5-(4-Phenoxy-phen-yl)-1,3,4-thia-diazol-2-amine.

The title compound, C(14)H(11)N(3)OS, was synthesized by the reaction of phenoxy-benzoic acid and thio-semicarbazide. The thia-diazole 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)°. Intra-molecular C-H⋯S contacts are present. In the crystal, inter-molecular N-H⋯N hydrogen bonds link the mol-ecules.

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 = 269.32

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.141

S = 1.00

2336 reflections

172 parameters

H-atom parameters constrained

Δρmax = 0.22 e Å−3

Δρmin = −0.22 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/S1600536809013257/at2760sup1.cif

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

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

C14H11N3OS	F(000) = 560
Mr = 269.32	Dx = 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

Enraf–Nonius CAD-4 diffractometer	1596 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.032
graphite	θmax = 25.3°, θmin = 2.5°
ω/2θ scans	h = 0→16
Absorption correction: ψ scan (North et al., 1968)	k = 0→12
Tmin = 0.930, Tmax = 0.953	l = −11→10
2438 measured reflections	3 standard reflections every 200 reflections
2336 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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.141	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.074P)2 + 0.12P] where P = (Fo2 + 2Fc2)/3
2336 reflections	(Δ/σ)max < 0.001
172 parameters	Δρmax = 0.22 e Å−3
0 restraints	Δρmin = −0.22 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	0.07308 (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)

	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)

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)

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

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) ; (ii) .