5-(2,4-Dichloro­phenoxy­meth­yl)-1,3,4-thia­diazol-2-amine

Wang, Y.; Wan, R.; Han, F.; Wang, P.

doi:10.1107/S1600536809025227

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1761

doi:10.1107/S1600536809025227

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5-(2,4-Dichlorophenoxymethyl)-1,3,4-thiadiazol-2-amine

Yao Wang,^a Rong Wan,^a ^* Feng Han ^a and Peng Wang ^a

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, No. 5 Xinmofan Road, Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: rwan@njut.edu.cn

(Received 17 June 2009; accepted 30 June 2009; online 4 July 2009)

The title compound, C₉H₇Cl₂N₃OS, was synthesized by the reaction of 2,4-dichlorophenoxyacetic acid and thiosemicarbazide. The dihedral angle between the thiadiazole and benzene rings is 21.5 (2)°. In the crystal, intermolecular N—H⋯N hydrogen bonding links the molecules 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_r = 276.14
Monoclinic, P 2₁ /c
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[F² > 2σ(F²)] = 0.055
wR(F²) = 0.145
S = 1.01
2065 reflections
145 parameters
13 restraints
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.34 e Å⁻³

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) -x+1, -y+1, -z+1.

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.

Supporting information

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

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

checkCIF report

Comment top

1,3,4-Thiadiazole derivatives represent an interesting class of compounds possessing broad spectrum biological activities (Nakagawa et al., 1996). These compounds are known to exhibit diverse biological effects, such as insecticidal and fungicidal activities (Wang et al., 1999). The structure of the title compound, (I), is shown in Fig. 1, in which the bond lengths (Allen et al., 1987) and angles are generally within normal ranges. The dihedral angle between the thiadiazole and benzene ring is 21.5 (2)°. There is intermolecular N—H···N hydrogen bond (Table 1, Fig. 2), forming chains along the b axis.

Related literature top

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 top

2,4-Dichloro phenoxyacetic acid (2 mmol) and thiosemicarbazide (5 mmol) were mixed in a 25 ml flask, and kept in the oil bath at 363 K for 6 h. After cooling, the crude product (I) precipitated and was filtered. Pure compound (I) was obtained by crystallization from ethanol (20 ml). Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of an acetone solution.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1989); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the molecular structure of (I). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Partial packing view showing the hydrogen-bonded network. Dashed lines indicate intermolecular N—H···N hydrogen bond.

5-(2,4-Dichlorophenoxymethyl)-1,3,4-thiadiazol-2-amine top

Crystal data top

C₉H₇Cl₂N₃OS	F(000) = 560
M_r = 276.14	D_x = 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

Data collection top

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

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.145	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.07P)² + 1.2P] where P = (F_o² + 2F_c²)/3
2065 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.37 e Å⁻³
13 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₉H₇Cl₂N₃OS	V = 1139.5 (4) Å³
M_r = 276.14	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.012 (3) Å	µ = 0.73 mm⁻¹
b = 6.5840 (13) Å	T = 293 K
c = 11.225 (2) Å	0.20 × 0.10 × 0.05 mm
β = 105.65 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1472 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.044
T_min = 0.867, T_max = 0.964	3 standard reflections every 200 reflections
2142 measured reflections	intensity decay: 1%
2065 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	13 restraints
wR(F²) = 0.145	H-atom parameters constrained
S = 1.01	Δρ_max = 0.37 e Å⁻³
2065 reflections	Δρ_min = −0.34 e Å⁻³
145 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
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₉H₇Cl₂N₃OS
M_r	276.14
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	16.012 (3), 6.5840 (13), 11.225 (2)
β (°)	105.65 (3)
V (Å³)	1139.5 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.73
Crystal size (mm)	0.20 × 0.10 × 0.05

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.867, 0.964
No. of measured, independent and observed [I > 2σ(I)] reflections	2142, 2065, 1472
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.145, 1.01
No. of reflections	2065
No. of parameters	145
No. of restraints	13
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.34

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), 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
N3—H3A···N2ⁱ	0.8600	2.1400	2.983 (5)	166.00

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

The authors gratefully acknowledge Professor Hua-Qin Wang of the Analysis Center, Nanjing University, for providing the Enraf–Nonius CAD-4 diffractometer for this research project.

References

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