N-[(4-Carbamoylphen­yl)carbamothio­yl]-2,3,4,5-tetra­fluoro­benzamide

Li-Dan Zhang; Chao Gao; Xue-Jiao Song; Luo-Ting Yu

doi:10.1107/S1600536811005915

. 2011 Feb 23;67(Pt 3):o688. doi: 10.1107/S1600536811005915

N-[(4-Carbamoylphenyl)carbamothioyl]-2,3,4,5-tetrafluorobenzamide

Li-Dan Zhang ^a, Chao Gao ^b, Xue-Jiao Song ^c, Luo-Ting Yu ^b,^*

PMCID: PMC3051937 PMID: 21522433

Abstract

In the title compound, C₁₅H₉F₄N₃O₂S, the N,N′-disubstituted thiourea fragment adopts a cis,trans geometry, stabilized by an intramolecular N—H⋯O hydrogen bond to the carbonyl O atom of the tetrafluorobenzoyl group. The central thiourea group makes dihedral angles of 47.79 (7) and 35.54 (8)° with the two aromatic rings. In the crystal, molecules are linked via N—H⋯O and N—H⋯S hydrogen bonds into two-dimensional polymeric structures parallel to (100). In turn, π–π stacking interactions between tetrafluorobenzene and benzene units [centroid–centroid distance = 3.996 (10) Å; dihedral angle = 13.60 (8)°] organize these two-dimensional assemblies into a three-dimensional framework.

Related literature

For the biological activity of thiourea derivatives, see: Zeng et al. (2003 ▶); Saeed et al. (2010 ▶). For the synthesis of thiourea derivatives, see: Nosova et al. (2007 ▶). For related structures, see: Saeed et al. (2008 ▶, 2009 ▶).

Experimental

Crystal data

C₁₅H₉F₄N₃O₂S
M _r = 371.31
Monoclinic,
a = 7.4246 (3) Å
b = 20.3368 (7) Å
c = 9.8954 (4) Å
β = 95.554 (3)°
V = 1487.12 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 294 K
0.38 × 0.30 × 0.26 mm

Data collection

Oxford Diffraction Xcalibur E CCD diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2006 ▶) T _min = 0.860, T _max = 1.0
6598 measured reflections
3031 independent reflections
2263 reflections with I > 2σ(I)
R _int = 0.014

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.103
S = 1.13
3031 reflections
226 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: OLEX2.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811005915/gk2335sup1.cif

e-67-0o688-sup1.cif^{(19.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811005915/gk2335Isup2.hkl

e-67-0o688-Isup2.hkl^{(148.8KB, 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
N1—H1B⋯S1ⁱ	0.86	2.69	3.4861 (16)	155
N1—H1A⋯O1ⁱⁱ	0.86	2.23	2.8654 (17)	130
N2—H2⋯O2	0.86	1.97	2.6708 (18)	138
N3—H3⋯O1ⁱⁱⁱ	0.86	2.09	2.9062 (18)	157

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

We thank the Analytical and Testing Center of Sichuan University for the X-ray measurements.

supplementary crystallographic information

Comment

N-(4-Carbamoylphenylcarbamothioyl)-2,3,4,5-tetrafluorobenzamide derivatives are of great importance owing to their interesting biological properties (Zeng et al., 2003; Saeed et al., 2010). The title compound is one of the key intermediates in our synthetic route to antiviral drugs. We report here its crystal structure.

In the title compound, C₁₅H₉F₄N₃O₂S, (Fig.1), the cis,trans geometry of the thiourea moiety is stabilized by intramolecular N2—H2···O2 and N3—H3···F1 hydrogen bonds. The central thiourea group makes dihedral angles of 47.79 (7) and 35.54 (8)° with the benzamide unit and the fluorobenzene ring, respectively. A combination of intermolecular π–π stacking interactions, N—H···O, N—H···F and N—H···S hydrogen bonds helps to stabilize the crystal structure (Table 1 and Fig.2).

Experimental

A solution of 0.23 g (3 mmol) of ammonium thiocyanate in 7 ml of acetonitrile was added to a solution of 0.64 g (3 mmol) of 2,3,4,5-tetrafluorobenzoyl chloride in 2.5 ml of toluene. The mixture was heated for 5 min at 40°C and filtered from ammonium chloride, the filtrate was added to a solution of 0.32 g (3 mmol) of 4-aminobenzamide in 5 ml of acetonitrile, the mixture was stirred for 2 h at room temperature and evaporated, and the residue was washed with ethanol and recrystallized from ethanol. Yield 0.91 g (82%). Crystals suitable for X-ray analysis were obtained by slow evaporation from ethyl acetate solution.