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

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

doi:10.1107/S1600536809022594

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1608

doi:10.1107/S1600536809022594

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5-(4-Pentylphenyl)-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 26 May 2009; accepted 12 June 2009; online 17 June 2009)

The title compound, C₁₃H₁₇N₃S, was synthesized by the reaction of 4-pentylbenzoic acid and thiosemicarbazide. The dihedral angle between the thiadiazole and phenyl rings is 29.9 (2)°. An intramolecular C—H⋯S interaction is observed. In the crystal, intermolecular N—H⋯N hydrogen bonding links the molecules into centrosymmetric dimers.

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

C₁₃H₁₇N₃S
M_r = 247.36
Monoclinic, P 2₁ /c
a = 14.012 (3) Å
b = 9.1300 (18) Å
c = 10.938 (2) Å
β = 100.64 (3)°
V = 1375.2 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.22 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 = 0.958, T_max = 0.989
2596 measured reflections
2492 independent reflections
1405 reflections with I > 2σ(I)
R_int = 0.023
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.179
S = 1.00
2492 reflections
148 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯S	0.93	2.81	3.177 (4)	104
N3—H3A⋯N2ⁱ	0.86	2.15	3.006 (4)	173
Symmetry code: (i) -x, -y+1, -z.

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/S1600536809022594/hg2519sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809022594/hg2519Isup2.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, 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 phenyl ring is 29.90 (19)°. An intramolecular C—H···S interaction is observed (Fig. 1). There is intermolecular N—H···N hydrogen bond (Fig. 2), forming chains along the c axis. The intermolecular N—H···N hydrogen bond creates centrosymmetric dimers.

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

4-Pentylbenzoic acid (5 mmol) and thiosemicarbazide (5 mmol) were mixed in a 25 ml flask, and kept in the oil bath at 90°C 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. Dashed lines indicate C—H···S short contact distance.
	Fig. 2. Partial packing view showing the hydrogen-bonded network. Dashed lines indicate intermolecular N—H···N hydrogen bond.

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

Crystal data top

C₁₃H₁₇N₃S	F(000) = 528
M_r = 247.36	D_x = 1.195 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 563 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 14.012 (3) Å	Cell parameters from 25 reflections
b = 9.1300 (18) Å	θ = 8–12°
c = 10.938 (2) Å	µ = 0.22 mm⁻¹
β = 100.64 (3)°	T = 293 K
V = 1375.2 (5) Å³	Block, colorless
Z = 4	0.20 × 0.10 × 0.05 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1405 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.023
Graphite monochromator	θ_max = 25.3°, θ_min = 1.5°
ω/2θ scans	h = −16→0
Absorption correction: ψ scan (North et al., 1968)	k = 0→10
T_min = 0.958, T_max = 0.989	l = −12→13
2596 measured reflections	3 standard reflections every 200 reflections
2492 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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.179	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.09P)²] where P = (F_o² + 2F_c²)/3
2492 reflections	(Δ/σ)_max < 0.001
148 parameters	Δρ_max = 0.18 e Å⁻³
1 restraint	Δρ_min = −0.52 e Å⁻³

Crystal data top

C₁₃H₁₇N₃S	V = 1375.2 (5) Å³
M_r = 247.36	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.012 (3) Å	µ = 0.22 mm⁻¹
b = 9.1300 (18) Å	T = 293 K
c = 10.938 (2) Å	0.20 × 0.10 × 0.05 mm
β = 100.64 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1405 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.023
T_min = 0.958, T_max = 0.989	3 standard reflections every 200 reflections
2596 measured reflections	intensity decay: 1%
2492 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	1 restraint
wR(F²) = 0.179	H-atom parameters constrained
S = 1.00	Δρ_max = 0.18 e Å⁻³
2492 reflections	Δρ_min = −0.52 e Å⁻³
148 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	0.10971 (8)	0.15085 (11)	0.16795 (8)	0.0627 (4)
N1	0.0965 (2)	0.1921 (3)	−0.0647 (2)	0.0595 (9)
N2	0.0606 (2)	0.3197 (3)	−0.0202 (2)	0.0596 (9)
N3	0.0292 (3)	0.4194 (3)	0.1651 (2)	0.0721 (10)
H3A	0.0054	0.4985	0.1290	0.087*
H3B	0.0321	0.4085	0.2438	0.087*
C1	0.4434 (5)	−0.9308 (7)	0.1391 (6)	0.143
H1B	0.4664	−0.9713	0.2201	0.214*
H1C	0.4927	−0.9409	0.0892	0.214*
H1D	0.3860	−0.9820	0.1001	0.214*
C2	0.4207 (5)	−0.7748 (8)	0.1509 (7)	0.165 (3)
H2B	0.4800	−0.7243	0.1875	0.198*
H2C	0.3761	−0.7660	0.2085	0.198*
C3	0.3778 (5)	−0.6986 (7)	0.0342 (7)	0.142 (2)
H3C	0.3235	−0.7561	−0.0083	0.170*
H3D	0.4259	−0.6949	−0.0191	0.170*
C4	0.3422 (5)	−0.5426 (6)	0.0510 (5)	0.135 (2)
H4A	0.3003	−0.5452	0.1123	0.162*
H4B	0.3981	−0.4828	0.0851	0.162*
C5	0.2901 (4)	−0.4706 (5)	−0.0597 (4)	0.0891 (14)
H5A	0.2378	−0.5344	−0.0983	0.107*
H5B	0.3340	−0.4591	−0.1180	0.107*
C6	0.2473 (3)	−0.3212 (4)	−0.0391 (4)	0.0714 (12)
C7	0.1937 (3)	−0.3008 (4)	0.0533 (4)	0.0773 (13)
H7A	0.1831	−0.3795	0.1031	0.093*
C8	0.1557 (3)	−0.1657 (4)	0.0731 (4)	0.0683 (11)
H8A	0.1218	−0.1544	0.1380	0.082*
C9	0.1665 (3)	−0.0480 (4)	0.0002 (3)	0.0555 (9)
C10	0.2190 (3)	−0.0673 (4)	−0.0951 (3)	0.0708 (12)
H10A	0.2275	0.0106	−0.1467	0.085*
C11	0.2583 (3)	−0.2025 (5)	−0.1123 (4)	0.0742 (12)
H11A	0.2935	−0.2138	−0.1759	0.089*
C12	0.1252 (3)	0.0956 (4)	0.0207 (3)	0.0548 (9)
C13	0.0617 (3)	0.3139 (4)	0.0991 (3)	0.0552 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S	0.0965 (8)	0.0583 (6)	0.0329 (5)	0.0097 (6)	0.0112 (4)	0.0063 (4)
N1	0.084 (2)	0.059 (2)	0.0356 (14)	0.0052 (17)	0.0115 (14)	0.0018 (14)
N2	0.087 (2)	0.061 (2)	0.0311 (14)	0.0078 (17)	0.0113 (14)	0.0040 (13)
N3	0.125 (3)	0.060 (2)	0.0326 (15)	0.023 (2)	0.0179 (17)	0.0032 (14)
C1	0.143	0.143	0.143	0.000	0.024	0.000
C2	0.162 (7)	0.139 (6)	0.190 (8)	0.050 (5)	0.024 (6)	0.014 (6)
C3	0.138 (6)	0.117 (5)	0.170 (7)	0.033 (4)	0.024 (5)	0.002 (5)
C4	0.157 (6)	0.103 (4)	0.129 (5)	0.064 (4)	−0.016 (4)	−0.027 (4)
C5	0.112 (4)	0.073 (3)	0.080 (3)	0.014 (3)	0.013 (3)	−0.015 (3)
C6	0.089 (3)	0.066 (3)	0.055 (2)	0.008 (2)	0.001 (2)	−0.009 (2)
C7	0.110 (4)	0.059 (3)	0.067 (3)	−0.003 (2)	0.025 (3)	0.002 (2)
C8	0.094 (3)	0.055 (2)	0.059 (2)	0.005 (2)	0.024 (2)	0.0064 (19)
C9	0.065 (2)	0.063 (2)	0.0365 (17)	0.002 (2)	0.0058 (16)	−0.0017 (17)
C10	0.098 (3)	0.068 (3)	0.050 (2)	0.007 (2)	0.024 (2)	0.003 (2)
C11	0.095 (3)	0.078 (3)	0.051 (2)	0.015 (3)	0.017 (2)	−0.004 (2)
C12	0.067 (2)	0.059 (2)	0.0358 (17)	−0.0042 (19)	0.0041 (16)	0.0006 (16)
C13	0.075 (3)	0.054 (2)	0.0349 (17)	0.0020 (19)	0.0045 (16)	0.0047 (16)

Geometric parameters (Å, º) top

S—C12	1.739 (3)	C4—C5	1.451 (6)
S—C13	1.746 (3)	C4—H4A	0.9700
N1—C12	1.293 (4)	C4—H4B	0.9700
N1—N2	1.392 (4)	C5—C6	1.524 (5)
N2—C13	1.304 (4)	C5—H5A	0.9700
N3—C13	1.333 (4)	C5—H5B	0.9700
N3—H3A	0.8600	C6—C11	1.373 (5)
N3—H3B	0.8600	C6—C7	1.378 (6)
C1—C2	1.471 (6)	C7—C8	1.377 (5)
C1—H1B	0.9600	C7—H7A	0.9300
C1—H1C	0.9600	C8—C9	1.362 (5)
C1—H1D	0.9600	C8—H8A	0.9300
C2—C3	1.480 (8)	C9—C10	1.393 (5)
C2—H2B	0.9700	C9—C12	1.467 (5)
C2—H2C	0.9700	C10—C11	1.379 (5)
C3—C4	1.531 (7)	C10—H10A	0.9300
C3—H3C	0.9700	C11—H11A	0.9300
C3—H3D	0.9700

C12—S—C13	87.26 (17)	C4—C5—C6	115.6 (4)
C12—N1—N2	113.7 (3)	C4—C5—H5A	108.4
C13—N2—N1	112.3 (3)	C6—C5—H5A	108.4
C13—N3—H3A	120.0	C4—C5—H5B	108.4
C13—N3—H3B	120.0	C6—C5—H5B	108.4
H3A—N3—H3B	120.0	H5A—C5—H5B	107.4
C2—C1—H1B	109.5	C11—C6—C7	117.2 (4)
C2—C1—H1C	109.5	C11—C6—C5	122.0 (4)
H1B—C1—H1C	109.5	C7—C6—C5	120.8 (4)
C2—C1—H1D	109.5	C8—C7—C6	121.0 (4)
H1B—C1—H1D	109.5	C8—C7—H7A	119.5
H1C—C1—H1D	109.5	C6—C7—H7A	119.5
C1—C2—C3	116.1 (6)	C9—C8—C7	121.8 (4)
C1—C2—H2B	108.3	C9—C8—H8A	119.1
C3—C2—H2B	108.3	C7—C8—H8A	119.1
C1—C2—H2C	108.3	C8—C9—C10	118.0 (4)
C3—C2—H2C	108.3	C8—C9—C12	121.7 (3)
H2B—C2—H2C	107.4	C10—C9—C12	120.3 (3)
C2—C3—C4	115.0 (6)	C11—C10—C9	119.7 (4)
C2—C3—H3C	108.5	C11—C10—H10A	120.2
C4—C3—H3C	108.5	C9—C10—H10A	120.2
C2—C3—H3D	108.5	C6—C11—C10	122.4 (4)
C4—C3—H3D	108.5	C6—C11—H11A	118.8
H3C—C3—H3D	107.5	C10—C11—H11A	118.8
C5—C4—C3	116.5 (5)	N1—C12—C9	125.3 (3)
C5—C4—H4A	108.2	N1—C12—S	113.3 (3)
C3—C4—H4A	108.2	C9—C12—S	121.4 (3)
C5—C4—H4B	108.2	N2—C13—N3	124.8 (3)
C3—C4—H4B	108.2	N2—C13—S	113.4 (3)
H4A—C4—H4B	107.3	N3—C13—S	121.7 (2)

C12—N1—N2—C13	−1.4 (5)	C5—C6—C11—C10	179.4 (4)
C1—C2—C3—C4	172.2 (6)	C9—C10—C11—C6	0.4 (7)
C2—C3—C4—C5	−173.4 (6)	N2—N1—C12—C9	−179.7 (3)
C3—C4—C5—C6	174.6 (5)	N2—N1—C12—S	0.8 (4)
C4—C5—C6—C11	133.0 (5)	C8—C9—C12—N1	−150.2 (4)
C4—C5—C6—C7	−48.4 (7)	C10—C9—C12—N1	30.3 (6)
C11—C6—C7—C8	−2.0 (7)	C8—C9—C12—S	29.2 (5)
C5—C6—C7—C8	179.4 (4)	C10—C9—C12—S	−150.3 (3)
C6—C7—C8—C9	2.2 (7)	C13—S—C12—N1	−0.1 (3)
C7—C8—C9—C10	−1.0 (6)	C13—S—C12—C9	−179.6 (3)
C7—C8—C9—C12	179.5 (4)	N1—N2—C13—N3	−178.2 (4)
C8—C9—C10—C11	−0.2 (6)	N1—N2—C13—S	1.3 (4)
C12—C9—C10—C11	179.3 (4)	C12—S—C13—N2	−0.7 (3)
C7—C6—C11—C10	0.7 (7)	C12—S—C13—N3	178.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···S	0.93	2.81	3.177 (4)	104
N3—H3A···N2ⁱ	0.86	2.15	3.006 (4)	173

Symmetry code: (i) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₇N₃S
M_r	247.36
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	14.012 (3), 9.1300 (18), 10.938 (2)
β (°)	100.64 (3)
V (Å³)	1375.2 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.22
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	0.958, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	2596, 2492, 1405
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.179, 1.00
No. of reflections	2492
No. of parameters	148
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.52

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
C8—H8A···S	0.93	2.81	3.177 (4)	104
N3—H3A···N2ⁱ	0.86	2.15	3.006 (4)	173

Symmetry code: (i) −x, −y+1, −z.

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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