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

Abstract

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,

• a = 16.012 (3) Å

• b = 6.5840 (13) Å

• c = 11.225 (2) Å

• β = 105.65 (3)°

• V = 1139.5 (4) ų

• 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

• Δρ_max = 0.37 e Å⁻³

• Δρ_min = −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.

Supplementary Material

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

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) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

All H atoms were placed geometrically with C—H = 0.93–0.97 Å, N—H = 0.86 Å and included in the refinement in riding motion approximation with U_iso(H) = 1.2U_eq of the carrier atom.

Figures

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.

Crystal data

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

Data collection

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

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

Special details

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 (Ų)

	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)

Atomic displacement parameters (Ų)

	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, °)

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, °)

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

Symmetry codes: (i) −x+1, −y+1, −z+1.