5-(2,4-Dichloro-phenoxy-meth-yl)-1,3,4-thia-diazol-2-amine.

The title compound, C(9)H(7)Cl(2)N(3)OS, was synthesized by the reaction of 2,4-dichloro-phenoxy-acetic acid and thio-semicarbazide. The dihedral angle between the thia-diazole and benzene rings is 21.5 (2)°. In the crystal, inter-molecular N-H⋯N hydrogen bonding links the mol-ecules into chains along the b axis.

Related literature

For general background to the biological activity of 1,3,4-thia­diazole derivatives, see: Nakagawa et al. (1996 ▶); Wang et al. (1999 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C9H7Cl2N3OS

M = 276.14

Monoclinic,

a = 16.012 (3) Å

b = 6.5840 (13) Å

c = 11.225 (2) Å

β = 105.65 (3)°

V = 1139.5 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.73 mm−1

T = 293 K

0.20 × 0.10 × 0.05 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.867, T max = 0.964

2142 measured reflections

2065 independent reflections

1472 reflections with I > 2σ(I)

R int = 0.044

3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.055

wR(F 2) = 0.145

S = 1.01

2065 reflections

145 parameters

13 restraints

H-atom parameters constrained

Δρmax = 0.37 e Å−3

Δρmin = −0.34 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); 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: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809025227/at2822sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809025227/at2822Isup2.hkl

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

C9H7Cl2N3OS	F(000) = 560
Mr = 276.14	Dx = 1.610 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 16.012 (3) Å	θ = 9–12°
b = 6.5840 (13) Å	µ = 0.73 mm−1
c = 11.225 (2) Å	T = 293 K
β = 105.65 (3)°	Block, colourless
V = 1139.5 (4) Å3	0.20 × 0.10 × 0.05 mm
Z = 4

Enraf–Nonius CAD-4 diffractometer	1472 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.044
graphite	θmax = 25.3°, θmin = 1.3°
ω/2θ scans	h = −19→0
Absorption correction: ψ scan (North et al., 1968)	k = 0→7
Tmin = 0.867, Tmax = 0.964	l = −12→13
2142 measured reflections	3 standard reflections every 200 reflections
2065 independent reflections	intensity decay: 1%

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.145	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.07P)2 + 1.2P] where P = (Fo2 + 2Fc2)/3
2065 reflections	(Δ/σ)max < 0.001
145 parameters	Δρmax = 0.37 e Å−3
13 restraints	Δρmin = −0.34 e Å−3

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
S	0.63610 (7)	0.07359 (17)	0.41374 (9)	0.0408 (3)
Cl1	0.95777 (9)	−0.98076 (19)	0.66498 (12)	0.0600 (4)
Cl2	0.85657 (8)	−0.29796 (18)	0.40088 (10)	0.0477 (3)
N1	0.5928 (2)	0.1009 (5)	0.6153 (3)	0.0348 (8)
N2	0.5586 (2)	0.2734 (5)	0.5485 (3)	0.0352 (8)
N3	0.5498 (3)	0.4294 (6)	0.3589 (3)	0.0559 (12)
H3A	0.5207	0.5297	0.3764	0.067*
H3B	0.5623	0.4261	0.2891	0.067*
O	0.7388 (2)	−0.2539 (5)	0.5496 (3)	0.0479 (8)
C1	0.8892 (3)	−0.7718 (6)	0.6285 (4)	0.0366 (10)
C2	0.8284 (3)	−0.7396 (6)	0.6931 (4)	0.0400 (10)
H2B	0.8224	−0.8314	0.7532	0.048*
C3	0.7761 (3)	−0.5675 (7)	0.6670 (4)	0.0417 (10)
H3C	0.7346	−0.5448	0.7097	0.050*
C4	0.7852 (3)	−0.4306 (6)	0.5786 (3)	0.0313 (9)
C5	0.8461 (3)	−0.4680 (6)	0.5143 (4)	0.0326 (9)
C6	0.8981 (3)	−0.6391 (7)	0.5372 (4)	0.0378 (10)
H6A	0.9381	−0.6642	0.4924	0.045*
C7	0.6719 (3)	−0.2139 (6)	0.6069 (4)	0.0358 (10)
H7A	0.6952	−0.2071	0.6960	0.043*
H7B	0.6283	−0.3200	0.5873	0.043*
C8	0.6334 (2)	−0.0139 (6)	0.5571 (4)	0.0324 (9)
C9	0.5755 (3)	0.2781 (6)	0.4406 (4)	0.0359 (10)

	U11	U22	U33	U12	U13	U23
S	0.0456 (7)	0.0430 (6)	0.0397 (6)	0.0169 (5)	0.0214 (5)	0.0012 (5)
Cl1	0.0573 (8)	0.0422 (7)	0.0793 (9)	0.0218 (6)	0.0166 (7)	0.0150 (6)
Cl2	0.0500 (7)	0.0449 (7)	0.0540 (7)	0.0090 (5)	0.0240 (5)	0.0130 (5)
N1	0.037 (2)	0.0338 (19)	0.0363 (18)	0.0077 (16)	0.0141 (15)	0.0023 (15)
N2	0.037 (2)	0.0342 (19)	0.0387 (18)	0.0093 (16)	0.0177 (15)	0.0007 (15)
N3	0.079 (3)	0.057 (3)	0.043 (2)	0.037 (2)	0.035 (2)	0.0209 (19)
O	0.0479 (19)	0.0354 (17)	0.072 (2)	0.0200 (15)	0.0357 (16)	0.0153 (15)
C1	0.034 (2)	0.025 (2)	0.044 (2)	0.0048 (18)	−0.0003 (19)	0.0016 (18)
C2	0.042 (3)	0.031 (2)	0.046 (2)	−0.001 (2)	0.012 (2)	0.0081 (19)
C3	0.035 (2)	0.041 (2)	0.054 (2)	0.002 (2)	0.021 (2)	0.000 (2)
C4	0.033 (2)	0.0232 (19)	0.038 (2)	0.0048 (17)	0.0101 (17)	0.0009 (16)
C5	0.030 (2)	0.028 (2)	0.042 (2)	0.0012 (17)	0.0128 (18)	−0.0059 (17)
C6	0.027 (2)	0.038 (2)	0.047 (2)	0.0055 (19)	0.0083 (18)	−0.0035 (19)
C7	0.034 (2)	0.036 (2)	0.041 (2)	0.0033 (19)	0.0159 (18)	−0.0004 (18)
C8	0.023 (2)	0.033 (2)	0.041 (2)	0.0002 (17)	0.0097 (17)	−0.0042 (18)
C9	0.032 (2)	0.039 (2)	0.038 (2)	0.0086 (19)	0.0117 (17)	−0.0003 (19)

S—C8	1.721 (4)	C1—C2	1.378 (6)
S—C9	1.733 (4)	C1—C6	1.383 (6)
Cl1—C1	1.739 (4)	C2—C3	1.393 (6)
Cl2—C5	1.737 (4)	C2—H2B	0.9300
N1—C8	1.284 (5)	C3—C4	1.377 (6)
N1—N2	1.389 (5)	C3—H3C	0.9300
N2—C9	1.311 (5)	C4—C5	1.382 (5)
N3—C9	1.341 (5)	C5—C6	1.383 (6)
N3—H3A	0.8600	C6—H6A	0.9300
N3—H3B	0.8600	C7—C8	1.497 (6)
O—C4	1.372 (5)	C7—H7A	0.9700
O—C7	1.414 (5)	C7—H7B	0.9700
C8—S—C9	86.61 (19)	C4—C5—C6	121.5 (4)
C8—N1—N2	112.8 (3)	C4—C5—Cl2	119.3 (3)
C9—N2—N1	111.6 (3)	C6—C5—Cl2	119.3 (3)
C9—N3—H3A	120.0	C1—C6—C5	118.4 (4)
C9—N3—H3B	120.0	C1—C6—H6A	120.8
H3A—N3—H3B	120.0	C5—C6—H6A	120.8
C4—O—C7	118.6 (3)	O—C7—C8	106.3 (3)
C2—C1—C6	121.4 (4)	O—C7—H7A	110.5
C2—C1—Cl1	119.3 (3)	C8—C7—H7A	110.5
C6—C1—Cl1	119.3 (3)	O—C7—H7B	110.5
C1—C2—C3	119.0 (4)	C8—C7—H7B	110.5
C1—C2—H2B	120.5	H7A—C7—H7B	108.7
C3—C2—H2B	120.5	N1—C8—C7	122.8 (4)
C4—C3—C2	120.6 (4)	N1—C8—S	115.0 (3)
C4—C3—H3C	119.7	C7—C8—S	122.1 (3)
C2—C3—H3C	119.7	N2—C9—N3	123.2 (4)
O—C4—C3	124.7 (4)	N2—C9—S	114.0 (3)
O—C4—C5	116.1 (3)	N3—C9—S	122.8 (3)
C3—C4—C5	119.1 (4)
C8—N1—N2—C9	0.4 (5)	C4—C5—C6—C1	−1.3 (6)
C6—C1—C2—C3	−1.1 (6)	Cl2—C5—C6—C1	179.6 (3)
Cl1—C1—C2—C3	177.4 (3)	C4—O—C7—C8	−179.7 (3)
C1—C2—C3—C4	−0.4 (6)	N2—N1—C8—C7	−176.7 (3)
C7—O—C4—C3	−5.1 (6)	N2—N1—C8—S	0.4 (4)
C7—O—C4—C5	176.1 (4)	O—C7—C8—N1	−156.2 (4)
C2—C3—C4—O	−177.7 (4)	O—C7—C8—S	26.9 (5)
C2—C3—C4—C5	1.1 (6)	C9—S—C8—N1	−0.8 (3)
O—C4—C5—C6	178.6 (4)	C9—S—C8—C7	176.3 (4)
C3—C4—C5—C6	−0.2 (6)	N1—N2—C9—N3	−179.7 (4)
O—C4—C5—Cl2	−2.2 (5)	N1—N2—C9—S	−1.1 (5)
C3—C4—C5—Cl2	178.9 (3)	C8—S—C9—N2	1.1 (3)
C2—C1—C6—C5	1.9 (6)	C8—S—C9—N3	179.8 (4)
Cl1—C1—C6—C5	−176.5 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N2i	0.86	2.14	2.983 (5)	166

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N2i	0.86	2.14	2.983 (5)	166

Symmetry code: (i) .