.9 (4)	C4—C5—C6	124.0 (4)
C1—S1—C3	91.69 (18)	C4—C5—N2	118.0 (4)
N1—C1—S2	126.0 (3)	C6—C5—N2	118.0 (4)
N1—C1—S1	109.9 (3)	C7—C6—C5	119.4 (4)
S2—C1—S1	124.1 (2)	C7—C6—H6	120.3
N1—C2—C7	127.0 (4)	C5—C6—H6	120.3
N1—C2—C3	111.7 (3)	C6—C7—C2	118.3 (4)
C7—C2—C3	121.3 (4)	C6—C7—H7	120.8
C4—C3—C2	120.8 (4)	C2—C7—H7	120.8

C2—N1—C1—S2	−179.4 (3)	S1—C3—C4—C5	179.8 (3)
C2—N1—C1—S1	0.5 (4)	C3—C4—C5—C6	−0.6 (6)
C3—S1—C1—N1	−0.3 (3)	C3—C4—C5—N2	−179.5 (4)
C3—S1—C1—S2	179.6 (3)	O2—N2—C5—C4	174.2 (4)
C1—N1—C2—C7	−179.7 (4)	O1—N2—C5—C4	−1.9 (7)
C1—N1—C2—C3	−0.4 (5)	O2—N2—C5—C6	−4.8 (7)
N1—C2—C3—C4	179.4 (4)	O1—N2—C5—C6	179.2 (5)
C7—C2—C3—C4	−1.3 (6)	C4—C5—C6—C7	1.0 (7)
N1—C2—C3—S1	0.2 (4)	N2—C5—C6—C7	179.8 (4)
C7—C2—C3—S1	179.5 (3)	C5—C6—C7—C2	−1.4 (6)
C1—S1—C3—C4	−179.1 (4)	N1—C2—C7—C6	−179.2 (4)
C1—S1—C3—C2	0.1 (3)	C3—C2—C7—C6	1.6 (6)
C2—C3—C4—C5	0.7 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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−1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₇H₄N₂O₂S₂
M_r	212.24
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	3.8645 (2), 26.345 (2), 7.8961 (4)
β (°)	92.509 (1)
V (Å³)	803.14 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.62
Crystal size (mm)	0.40 × 0.35 × 0.27

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.789, 0.850
No. of measured, independent and observed [I > 2σ(I)] reflections	4092, 1425, 1104
R_int	0.109
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.165, 1.04
No. of reflections	1425
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	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−1/2, −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

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