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

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

doi:10.1107/S1600536809013257

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o1044

doi:10.1107/S1600536809013257

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

Rong Wan,^a ^* Yao Wang,^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 5 April 2009; accepted 7 April 2009; online 18 April 2009)

The title compound, C₁₄H₁₁N₃OS, was synthesized by the reaction of phenoxybenzoic acid and thiosemicarbazide. The thiadiazole ring makes dihedral angles of 0.99 (16) and 86.53 (18)°, respectively, with the benzene and phenyl rings. The dihedral angle between the benzene and phenyl rings is 87.17 (19)°. Intramolecular C—H⋯S contacts are present. In the crystal, intermolecular N—H⋯N hydrogen bonds link the molecules.

Related literature

For the fungicidal and herbicidal activities of thiadiazole derivatives, see: Chen et al. (2000 ); Kidwai et al. (2000 ); Vicentini et al. (1998 ). For their insecticidal activities, see: Arun et al. (1999 ); Wasfy et al. (1996 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₄H₁₁N₃OS
M_r = 269.32
Monoclinic, P 2₁ /c
a = 13.409 (3) Å
b = 10.582 (2) Å
c = 9.5710 (19) Å
β = 108.58 (3)°
V = 1287.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.930, T_max = 0.953
2438 measured reflections
2336 independent reflections
1596 reflections with I > 2σ(I)
R_int = 0.032
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.141
S = 1.00
2336 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.22 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	2.21	3.042 (4)	162
N3—H3B⋯N1ⁱⁱ	0.86	2.26	3.094 (3)	163
C9—H9A⋯S	0.93	2.72	3.133 (4)	108
Symmetry codes: (i) -x, -y, -z+1; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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/S1600536809013257/at2760sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809013257/at2760Isup2.hkl

checkCIF report

Comment top

Thiadiazole derivatives containing the thiazolidinone unit are of great interest because of their chemical and pharmaceutical properties. Some derivatives have fungicidal and herbicidal activities (Chen et al., 2000; Kidwai et al., 2000; Vicentini et al., 1998); some show insecticidal activities (Arun et al., 1999; Wasfy et al., 1996). We report here the crystal structure of the title compound, (I).

The molecular structure of (I) is shown in Fig.1, in which the bond lengths (Allen et al., 1987) and angles are generally within normal ranges. The thiadiazole ring makes dihedral angles of 0.99 (16)° and 86.53 (18) ° with the benzene and phenyl rings, respectively. The dihedral angle between the benzene and phenyl rings is 87.17 (19)°. There are intramolecular C—H···S contacts (Fig. 1), and intermolecular N—H···N hydrogen bonds, linking the molecules into chains along the b axis (Fig. 2).

Related literature top

For thefungicidal and herbicidal activities of thiadiazole derivatives, see: Chen et al. (2000); Kidwai et al. (2000); Vicentini et al. (1998). For insecticidal activities, see: Arun et al. (1999); Wasfy et al. (1996). For bond-length data, see: Allen et al. (1987).

Experimental top

Phenoxybenzoic acid (5 mmol) and thiosemicarbazide (5 mmol) were added in toluene (50 ml), which is heated under reflux for 4 h. The reaction mixture was left to cool to room temperature, poured into ice water, filtered, and the filter cake was crystallized from acetone to give pure compound (I) [m.p. 513–514 K]. 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. Dashed lines indicate the intramolecular C—H···S contact.
	Fig. 2. Partial packing view showing the hydrogen-bonded network. Dashed lines indicate intermolecular N—H···N hydrogen bonds.

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

Crystal data top

C₁₄H₁₁N₃OS	F(000) = 560
M_r = 269.32	D_x = 1.390 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 542 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 13.409 (3) Å	Cell parameters from 25 reflections
b = 10.582 (2) Å	θ = 10–13°
c = 9.5710 (19) Å	µ = 0.25 mm⁻¹
β = 108.58 (3)°	T = 293 K
V = 1287.3 (4) Å³	Block, colourless
Z = 4	0.30 × 0.20 × 0.20 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1596 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.032
Graphite monochromator	θ_max = 25.3°, θ_min = 2.5°
ω/2θ scans	h = 0→16
Absorption correction: ψ scan (North et al., 1968)	k = 0→12
T_min = 0.930, T_max = 0.953	l = −11→10
2438 measured reflections	3 standard reflections every 200 reflections
2336 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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.141	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.074P)² + 0.12P] where P = (F_o² + 2F_c²)/3
2336 reflections	(Δ/σ)_max < 0.001
172 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₄H₁₁N₃OS	V = 1287.3 (4) Å³
M_r = 269.32	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.409 (3) Å	µ = 0.25 mm⁻¹
b = 10.582 (2) Å	T = 293 K
c = 9.5710 (19) Å	0.30 × 0.20 × 0.20 mm
β = 108.58 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1596 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.032
T_min = 0.930, T_max = 0.953	3 standard reflections every 200 reflections
2438 measured reflections	intensity decay: 1%
2336 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.141	H-atom parameters constrained
S = 1.00	Δρ_max = 0.22 e Å⁻³
2336 reflections	Δρ_min = −0.22 e Å⁻³
172 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	0.07308 (7)	0.15388 (7)	0.18224 (8)	0.0444 (3)
O	0.3343 (2)	−0.0997 (2)	−0.2453 (3)	0.0751 (8)
N1	0.0991 (2)	−0.0816 (2)	0.2420 (3)	0.0438 (6)
N2	0.0458 (2)	−0.0359 (2)	0.3336 (3)	0.0450 (6)
N3	−0.0237 (2)	0.1545 (2)	0.3882 (3)	0.0564 (7)
H3A	−0.0449	0.1197	0.4550	0.068*
H3B	−0.0344	0.2337	0.3693	0.068*
C1	0.4549 (4)	0.1716 (4)	−0.4561 (5)	0.0764 (12)
H1B	0.4826	0.2314	−0.5046	0.092*
C2	0.3629 (4)	0.1137 (4)	−0.5265 (5)	0.0870 (13)
H2B	0.3273	0.1343	−0.6242	0.104*
C3	0.3208 (3)	0.0249 (4)	−0.4566 (5)	0.0729 (11)
H3C	0.2572	−0.0142	−0.5061	0.087*
C4	0.3732 (3)	−0.0048 (3)	−0.3145 (4)	0.0526 (8)
C5	0.4662 (3)	0.0517 (4)	−0.2422 (4)	0.0721 (11)
H5A	0.5027	0.0301	−0.1451	0.086*
C6	0.5062 (3)	0.1415 (4)	−0.3144 (5)	0.0834 (13)
H6A	0.5691	0.1818	−0.2648	0.100*
C7	0.2835 (3)	−0.0671 (3)	−0.1459 (4)	0.0501 (8)
C8	0.2482 (3)	0.0534 (3)	−0.1339 (4)	0.0586 (9)
H8A	0.2603	0.1185	−0.1918	0.070*
C9	0.1947 (3)	0.0763 (3)	−0.0349 (4)	0.0537 (9)
H9A	0.1701	0.1573	−0.0272	0.064*
C10	0.1769 (2)	−0.0194 (3)	0.0532 (3)	0.0383 (7)
C11	0.2148 (2)	−0.1399 (3)	0.0400 (4)	0.0481 (8)
H11A	0.2044	−0.2051	0.0989	0.058*
C12	0.2673 (2)	−0.1634 (3)	−0.0592 (4)	0.0516 (8)
H12A	0.2919	−0.2443	−0.0677	0.062*
C13	0.1199 (2)	0.0043 (3)	0.1577 (3)	0.0375 (7)
C14	0.0255 (2)	0.0854 (3)	0.3138 (3)	0.0406 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S	0.0627 (5)	0.0291 (4)	0.0463 (4)	0.0030 (4)	0.0244 (4)	0.0026 (3)
O	0.101 (2)	0.0436 (14)	0.115 (2)	−0.0098 (13)	0.0814 (18)	−0.0134 (14)
N1	0.0596 (16)	0.0287 (13)	0.0480 (14)	0.0027 (11)	0.0241 (12)	0.0010 (11)
N2	0.0619 (17)	0.0319 (13)	0.0483 (15)	0.0004 (12)	0.0274 (13)	0.0014 (11)
N3	0.091 (2)	0.0384 (14)	0.0525 (15)	0.0099 (14)	0.0404 (15)	0.0044 (13)
C1	0.085 (3)	0.072 (3)	0.082 (3)	−0.004 (2)	0.040 (2)	0.017 (2)
C2	0.097 (3)	0.081 (3)	0.070 (3)	0.009 (3)	0.008 (2)	0.018 (2)
C3	0.052 (2)	0.066 (3)	0.088 (3)	−0.0005 (19)	0.005 (2)	−0.004 (2)
C4	0.057 (2)	0.0439 (18)	0.069 (2)	−0.0033 (16)	0.0369 (18)	−0.0102 (17)
C5	0.081 (3)	0.084 (3)	0.049 (2)	−0.020 (2)	0.0162 (19)	0.0017 (19)
C6	0.068 (3)	0.095 (3)	0.086 (3)	−0.035 (2)	0.021 (2)	0.006 (3)
C7	0.055 (2)	0.0393 (18)	0.067 (2)	−0.0050 (15)	0.0341 (17)	−0.0090 (16)
C8	0.079 (2)	0.0385 (18)	0.075 (2)	0.0031 (16)	0.049 (2)	0.0069 (16)
C9	0.074 (2)	0.0316 (16)	0.069 (2)	0.0056 (16)	0.0412 (19)	0.0000 (15)
C10	0.0392 (16)	0.0307 (15)	0.0458 (16)	−0.0012 (12)	0.0147 (13)	−0.0015 (12)
C11	0.0474 (18)	0.0367 (17)	0.065 (2)	0.0023 (14)	0.0253 (16)	0.0064 (15)
C12	0.0516 (19)	0.0341 (16)	0.077 (2)	−0.0005 (14)	0.0322 (17)	−0.0031 (16)
C13	0.0410 (16)	0.0299 (14)	0.0392 (15)	−0.0004 (12)	0.0093 (13)	0.0004 (12)
C14	0.0527 (19)	0.0329 (16)	0.0358 (15)	−0.0009 (13)	0.0137 (14)	−0.0029 (12)

Geometric parameters (Å, º) top

S—C14	1.740 (3)	C3—H3C	0.9300
S—C13	1.746 (3)	C4—C5	1.357 (5)
O—C7	1.378 (4)	C5—C6	1.380 (5)
O—C4	1.393 (4)	C5—H5A	0.9300
N1—C13	1.303 (4)	C6—H6A	0.9300
N1—N2	1.383 (3)	C7—C12	1.374 (4)
N2—C14	1.314 (4)	C7—C8	1.378 (4)
N3—C14	1.333 (4)	C8—C9	1.381 (4)
N3—H3A	0.8600	C8—H8A	0.9300
N3—H3B	0.8600	C9—C10	1.386 (4)
C1—C6	1.349 (5)	C9—H9A	0.9300
C1—C2	1.349 (6)	C10—C11	1.393 (4)
C1—H1B	0.9300	C10—C13	1.462 (4)
C2—C3	1.375 (6)	C11—C12	1.373 (4)
C2—H2B	0.9300	C11—H11A	0.9300
C3—C4	1.354 (5)	C12—H12A	0.9300

C14—S—C13	87.14 (13)	C12—C7—C8	120.7 (3)
C7—O—C4	119.3 (2)	C12—C7—O	116.0 (3)
C13—N1—N2	113.8 (2)	C8—C7—O	123.2 (3)
C14—N2—N1	112.0 (2)	C7—C8—C9	119.2 (3)
C14—N3—H3A	120.0	C7—C8—H8A	120.4
C14—N3—H3B	120.0	C9—C8—H8A	120.4
H3A—N3—H3B	120.0	C8—C9—C10	121.1 (3)
C6—C1—C2	119.2 (4)	C8—C9—H9A	119.4
C6—C1—H1B	120.4	C10—C9—H9A	119.4
C2—C1—H1B	120.4	C9—C10—C11	118.4 (3)
C1—C2—C3	121.2 (4)	C9—C10—C13	121.3 (3)
C1—C2—H2B	119.4	C11—C10—C13	120.3 (3)
C3—C2—H2B	119.4	C12—C11—C10	120.7 (3)
C4—C3—C2	119.0 (4)	C12—C11—H11A	119.6
C4—C3—H3C	120.5	C10—C11—H11A	119.6
C2—C3—H3C	120.5	C11—C12—C7	119.9 (3)
C3—C4—C5	120.6 (3)	C11—C12—H12A	120.1
C3—C4—O	119.5 (3)	C7—C12—H12A	120.1
C5—C4—O	119.9 (3)	N1—C13—C10	124.5 (3)
C4—C5—C6	119.2 (4)	N1—C13—S	113.1 (2)
C4—C5—H5A	120.4	C10—C13—S	122.4 (2)
C6—C5—H5A	120.4	N2—C14—N3	125.0 (3)
C1—C6—C5	120.7 (4)	N2—C14—S	113.9 (2)
C1—C6—H6A	119.6	N3—C14—S	121.1 (2)
C5—C6—H6A	119.6

C13—N1—N2—C14	1.2 (4)	C9—C10—C11—C12	−0.7 (5)
C6—C1—C2—C3	−0.1 (7)	C13—C10—C11—C12	179.2 (3)
C1—C2—C3—C4	−0.2 (7)	C10—C11—C12—C7	0.4 (5)
C2—C3—C4—C5	−0.3 (6)	C8—C7—C12—C11	0.5 (5)
C2—C3—C4—O	−176.4 (3)	O—C7—C12—C11	−178.2 (3)
C7—O—C4—C3	−103.8 (4)	N2—N1—C13—C10	178.9 (3)
C7—O—C4—C5	80.0 (4)	N2—N1—C13—S	−0.7 (3)
C3—C4—C5—C6	1.0 (6)	C9—C10—C13—N1	178.9 (3)
O—C4—C5—C6	177.1 (4)	C11—C10—C13—N1	−1.0 (4)
C2—C1—C6—C5	0.8 (7)	C9—C10—C13—S	−1.6 (4)
C4—C5—C6—C1	−1.3 (7)	C11—C10—C13—S	178.6 (2)
C4—O—C7—C12	−166.5 (3)	C14—S—C13—N1	0.1 (2)
C4—O—C7—C8	14.8 (5)	C14—S—C13—C10	−179.6 (2)
C12—C7—C8—C9	−1.0 (6)	N1—N2—C14—N3	−179.2 (3)
O—C7—C8—C9	177.6 (3)	N1—N2—C14—S	−1.2 (3)
C7—C8—C9—C10	0.7 (5)	C13—S—C14—N2	0.6 (2)
C8—C9—C10—C11	0.2 (5)	C13—S—C14—N3	178.7 (3)
C8—C9—C10—C13	−179.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N2ⁱ	0.86	2.21	3.042 (4)	162
N3—H3B···N1ⁱⁱ	0.86	2.26	3.094 (3)	163
C9—H9A···S	0.93	2.72	3.133 (4)	108

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₁N₃OS
M_r	269.32
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	13.409 (3), 10.582 (2), 9.5710 (19)
β (°)	108.58 (3)
V (Å³)	1287.3 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.930, 0.953
No. of measured, independent and observed [I > 2σ(I)] reflections	2438, 2336, 1596
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.141, 1.00
No. of reflections	2336
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.22

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	2.2100	3.042 (4)	162.00
N3—H3B···N1ⁱⁱ	0.8600	2.2600	3.094 (3)	163.00
C9—H9A···S	0.9300	2.7200	3.133 (4)	108.00

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

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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