1-(6-Chloro-1,3-benzothia-zol-2-yl)hydrazine.

The asymmetric unit of the title compound, C(7)H(6)ClN(3)S, consists of two crystallographically independent mol-ecules (A and B). The dihedral angle between the benzothia-zole ring system and the hydrazine group is 8.71 (6)° in mol-ecule A and 7.16 (6)° in mol-ecule B. The N-N-C-N and N-N-C-S torsion angles involving the hydrazine group are 170.89 (9) and -9.96 (13)°, respectively, in mol-ecule A and 172.50 (9) and -7.43 (13)°, respectively, in mol-ecule B. In the crystal, neighbouring mol-ecules are connected via pairs of N-H⋯N hydrogen bonds, generating R(2) (2)(8) ring motifs, and are connected further by N-H⋯N hydrogen bonds into sheets lying parallel to the ab plane. The crystal studied was an inversion twin, the refined ratio of the twin components being 0.50 (3):0.50 (3).

Related literature

For the biological activity of benzothia­zole derivatives, see: Bowyer et al. (2007 ▶); Gurupadayya et al. (2008 ▶); Kini et al. (2007 ▶); Mittal et al. (2007 ▶); Munirajasekhar et al. (2011 ▶); Rana et al. (2008 ▶); Pozas et al. (2005 ▶); Yaseen et al. (2006 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For related structures, see: Fun et al. (2011a ▶,b ▶,c ▶,d ▶). For bond-length data, see: Allen et al. (1987 ▶). For the stability of the temperature controller used for data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C7H6ClN3S

M = 199.66

Orthorhombic,

a = 13.0225 (13) Å

b = 5.7767 (6) Å

c = 21.708 (2) Å

V = 1633.0 (3) Å3

Z = 8

Mo Kα radiation

μ = 0.66 mm−1

T = 100 K

0.46 × 0.33 × 0.22 mm

Data collection

Bruker APEX DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.752, T max = 0.867

12527 measured reflections

5771 independent reflections

5686 reflections with I > 2σ(I)

R int = 0.015

Refinement

R[F 2 > 2σ(F 2)] = 0.019

wR(F 2) = 0.052

S = 1.04

5771 reflections

242 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.39 e Å−3

Δρmin = −0.21 e Å−3

Absolute structure: Flack (1983 ▶), with 2734 Friedel pairs

Flack parameter: 0.50 (3)

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812005442/lh5415sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812005442/lh5415Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812005442/lh5415Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C7H6ClN3S	F(000) = 816
Mr = 199.66	Dx = 1.624 Mg m−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 9942 reflections
a = 13.0225 (13) Å	θ = 3.1–32.6°
b = 5.7767 (6) Å	µ = 0.66 mm−1
c = 21.708 (2) Å	T = 100 K
V = 1633.0 (3) Å3	Block, colourless
Z = 8	0.46 × 0.33 × 0.22 mm

Bruker APEX DUO CCD area-detector diffractometer	5771 independent reflections
Radiation source: fine-focus sealed tube	5686 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.015
φ and ω scans	θmax = 32.6°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −18→19
Tmin = 0.752, Tmax = 0.867	k = −8→8
12527 measured reflections	l = −32→32

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)] = 0.019	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.052	w = 1/[σ2(Fo2) + (0.030P)2 + 0.2349P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
5771 reflections	Δρmax = 0.39 e Å−3
242 parameters	Δρmin = −0.21 e Å−3
1 restraint	Absolute structure: Flack (1983), with 2734 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.50 (3)

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K

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.

	x	y	z	Uiso*/Ueq
Cl1A	0.87218 (2)	0.41653 (5)	0.717085 (12)	0.02134 (5)
S1A	0.552566 (17)	0.69138 (4)	0.565134 (11)	0.01203 (5)
N1A	0.66692 (7)	1.05970 (15)	0.54585 (4)	0.01308 (15)
N2A	0.51172 (7)	1.05780 (16)	0.49160 (4)	0.01507 (16)
N3A	0.42819 (7)	0.91902 (16)	0.47219 (4)	0.01386 (15)
C1A	0.71962 (7)	0.91958 (17)	0.58718 (4)	0.01122 (15)
C2A	0.81645 (8)	0.96993 (18)	0.61154 (5)	0.01342 (17)
H2AA	0.8505	1.1099	0.6009	0.016*
C3A	0.86228 (8)	0.81302 (19)	0.65137 (5)	0.01533 (18)
H3AA	0.9280	0.8454	0.6683	0.018*
C4A	0.81171 (8)	0.60698 (18)	0.66667 (5)	0.01434 (17)
C5A	0.71540 (8)	0.55065 (17)	0.64323 (5)	0.01318 (16)
H5AA	0.6819	0.4103	0.6540	0.016*
C6A	0.67048 (7)	0.71010 (16)	0.60320 (5)	0.01111 (15)
C7A	0.57964 (8)	0.96117 (17)	0.53072 (5)	0.01172 (16)
Cl1B	−0.11478 (2)	−0.03607 (5)	0.236826 (13)	0.02216 (6)
S1B	0.204579 (17)	0.20760 (4)	0.392197 (11)	0.01240 (5)
N1B	0.09520 (7)	0.58201 (14)	0.41251 (4)	0.01264 (14)
N2B	0.24932 (7)	0.56551 (15)	0.46758 (4)	0.01454 (15)
N3B	0.33266 (7)	0.42272 (15)	0.48545 (4)	0.01366 (15)
C1B	0.04080 (7)	0.44800 (16)	0.37042 (4)	0.01125 (15)
C2B	−0.05487 (8)	0.50641 (18)	0.34582 (5)	0.01351 (17)
H2BA	−0.0869	0.6485	0.3566	0.016*
C3B	−0.10279 (8)	0.3538 (2)	0.30526 (5)	0.01507 (17)
H3BA	−0.1683	0.3902	0.2886	0.018*
C4B	−0.05411 (8)	0.14744 (19)	0.28917 (5)	0.01476 (17)
C5B	0.04124 (8)	0.08359 (18)	0.31282 (5)	0.01425 (16)
H5BA	0.0731	−0.0582	0.3016	0.017*
C6B	0.08771 (7)	0.23707 (17)	0.35371 (4)	0.01162 (15)
C7B	0.18114 (8)	0.47712 (17)	0.42752 (5)	0.01170 (16)
H3N3	0.3862 (12)	0.510 (3)	0.4823 (8)	0.020 (4)*
H1N2	0.5300 (15)	1.169 (4)	0.4657 (9)	0.032 (5)*
H2N2	0.2275 (13)	0.679 (3)	0.4927 (8)	0.021 (4)*
H1N3	0.3749 (13)	0.997 (4)	0.4765 (9)	0.026 (5)*
H2N3	0.4325 (13)	0.893 (3)	0.4319 (8)	0.019 (4)*
H4N3	0.3195 (15)	0.373 (3)	0.5273 (8)	0.032 (5)*

	U11	U22	U33	U12	U13	U23
Cl1A	0.02667 (12)	0.01723 (10)	0.02012 (11)	0.00445 (9)	−0.01095 (10)	0.00160 (9)
S1A	0.01053 (9)	0.01123 (9)	0.01432 (9)	−0.00103 (7)	−0.00095 (8)	0.00210 (8)
N1A	0.0121 (4)	0.0126 (3)	0.0145 (4)	−0.0016 (3)	−0.0014 (3)	0.0022 (3)
N2A	0.0122 (4)	0.0141 (4)	0.0189 (4)	−0.0023 (3)	−0.0038 (3)	0.0051 (3)
N3A	0.0108 (3)	0.0150 (4)	0.0158 (4)	−0.0001 (3)	−0.0018 (3)	−0.0004 (3)
C1A	0.0106 (4)	0.0124 (4)	0.0107 (4)	0.0002 (3)	0.0000 (3)	0.0002 (3)
C2A	0.0116 (4)	0.0150 (4)	0.0137 (4)	−0.0014 (3)	−0.0007 (3)	−0.0004 (3)
C3A	0.0140 (4)	0.0175 (5)	0.0144 (4)	0.0004 (3)	−0.0034 (3)	−0.0016 (3)
C4A	0.0162 (4)	0.0145 (4)	0.0123 (4)	0.0033 (3)	−0.0036 (3)	0.0001 (3)
C5A	0.0156 (4)	0.0115 (4)	0.0124 (4)	0.0017 (3)	−0.0018 (3)	0.0009 (3)
C6A	0.0106 (4)	0.0112 (4)	0.0116 (4)	−0.0002 (3)	−0.0004 (3)	−0.0003 (3)
C7A	0.0113 (4)	0.0117 (4)	0.0122 (4)	0.0007 (3)	0.0001 (3)	0.0013 (3)
Cl1B	0.02443 (12)	0.02047 (12)	0.02156 (12)	−0.00247 (9)	−0.01001 (10)	−0.00638 (9)
S1B	0.01040 (9)	0.01177 (9)	0.01504 (10)	0.00135 (7)	−0.00118 (8)	−0.00246 (8)
N1B	0.0123 (3)	0.0124 (3)	0.0132 (3)	0.0009 (3)	−0.0013 (3)	−0.0035 (3)
N2B	0.0113 (3)	0.0148 (4)	0.0175 (4)	0.0021 (3)	−0.0040 (3)	−0.0052 (3)
N3B	0.0109 (3)	0.0148 (4)	0.0154 (4)	−0.0004 (3)	−0.0020 (3)	0.0011 (3)
C1B	0.0109 (4)	0.0120 (4)	0.0109 (4)	−0.0001 (3)	0.0007 (3)	−0.0012 (3)
C2B	0.0119 (4)	0.0150 (4)	0.0137 (4)	0.0016 (3)	−0.0004 (3)	−0.0017 (3)
C3B	0.0124 (4)	0.0184 (4)	0.0143 (4)	−0.0001 (3)	−0.0024 (3)	−0.0005 (3)
C4B	0.0161 (4)	0.0154 (4)	0.0129 (4)	−0.0033 (3)	−0.0027 (3)	−0.0025 (3)
C5B	0.0152 (4)	0.0134 (4)	0.0141 (4)	−0.0005 (3)	−0.0011 (3)	−0.0029 (3)
C6B	0.0113 (4)	0.0116 (4)	0.0119 (4)	0.0003 (3)	0.0002 (3)	−0.0008 (3)
C7B	0.0114 (4)	0.0112 (4)	0.0126 (4)	−0.0013 (3)	0.0003 (3)	−0.0016 (3)

Cl1A—C4A	1.7402 (10)	Cl1B—C4B	1.7434 (10)
S1A—C6A	1.7471 (10)	S1B—C6B	1.7445 (10)
S1A—C7A	1.7639 (10)	S1B—C7B	1.7621 (10)
N1A—C7A	1.3129 (13)	N1B—C7B	1.3137 (13)
N1A—C1A	1.3896 (13)	N1B—C1B	1.3913 (13)
N2A—C7A	1.3473 (13)	N2B—C7B	1.3437 (13)
N2A—N3A	1.4154 (13)	N2B—N3B	1.4173 (13)
N2A—H1N2	0.89 (2)	N2B—H2N2	0.897 (17)
N3A—H1N3	0.831 (18)	N3B—H3N3	0.862 (17)
N3A—H2N3	0.890 (17)	N3B—H4N3	0.968 (19)
C1A—C2A	1.3979 (14)	C1B—C2B	1.3968 (14)
C1A—C6A	1.4124 (14)	C1B—C6B	1.4106 (13)
C2A—C3A	1.3877 (15)	C2B—C3B	1.3935 (14)
C2A—H2AA	0.9500	C2B—H2BA	0.9500
C3A—C4A	1.4002 (15)	C3B—C4B	1.3946 (15)
C3A—H3AA	0.9500	C3B—H3BA	0.9500
C4A—C5A	1.3921 (15)	C4B—C5B	1.3934 (15)
C5A—C6A	1.3948 (14)	C5B—C6B	1.3929 (14)
C5A—H5AA	0.9500	C5B—H5BA	0.9500
C6A—S1A—C7A	88.28 (5)	C6B—S1B—C7B	88.34 (5)
C7A—N1A—C1A	109.67 (9)	C7B—N1B—C1B	109.88 (8)
C7A—N2A—N3A	117.22 (8)	C7B—N2B—N3B	117.51 (8)
C7A—N2A—H1N2	121.6 (13)	C7B—N2B—H2N2	117.4 (11)
N3A—N2A—H1N2	115.4 (13)	N3B—N2B—H2N2	120.0 (11)
N2A—N3A—H1N3	107.6 (13)	N2B—N3B—H3N3	105.0 (12)
N2A—N3A—H2N3	109.9 (11)	N2B—N3B—H4N3	107.2 (12)
H1N3—N3A—H2N3	104.8 (17)	H3N3—N3B—H4N3	113.0 (17)
N1A—C1A—C2A	124.65 (9)	N1B—C1B—C2B	124.81 (9)
N1A—C1A—C6A	115.73 (9)	N1B—C1B—C6B	115.41 (9)
C2A—C1A—C6A	119.59 (9)	C2B—C1B—C6B	119.78 (9)
C3A—C2A—C1A	119.20 (9)	C3B—C2B—C1B	119.23 (9)
C3A—C2A—H2AA	120.4	C3B—C2B—H2BA	120.4
C1A—C2A—H2AA	120.4	C1B—C2B—H2BA	120.4
C2A—C3A—C4A	120.04 (9)	C2B—C3B—C4B	119.69 (9)
C2A—C3A—H3AA	120.0	C2B—C3B—H3BA	120.2
C4A—C3A—H3AA	120.0	C4B—C3B—H3BA	120.2
C5A—C4A—C3A	122.39 (9)	C5B—C4B—C3B	122.63 (9)
C5A—C4A—Cl1A	119.33 (8)	C5B—C4B—Cl1B	118.88 (8)
C3A—C4A—Cl1A	118.28 (8)	C3B—C4B—Cl1B	118.49 (8)
C4A—C5A—C6A	116.82 (9)	C6B—C5B—C4B	116.96 (9)
C4A—C5A—H5AA	121.6	C6B—C5B—H5BA	121.5
C6A—C5A—H5AA	121.6	C4B—C5B—H5BA	121.5
C5A—C6A—C1A	121.95 (9)	C5B—C6B—C1B	121.71 (9)
C5A—C6A—S1A	128.49 (8)	C5B—C6B—S1B	128.47 (8)
C1A—C6A—S1A	109.56 (7)	C1B—C6B—S1B	109.81 (7)
N1A—C7A—N2A	123.12 (9)	N1B—C7B—N2B	123.24 (9)
N1A—C7A—S1A	116.75 (8)	N1B—C7B—S1B	116.56 (8)
N2A—C7A—S1A	120.12 (7)	N2B—C7B—S1B	120.20 (7)
C7A—N1A—C1A—C2A	178.40 (10)	C7B—N1B—C1B—C2B	178.69 (10)
C7A—N1A—C1A—C6A	0.22 (12)	C7B—N1B—C1B—C6B	0.05 (12)
N1A—C1A—C2A—C3A	−178.45 (9)	N1B—C1B—C2B—C3B	−178.22 (9)
C6A—C1A—C2A—C3A	−0.33 (15)	C6B—C1B—C2B—C3B	0.37 (15)
C1A—C2A—C3A—C4A	0.10 (16)	C1B—C2B—C3B—C4B	−0.92 (15)
C2A—C3A—C4A—C5A	0.06 (16)	C2B—C3B—C4B—C5B	0.97 (16)
C2A—C3A—C4A—Cl1A	−179.72 (8)	C2B—C3B—C4B—Cl1B	−178.42 (8)
C3A—C4A—C5A—C6A	0.02 (15)	C3B—C4B—C5B—C6B	−0.41 (16)
Cl1A—C4A—C5A—C6A	179.80 (8)	Cl1B—C4B—C5B—C6B	178.97 (8)
C4A—C5A—C6A—C1A	−0.26 (15)	C4B—C5B—C6B—C1B	−0.17 (15)
C4A—C5A—C6A—S1A	178.95 (8)	C4B—C5B—C6B—S1B	178.78 (8)
N1A—C1A—C6A—C5A	178.70 (9)	N1B—C1B—C6B—C5B	178.90 (9)
C2A—C1A—C6A—C5A	0.42 (15)	C2B—C1B—C6B—C5B	0.18 (15)
N1A—C1A—C6A—S1A	−0.64 (11)	N1B—C1B—C6B—S1B	−0.22 (11)
C2A—C1A—C6A—S1A	−178.92 (8)	C2B—C1B—C6B—S1B	−178.94 (8)
C7A—S1A—C6A—C5A	−178.65 (10)	C7B—S1B—C6B—C5B	−178.81 (10)
C7A—S1A—C6A—C1A	0.64 (8)	C7B—S1B—C6B—C1B	0.24 (8)
C1A—N1A—C7A—N2A	179.49 (9)	C1B—N1B—C7B—N2B	−179.78 (9)
C1A—N1A—C7A—S1A	0.32 (11)	C1B—N1B—C7B—S1B	0.15 (11)
N3A—N2A—C7A—N1A	170.89 (9)	N3B—N2B—C7B—N1B	172.50 (10)
N3A—N2A—C7A—S1A	−9.96 (13)	N3B—N2B—C7B—S1B	−7.43 (13)
C6A—S1A—C7A—N1A	−0.58 (8)	C6B—S1B—C7B—N1B	−0.23 (9)
C6A—S1A—C7A—N2A	−179.78 (9)	C6B—S1B—C7B—N2B	179.70 (9)

D—H···A	D—H	H···A	D···A	D—H···A
N2A—H1N2···N1Bi	0.89 (2)	2.03 (2)	2.9084 (12)	170.5 (18)
N2B—H2N2···N1Aii	0.897 (17)	2.059 (18)	2.9539 (13)	175.3 (16)
N3A—H1N3···N3Biii	0.831 (18)	2.53 (2)	3.1776 (13)	135.6 (16)
N3B—H3N3···N3A	0.863 (16)	2.435 (17)	3.1383 (13)	139.1 (14)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2A—H1N2⋯N1Bi	0.89 (2)	2.03 (2)	2.9084 (12)	170.5 (18)
N2B—H2N2⋯N1Aii	0.897 (17)	2.059 (18)	2.9539 (13)	175.3 (16)
N3A—H1N3⋯N3Biii	0.831 (18)	2.53 (2)	3.1776 (13)	135.6 (16)
N3B—H3N3⋯N3A	0.863 (16)	2.435 (17)	3.1383 (13)	139.1 (14)

Symmetry codes: (i) ; (ii) ; (iii) .