1-[3,5-Bis(trifluoro­meth­yl)phen­yl]-3-(2-pyrid­yl)thio­urea

Huadong Yue; Yifeng Wang; Aibao Xia; Shuping Luo; Danqian Xu

doi:10.1107/S1600536808009768

. 2008 Apr 16;64(Pt 5):o858. doi: 10.1107/S1600536808009768

1-[3,5-Bis(trifluoromethyl)phenyl]-3-(2-pyridyl)thiourea

Huadong Yue ^a, Yifeng Wang ^a, Aibao Xia ^a, Shuping Luo ^a, Danqian Xu ^a,^*

PMCID: PMC2961226 PMID: 21202345

Abstract

The title compound, C₁₄H₉F₆N₃S, exhibits a nearly planar conformation in the solid state, with a dihedral angle between the planes of the benzene and pyridine rings of 14.86 (3)°. The pyridine N atom allows for the formation of a six-membered N—H⋯N_py hydrogen-bonded ring, thus forcing the two amide H atoms of the thiourea group to point in opposite directions. The second N—H group forms an intermolecular N—H⋯S hydrogen bond with the S atom of an adjacent molecule. The F atoms of the two trifluoromethyl groups display rotational disorder around the C—CF₃ axis, with an occupancy ratio of 0.54 (1):0.46 (1).

Related literature

For related literature, see: Akiyama et al. (2006 ▶); Struga et al. (2007 ▶).

Experimental

Crystal data

C₁₄H₉F₆N₃S
M _r = 365.30
Orthorhombic,
a = 15.0907 (17) Å
b = 7.7491 (9) Å
c = 26.709 (3) Å
V = 3123.3 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 293 (2) K
0.41 × 0.31 × 0.17 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.873, T _max = 0.962
17235 measured reflections
3406 independent reflections
2585 reflections with I > 2σ(I)
R _int = 0.102

Refinement

R[F ² > 2σ(F ²)] = 0.058
wR(F ²) = 0.151
S = 1.06
3406 reflections
280 parameters
13 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2000 ▶); data reduction: SAINT-Plus and SHELXTL (Sheldrick, 2008 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808009768/zl2103sup1.cif

e-64-0o858-sup1.cif^{(20.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808009768/zl2103Isup2.hkl

e-64-0o858-Isup2.hkl^{(167.2KB, hkl)}

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
N2—H2⋯N3	0.83 (2)	1.92 (2)	2.641 (3)	144 (2)
N1—H1⋯S1ⁱ	0.798 (17)	2.617 (18)	3.3931 (19)	165 (3)

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Symmetry code: (i) Inline graphic .

Acknowledgments

We acknowledge the help of Professor Jie Sun of Shanghai Institute of Organic Chemistry.

supplementary crystallographic information

Comment

Thiourea compounds have been extensively studied over the last few years due to their pharmacological and biological activities (Struga et al., 2007). Recently, excellent results have been also achieved with the use of the bifunctional thiourea catalysts, which effectively activate carbonyl groups and imines through double hydrogen-bonding interactions in asymmetric synthesis (Akiyama et al., 2006). Herein, we synthesized the title compound (I) and determined its crystal structure (Fig.1). The benzene and pyridine rings in the structural unit of (I) are almost perfectly coplanar with a dihedral angle between their planes of only 14.86 (3)°. Like other 2-pyridyl thioureas, the title compound exhibits both intramolecular and intermolecular hydrogen bonding interactions. The pyridine nitrogen N3 allows for the formation of a six membered N—H···N_pyr hydrogen bonded ring which forces the two amide hydrogen atoms of the thiourea group to point in opposite directions. At the same time, the N1—H1 and C9—H9 moieties of the pyridine ring form intermolecular N—H···S and C—H···S hydrogen bonds with the S atom of an adjacent molecule (Fig. 2). This weak hydrogen-bonding network leads to the formation of infinite chains of molecules thus stabilizing the crystal packing.

Experimental

The title compound was synthesized by treating 3,5-bis-trifluoromethyl-phenyl isothiocyanate (2.71 g, 10 mmol) with 2-amino pyridine (0.94 g, 10 mmol) in MeCN (30 ml) under stirring at room temperature for 24 h. Suitable crystals of the title compound were obtained by slow evaporation of an actonitrile solution at room temperature (3.28 g, 10 mmol). Yield 90%, m.p. 431–433 K, ¹H NMR (500 MHz, CDCl₃): 6.91 (d, J = 8 Hz, 1H), 7.08–7.11 (m, 1H), 7.73–7.77 (m, 2H), 8.27 (s, 1H), 8.29–8.31 (m, 2H), 8.95 (s, 1H), 14.17 (s, 1H).