2-Amino-6-nitro-1,3-benzothia­zol-3-ium hydrogen sulfate

Qian, H.-F.; Huang, W.

doi:10.1107/S1600536811027620

organic compounds

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Volume 67| Part 8| August 2011| Page o2044

doi:10.1107/S1600536811027620

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2-Amino-6-nitro-1,3-benzothiazol-3-ium hydrogen sulfate

Hui-Fen Qian ^a ^* and Wei Huang ^b

^aCollege of Sciences, Nanjing University of Technology, Nanjing 210009, People's Republic of China, and ^bState Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, People's Republic of China
^*Correspondence e-mail: qhf@njut.edu.cn

(Received 8 July 2011; accepted 11 July 2011; online 16 July 2011)

In the title molecular salt, C₇H₆N₃O₂S⁺·HSO₄⁻, the 2-amino-6-nitro-1,3-benzothiazole ring system is essentially planar [mean deviation = 0.0605 (4) Å]. In the crystal, N—H⋯O and O—H⋯O hydrogen-bonding interactions result in a layer motif.

Related literature

For related compounds, see Glidewell et al. (2001 ); Lynch (2002 ); Lynch & Duckhouse (2001 ); You et al. (2009 ).

Experimental

Crystal data

C₇H₆N₃O₂S⁺·HSO₄⁻
M_r = 293.28
Monoclinic, P 2₁ /n
a = 7.849 (6) Å
b = 16.219 (12) Å
c = 9.191 (7) Å
β = 108.584 (10)°
V = 1109.0 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.51 mm⁻¹
T = 291 K
0.16 × 0.14 × 0.12 mm

Data collection

Bruker 1K CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.923, T_max = 0.942
5436 measured reflections
1958 independent reflections
1586 reflections with I > 2σ(I)
R_int = 0.097

Refinement

R[F² > 2σ(F²)] = 0.061
wR(F²) = 0.159
S = 0.98
1958 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4ⁱ	0.86	1.97	2.825 (4)	171
N2—H2A⋯O6ⁱ	0.86	2.02	2.867 (4)	170
N2—H2B⋯O6ⁱⁱ	0.86	2.10	2.888 (4)	151
O3—H3A⋯O4ⁱⁱⁱ	0.82	1.86	2.664 (4)	166
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) -x+1, -y+2, -z+2.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811027620/ff2020sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811027620/ff2020Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811027620/ff2020Isup3.cml

checkCIF report

Comment top

There have been three single-crystal structural investigations on 2-amino-6-nitro-1,3-benzothiazole, namely 2-amino-6-nitro-1,3-benzothiazole (Glidewell et al., 2001),its monohydrate (Lynch et al., 2002) and its PtCl₂ complex (Lynch & Duckhouse, 2001). We have previously reported the single-crystal structure of 2-aminobenzimidazolium hydrogen sulfate (You et al., 2009). In this work, we describe the single-crystal structure of a hydrogen sulfate salt of 2-amino-6-nitro-1,3-benzothiazole.

The atom-numbering scheme of the title compound is shown in Fig. 1, while selected bond distances and bond angles are given in Table 1. The 2-amino-6-nitro-1,3-benzothiazole skeleton of the title compound is is essentially planar with the mean deviation of 0.0605 (4) Å. The proton is delocalized within the thiozole ring although it is added to the nitrogen atom. With regard to the hydrogen sulfate anion, the hydrogen atom is added to the O3 atom of SO₄ group due to the obviously longer O3–S2 bond length. In the crystal packing, N—H···O and O—H···O hydrogen-bond interactions are found between adjacent molecules giving rise to a layer motif.

Related literature top

For related compounds, see Glidewell et al. (2001); Lynch et al. (2002); Lynch & Duckhouse (2001); You et al. (2009).

Experimental top

The treatment of 2-amino-6-nitro-1,3-benzothiazole dissolved in methanol with an excess of sulfuric acid yields the title compound. Single crystals suitable for X-ray diffraction measurement were obtained after 7 days' slow evaporation of the mother liquid at room temperature in air. Anal. Calcd. For C₇H₆N₃O₂S⁺.HSO₄^-: C, 28.67; H, 2.41; N, 14.33%. Found: C, 28.53; H, 2.66; N, 14.44%.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. An ORTEP drawing of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

2-Amino-6-nitro-1,3-benzothiazol-3-ium hydrogen sulfate top

Crystal data top

C₇H₆N₃O₂S⁺·HSO₄⁻	F(000) = 600
M_r = 293.28	D_x = 1.757 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2618 reflections
a = 7.849 (6) Å	θ = 2.3–28.0°
b = 16.219 (12) Å	µ = 0.51 mm⁻¹
c = 9.191 (7) Å	T = 291 K
β = 108.584 (10)°	Block, colourless
V = 1109.0 (14) Å³	0.16 × 0.14 × 0.12 mm
Z = 4

Data collection top

Bruker 1K CCD area-detector diffractometer	1958 independent reflections
Radiation source: fine-focus sealed tube	1586 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.097
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −9→6
T_min = 0.923, T_max = 0.942	k = −19→18
5436 measured reflections	l = −8→10

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.159	H-atom parameters constrained
S = 0.98	w = 1/[σ²(F_o²) + (0.1126P)²] where P = (F_o² + 2F_c²)/3
1958 reflections	(Δ/σ)_max < 0.001
163 parameters	Δρ_max = 0.52 e Å⁻³
0 restraints	Δρ_min = −0.60 e Å⁻³

Crystal data top

C₇H₆N₃O₂S⁺·HSO₄⁻	V = 1109.0 (14) Å³
M_r = 293.28	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.849 (6) Å	µ = 0.51 mm⁻¹
b = 16.219 (12) Å	T = 291 K
c = 9.191 (7) Å	0.16 × 0.14 × 0.12 mm
β = 108.584 (10)°

Data collection top

Bruker 1K CCD area-detector diffractometer	1958 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1586 reflections with I > 2σ(I)
T_min = 0.923, T_max = 0.942	R_int = 0.097
5436 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.061	0 restraints
wR(F²) = 0.159	H-atom parameters constrained
S = 0.98	Δρ_max = 0.52 e Å⁻³
1958 reflections	Δρ_min = −0.60 e Å⁻³
163 parameters

Special details top

Experimental. The structure was solved by direct methods (Bruker, 2000) and successive difference Fourier syntheses.

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
C1	0.7190 (4)	0.12918 (17)	0.4541 (3)	0.0400 (7)
C2	0.7416 (4)	−0.00938 (16)	0.5027 (3)	0.0379 (7)
C3	0.7086 (5)	−0.09352 (18)	0.4792 (4)	0.0483 (8)
H3	0.6294	−0.1131	0.3874	0.058*
C4	0.7959 (5)	−0.14661 (19)	0.5950 (4)	0.0501 (8)
H4	0.7790	−0.2032	0.5815	0.060*
C5	0.9089 (4)	−0.11571 (17)	0.7315 (4)	0.0427 (7)
C6	0.9441 (4)	−0.03251 (17)	0.7588 (3)	0.0427 (7)
H6	1.0207	−0.0132	0.8520	0.051*
C7	0.8588 (4)	0.02045 (17)	0.6393 (3)	0.0387 (7)
N1	0.6668 (3)	0.05352 (15)	0.4010 (3)	0.0412 (6)
H1A	0.5927	0.0447	0.3107	0.049*
N2	0.6630 (4)	0.19655 (15)	0.3774 (3)	0.0524 (8)
H2A	0.5874	0.1941	0.2861	0.063*
H2B	0.7014	0.2436	0.4178	0.063*
N3	0.9911 (4)	−0.17264 (18)	0.8562 (3)	0.0538 (7)
O1	1.0531 (3)	−0.14566 (16)	0.9864 (3)	0.0651 (7)
O2	0.9914 (5)	−0.24573 (18)	0.8252 (3)	0.0885 (10)
O3	0.4172 (3)	0.88694 (13)	1.0011 (3)	0.0602 (7)
H3A	0.3934	0.9305	1.0357	0.090*
O4	0.6040 (3)	0.96348 (13)	0.8861 (2)	0.0479 (6)
O5	0.7360 (3)	0.90117 (14)	1.1335 (3)	0.0607 (7)
O6	0.6226 (3)	0.81597 (13)	0.9086 (3)	0.0549 (7)
S1	0.87176 (11)	0.12757 (5)	0.63686 (9)	0.0506 (3)
S2	0.60859 (9)	0.89227 (4)	0.98544 (8)	0.0401 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0477 (16)	0.0359 (15)	0.0280 (16)	−0.0021 (12)	0.0003 (13)	0.0006 (12)
C2	0.0509 (16)	0.0330 (14)	0.0274 (15)	−0.0023 (12)	0.0092 (13)	0.0000 (11)
C3	0.067 (2)	0.0398 (16)	0.0321 (16)	−0.0075 (15)	0.0077 (14)	−0.0101 (13)
C4	0.072 (2)	0.0347 (15)	0.0430 (19)	0.0010 (15)	0.0172 (16)	0.0014 (14)
C5	0.0461 (16)	0.0434 (17)	0.0365 (17)	0.0047 (13)	0.0103 (14)	0.0073 (13)
C6	0.0451 (16)	0.0452 (16)	0.0315 (16)	−0.0033 (13)	0.0034 (13)	0.0035 (13)
C7	0.0449 (15)	0.0351 (15)	0.0312 (15)	−0.0024 (12)	0.0053 (12)	−0.0006 (11)
N1	0.0530 (14)	0.0383 (13)	0.0239 (12)	−0.0053 (11)	0.0005 (10)	−0.0023 (10)
N2	0.0697 (18)	0.0341 (13)	0.0363 (15)	−0.0036 (12)	−0.0073 (13)	−0.0003 (11)
N3	0.0579 (16)	0.0541 (17)	0.0479 (19)	0.0046 (13)	0.0149 (14)	0.0168 (14)
O1	0.0650 (15)	0.0766 (18)	0.0433 (16)	−0.0019 (13)	0.0025 (12)	0.0191 (13)
O2	0.131 (3)	0.0496 (15)	0.073 (2)	0.0216 (16)	0.0161 (17)	0.0176 (14)
O3	0.0525 (14)	0.0479 (13)	0.081 (2)	−0.0029 (10)	0.0230 (14)	−0.0050 (12)
O4	0.0656 (14)	0.0382 (11)	0.0354 (12)	0.0087 (10)	0.0099 (10)	0.0037 (9)
O5	0.0633 (15)	0.0678 (16)	0.0346 (13)	−0.0024 (11)	−0.0077 (11)	−0.0017 (11)
O6	0.0696 (15)	0.0379 (12)	0.0450 (14)	0.0118 (10)	0.0013 (11)	−0.0044 (10)
S1	0.0641 (6)	0.0364 (5)	0.0329 (5)	−0.0078 (3)	−0.0104 (4)	−0.0014 (3)
S2	0.0452 (5)	0.0362 (5)	0.0297 (5)	0.0029 (3)	−0.0010 (4)	−0.0023 (3)

Geometric parameters (Å, º) top

C1—N2	1.299 (4)	C6—H6	0.9300
C1—N1	1.336 (3)	C7—S1	1.741 (3)
C1—S1	1.725 (3)	N1—H1A	0.8600
C2—N1	1.382 (3)	N2—H2A	0.8600
C2—C7	1.386 (4)	N2—H2B	0.8600
C2—C3	1.393 (4)	N3—O1	1.220 (4)
C3—C4	1.370 (4)	N3—O2	1.220 (4)
C3—H3	0.9300	O3—S2	1.557 (3)
C4—C5	1.380 (5)	O3—H3A	0.8200
C4—H4	0.9300	O4—S2	1.466 (2)
C5—C6	1.384 (4)	O5—S2	1.416 (2)
C5—N3	1.453 (4)	O6—S2	1.446 (2)
C6—C7	1.387 (4)

N2—C1—N1	124.2 (3)	C2—C7—S1	111.2 (2)
N2—C1—S1	123.5 (2)	C6—C7—S1	127.8 (2)
N1—C1—S1	112.3 (2)	C1—N1—C2	114.6 (2)
N1—C2—C7	111.8 (2)	C1—N1—H1A	122.7
N1—C2—C3	126.9 (3)	C2—N1—H1A	122.7
C7—C2—C3	121.3 (3)	C1—N2—H2A	120.0
C4—C3—C2	118.2 (3)	C1—N2—H2B	120.0
C4—C3—H3	120.9	H2A—N2—H2B	120.0
C2—C3—H3	120.9	O1—N3—O2	123.3 (3)
C3—C4—C5	119.7 (3)	O1—N3—C5	118.9 (3)
C3—C4—H4	120.2	O2—N3—C5	117.8 (3)
C5—C4—H4	120.2	S2—O3—H3A	109.5
C4—C5—C6	123.5 (3)	C1—S1—C7	90.14 (13)
C4—C5—N3	118.8 (3)	O5—S2—O6	114.58 (14)
C6—C5—N3	117.6 (3)	O5—S2—O4	112.84 (14)
C5—C6—C7	116.2 (3)	O6—S2—O4	111.16 (15)
C5—C6—H6	121.9	O5—S2—O3	108.89 (16)
C7—C6—H6	121.9	O6—S2—O3	102.90 (14)
C2—C7—C6	121.0 (3)	O4—S2—O3	105.57 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4ⁱ	0.86	1.97	2.825 (4)	171
N2—H2A···O6ⁱ	0.86	2.02	2.867 (4)	170
N2—H2B···O6ⁱⁱ	0.86	2.10	2.888 (4)	151
O3—H3A···O4ⁱⁱⁱ	0.82	1.86	2.664 (4)	166

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

Experimental details

Crystal data
Chemical formula	C₇H₆N₃O₂S⁺·HSO₄⁻
M_r	293.28
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	291
a, b, c (Å)	7.849 (6), 16.219 (12), 9.191 (7)
β (°)	108.584 (10)
V (Å³)	1109.0 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.51
Crystal size (mm)	0.16 × 0.14 × 0.12

Data collection
Diffractometer	Bruker 1K CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.923, 0.942
No. of measured, independent and observed [I > 2σ(I)] reflections	5436, 1958, 1586
R_int	0.097
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.159, 0.98
No. of reflections	1958
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.60

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4ⁱ	0.86	1.97	2.825 (4)	171
N2—H2A···O6ⁱ	0.86	2.02	2.867 (4)	170
N2—H2B···O6ⁱⁱ	0.86	2.10	2.888 (4)	151
O3—H3A···O4ⁱⁱⁱ	0.82	1.86	2.664 (4)	166

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

Acknowledgements

We would like to acknowledge the National Natural Science Foundation of China (No. 20871065) and the Jiangsu Province Department of Science and Technology (No. BK2009226) for financial aid.

References

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