2-Hydrazinyl-4-methyl-1,3-benzothia­zole

Liu, X.-F.; Yu, X.-Y.; Jiang, S.-L.

doi:10.1107/S1600536811020149

organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page o1641

doi:10.1107/S1600536811020149

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2-Hydrazinyl-4-methyl-1,3-benzothiazole

Xu-Feng Liu,^a Xiao-Yong Yu ^a and Shao-Liang Jiang ^b ^*

^aDepartment of Chemical Engineering, Ningbo University of Technology, Ningbo 315016, People's Republic of China, and ^bCollege of Pharmaceutical Science, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China
^*Correspondence e-mail: naka80@yahoo.cn

(Received 24 May 2011; accepted 26 May 2011; online 11 June 2011)

The title compound, C₈H₉N₃S, is almost planar (r.m.s. deviation = 0.019 Å) apart from the terminal –NH₂ grouping [deviation of the N atom = 0.286 (2) Å]. In the crystal, molecules are linked by N—H⋯N hydrogen bonds, generating (001) sheets.

Related literature

For related structures and their biactivity, see Sun & Cui (2008 ); Liu & Liu (2011 ); Liuet al. (2011a ,b ). For the synthesis, see: Patel et al. (2010 ).

Experimental

Crystal data

C₈H₉N₃S
M_r = 179.24
Monoclinic, P 2₁
a = 3.893 (2) Å
b = 7.312 (4) Å
c = 14.137 (8) Å
β = 93.416 (13)°
V = 401.7 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 113 K
0.28 × 0.18 × 0.10 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.910, T_max = 0.967
4186 measured reflections
1864 independent reflections
1614 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.057
S = 1.02
1864 reflections
122 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.20 e Å⁻³
Absolute structure: Flack (1983 ), 836 Friedel pairs
Flack parameter: −0.09 (6)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N3ⁱ	0.89 (1)	2.30 (2)	2.996 (3)	135 (2)
N3—H3A⋯N1ⁱⁱ	0.92 (1)	2.21 (1)	3.077 (3)	156 (2)
Symmetry codes: (i) $[-x+2, y+{\script{1\over 2}}, -z+1]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+1]$ .

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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/S1600536811020149/hb5894sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811020149/hb5894Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811020149/hb5894Isup3.cml

checkCIF report

Comment top

Sulfur and nitrogen heterocyclic compounds have received considerable attention in recent years because of their medicinal and pesticidal importance, such as 1,3,4-thiadiazoles, pyrimidines, and 1,2,4-triazoles (Liu & Liu, 2011; Liu et al., 2011a,b). For a related structure, see Sun & Cui (2008).

Single-crystal X-ray diffraction analysis reveals that the title compound crystallizes in the monoclinic space group P2(1). As shown in Fig. 1, the benzene and thiazole rings are almost in the same plane. As shown in Fig. 2, there are intermolecular N—H···N hydrogen bonds in the crystal.

Related literature top

For related structures and their biactivity, see Sun & Cui (2008); Liu & Liu (2011); Liu et al. (2011a,b). For the synthesis, see: Patel et al. (2010).

Experimental top

The title compound was prepared according to the literature procedures (Patel et al., (2010). Colourless prisms of (I) were grown by the slow evaporation of an ethanol solution at room temperature.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); 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). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The crystal packing for (I).

2-Hydrazinyl-4-methyl-1,3-benzothiazole top

Crystal data top

C₈H₉N₃S	F(000) = 188
M_r = 179.24	D_x = 1.482 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 3.893 (2) Å	Cell parameters from 1356 reflections
b = 7.312 (4) Å	θ = 2.9–27.9°
c = 14.137 (8) Å	µ = 0.34 mm⁻¹
β = 93.416 (13)°	T = 113 K
V = 401.7 (4) Å³	Prism, colorless
Z = 2	0.28 × 0.18 × 0.10 mm

Data collection top

Rigaku Saturn CCD area-detector diffractometer	1864 independent reflections
Radiation source: rotating anode	1614 reflections with I > 2σ(I)
Multilayer monochromator	R_int = 0.043
Detector resolution: 14.63 pixels mm^-1	θ_max = 27.9°, θ_min = 1.4°
ω and ϕ scans	h = −5→5
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −9→9
T_min = 0.910, T_max = 0.967	l = −18→18
4186 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.057	w = 1/[σ²(F_o²) + (0.006P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
1864 reflections	Δρ_max = 0.28 e Å⁻³
122 parameters	Δρ_min = −0.20 e Å⁻³
5 restraints	Absolute structure: Flack (1983), 836 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.09 (6)

Crystal data top

C₈H₉N₃S	V = 401.7 (4) Å³
M_r = 179.24	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 3.893 (2) Å	µ = 0.34 mm⁻¹
b = 7.312 (4) Å	T = 113 K
c = 14.137 (8) Å	0.28 × 0.18 × 0.10 mm
β = 93.416 (13)°

Data collection top

Rigaku Saturn CCD area-detector diffractometer	1864 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	1614 reflections with I > 2σ(I)
T_min = 0.910, T_max = 0.967	R_int = 0.043
4186 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.057	Δρ_max = 0.28 e Å⁻³
S = 1.02	Δρ_min = −0.20 e Å⁻³
1864 reflections	Absolute structure: Flack (1983), 836 Friedel pairs
122 parameters	Absolute structure parameter: −0.09 (6)
5 restraints

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
S1	0.74281 (13)	0.41481 (6)	0.33097 (3)	0.01462 (12)
C5	0.2809 (5)	0.8047 (3)	0.18122 (14)	0.0144 (5)
N3	0.9465 (5)	0.4807 (2)	0.52579 (12)	0.0163 (4)
C2	0.5274 (5)	0.4513 (3)	0.13713 (13)	0.0163 (5)
H2A	0.6107	0.3333	0.1221	0.020*
N1	0.4899 (4)	0.7443 (2)	0.34709 (11)	0.0136 (4)
C4	0.2524 (5)	0.7352 (3)	0.08962 (14)	0.0158 (5)
H4	0.1480	0.8083	0.0403	0.019*
C6	0.4388 (5)	0.6942 (3)	0.25178 (13)	0.0127 (4)
C7	0.6412 (5)	0.6127 (3)	0.39382 (13)	0.0130 (4)
N2	0.7110 (4)	0.6159 (2)	0.49033 (12)	0.0150 (4)
C3	0.3711 (5)	0.5633 (3)	0.06809 (13)	0.0185 (5)
H3	0.3451	0.5208	0.0046	0.022*
C1	0.5572 (5)	0.5186 (3)	0.22906 (13)	0.0124 (4)
C8	0.1482 (5)	0.9932 (3)	0.20484 (14)	0.0182 (5)
H8A	0.3296	1.0618	0.2404	0.027*
H8B	−0.0518	0.9812	0.2433	0.027*
H8C	0.0810	1.0585	0.1461	0.027*
H2	0.761 (6)	0.7236 (19)	0.5172 (16)	0.060 (10)*
H3A	0.861 (4)	0.423 (3)	0.5774 (10)	0.043 (7)*
H3B	1.153 (3)	0.531 (3)	0.5428 (12)	0.038 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0167 (3)	0.0120 (2)	0.0151 (2)	0.0012 (3)	0.00115 (18)	0.0003 (2)
C5	0.0078 (11)	0.0166 (11)	0.0191 (11)	−0.0007 (10)	0.0026 (9)	0.0030 (9)
N3	0.0141 (11)	0.0180 (10)	0.0163 (9)	0.0006 (8)	−0.0015 (7)	0.0049 (8)
C2	0.0142 (11)	0.0169 (14)	0.0180 (10)	−0.0005 (9)	0.0029 (8)	−0.0029 (9)
N1	0.0139 (10)	0.0126 (9)	0.0142 (9)	0.0000 (7)	0.0007 (7)	0.0017 (7)
C4	0.0124 (12)	0.0188 (11)	0.0163 (11)	−0.0008 (9)	0.0004 (8)	0.0044 (9)
C6	0.0091 (10)	0.0132 (10)	0.0160 (10)	−0.0037 (9)	0.0032 (8)	0.0004 (9)
C7	0.0125 (11)	0.0137 (10)	0.0133 (10)	−0.0043 (9)	0.0033 (9)	−0.0010 (9)
N2	0.0186 (11)	0.0117 (9)	0.0145 (9)	0.0011 (8)	−0.0009 (7)	0.0004 (8)
C3	0.0189 (13)	0.0231 (12)	0.0133 (10)	−0.0065 (9)	0.0009 (9)	−0.0015 (10)
C1	0.0113 (11)	0.0129 (11)	0.0129 (10)	0.0004 (9)	0.0005 (8)	0.0027 (8)
C8	0.0167 (13)	0.0162 (10)	0.0215 (11)	0.0010 (10)	−0.0008 (9)	0.0034 (9)

Geometric parameters (Å, º) top

S1—C1	1.746 (2)	N1—C7	1.289 (2)
S1—C7	1.756 (2)	N1—C6	1.399 (2)
C5—C4	1.389 (3)	C4—C3	1.379 (3)
C5—C6	1.397 (3)	C4—H4	0.9500
C5—C8	1.516 (3)	C6—C1	1.407 (2)
N3—N2	1.420 (2)	C7—N2	1.375 (3)
N3—H3A	0.923 (9)	N2—H2	0.891 (9)
N3—H3B	0.903 (9)	C3—H3	0.9500
C2—C3	1.387 (3)	C8—H8A	0.9800
C2—C1	1.388 (2)	C8—H8B	0.9800
C2—H2A	0.9500	C8—H8C	0.9800

C1—S1—C7	87.97 (10)	N1—C7—S1	117.74 (15)
C4—C5—C6	117.47 (18)	N2—C7—S1	118.61 (15)
C4—C5—C8	121.90 (18)	C7—N2—N3	115.08 (15)
C6—C5—C8	120.64 (17)	C7—N2—H2	117.6 (16)
N2—N3—H3A	110.0 (13)	N3—N2—H2	110.2 (17)
N2—N3—H3B	110.7 (14)	C4—C3—C2	121.44 (19)
H3A—N3—H3B	109.6 (12)	C4—C3—H3	119.3
C3—C2—C1	117.26 (17)	C2—C3—H3	119.3
C3—C2—H2A	121.4	C2—C1—C6	121.80 (18)
C1—C2—H2A	121.4	C2—C1—S1	128.72 (15)
C7—N1—C6	109.43 (16)	C6—C1—S1	109.47 (14)
C3—C4—C5	121.98 (19)	C5—C8—H8A	109.5
C3—C4—H4	119.0	C5—C8—H8B	109.5
C5—C4—H4	119.0	H8A—C8—H8B	109.5
C5—C6—N1	124.57 (18)	C5—C8—H8C	109.5
C5—C6—C1	120.04 (17)	H8A—C8—H8C	109.5
N1—C6—C1	115.39 (17)	H8B—C8—H8C	109.5
N1—C7—N2	123.57 (18)

C6—C5—C4—C3	0.6 (3)	N1—C7—N2—N3	−165.94 (18)
C8—C5—C4—C3	−179.61 (17)	S1—C7—N2—N3	17.4 (2)
C4—C5—C6—N1	179.46 (18)	C5—C4—C3—C2	−0.4 (3)
C8—C5—C6—N1	−0.3 (3)	C1—C2—C3—C4	0.5 (3)
C4—C5—C6—C1	−0.9 (3)	C3—C2—C1—C6	−0.9 (3)
C8—C5—C6—C1	179.27 (16)	C3—C2—C1—S1	−179.19 (14)
C7—N1—C6—C5	179.87 (19)	C5—C6—C1—C2	1.1 (3)
C7—N1—C6—C1	0.3 (2)	N1—C6—C1—C2	−179.26 (17)
C6—N1—C7—N2	−176.41 (18)	C5—C6—C1—S1	179.73 (15)
C6—N1—C7—S1	0.3 (2)	N1—C6—C1—S1	−0.6 (2)
C1—S1—C7—N1	−0.54 (17)	C7—S1—C1—C2	179.11 (18)
C1—S1—C7—N2	176.31 (16)	C7—S1—C1—C6	0.61 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N3ⁱ	0.89 (1)	2.30 (2)	2.996 (3)	135 (2)
N3—H3A···N1ⁱⁱ	0.92 (1)	2.21 (1)	3.077 (3)	156 (2)

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

Experimental details

Crystal data
Chemical formula	C₈H₉N₃S
M_r	179.24
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	113
a, b, c (Å)	3.893 (2), 7.312 (4), 14.137 (8)
β (°)	93.416 (13)
V (Å³)	401.7 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.28 × 0.18 × 0.10

Data collection
Diffractometer	Rigaku Saturn CCD area-detector diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.910, 0.967
No. of measured, independent and observed [I > 2σ(I)] reflections	4186, 1864, 1614
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.057, 1.02
No. of reflections	1864
No. of parameters	122
No. of restraints	5
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.20
Absolute structure	Flack (1983), 836 Friedel pairs
Absolute structure parameter	−0.09 (6)

Computer programs: CrystalClear (Rigaku/MSC, 2005), 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
N2—H2···N3ⁱ	0.891 (9)	2.298 (18)	2.996 (3)	135 (2)
N3—H3A···N1ⁱⁱ	0.923 (9)	2.209 (10)	3.077 (3)	156.3 (16)

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

Acknowledgements

We thank the Social Practice of the Excellent Engineer Programs of Ningbo University of Technology.

References

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