N-(4-Chloro­butano­yl)-N′-[2-(trifluoro­meth­yl)phen­yl]thio­urea

Mohd Sukeri Mohd Yusof; Nur Farhana Embong; Suhana Arshad; Ibrahim Abdul Razak

doi:10.1107/S1600536812008859

. 2012 Mar 10;68(Pt 4):o1029. doi: 10.1107/S1600536812008859

N-(4-Chlorobutanoyl)-N′-[2-(trifluoromethyl)phenyl]thiourea

Mohd Sukeri Mohd Yusof ^a, Nur Farhana Embong ^a, Suhana Arshad ^b, Ibrahim Abdul Razak ^b,^*,^‡

PMCID: PMC3343992 PMID: 22589901

Abstract

In the title compound, C₁₂H₁₂ClF₃N₂OS, the dihedral angle between the benzene ring and the thiourea fragment is 69.41 (5)°. The thiourea N—H atoms adopt an anti conformation, such that one of them forms an intramolecular N—H⋯O hydrogen bond, generating an S(6) ring. In the crystal, both N—H groups form inversion dimers, one via a pair of N—H⋯S hydrogen bonds and one via a pair of N—H⋯O hydrogen bonds. These lead to R ₂ ²(8) and R ₂ ²(12) loops, respectively. Weak C—H⋯Cl, C—H⋯F, C—H⋯S and π–π [centroid–centroid separation = 3.7098 (6)Å and slippage = 1.853 Å] interactions also occur.

Related literature

For a related structure and background to thiourea derivatives, see: Yusof et al. (2011 ▶). For related structures, see: Khawar Rauf et al. (2006 ▶); Yusof et al. (2007 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₁₂H₁₂ClF₃N₂OS
M _r = 324.75
Triclinic,
a = 7.8622 (1) Å
b = 8.9073 (1) Å
c = 11.0341 (1) Å
α = 113.687 (1)°
β = 103.419 (1)°
γ = 95.653 (1)°
V = 672.18 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.47 mm⁻¹
T = 100 K
0.41 × 0.19 × 0.15 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009) ▶ T _min = 0.829, T _max = 0.932
18148 measured reflections
4884 independent reflections
4304 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.078
S = 0.97
4884 reflections
189 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: APEX2 (Bruker, 2009) ▶; cell refinement: SAINT (Bruker, 2009) ▶; data reduction: SAINT ▶; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812008859/hb6655sup1.cif

e-68-o1029-sup1.cif^{(23.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812008859/hb6655Isup2.hkl

e-68-o1029-Isup2.hkl^{(239.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812008859/hb6655Isup3.cml

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—H1N1⋯O1	0.855 (16)	1.971 (17)	2.6486 (12)	135.4 (16)
N1—H1N1⋯O1ⁱ	0.855 (16)	2.514 (17)	3.2273 (12)	141.6 (14)
N2—H1N2⋯S1ⁱⁱ	0.849 (17)	2.682 (17)	3.5079 (10)	164.7 (14)
C2—H2A⋯Cl1ⁱⁱⁱ	0.95	2.82	3.5535 (11)	135
C3—H3A⋯F1^iv	0.95	2.47	3.2617 (13)	140
C9—H9A⋯S1ⁱⁱ	0.99	2.84	3.7829 (10)	159

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

Acknowledgments

The authors thank the Malaysian Government, Universiti Malaysia Terengganu and Universiti Sains Malaysia for research facilities and the Fundamental Research Grant Scheme (FRGS) No. 203/PFIZIK/6711171 and FRGS 59178 to conduct this work.

supplementary crystallographic information

Comment

As part of our ongoing studies of thiourea derivatives we now describe the title compound. It is analogous to the previously reported N-(4-chlorobutanoyl)-N'- (2-fluorophenyl)thiourea (Yusof et al., 2011) except the fluoro atom is replaced by trifluoromethyl atom.

In the molecular structure (Fig. 1), the benzene ring (C1–C6) is essentially planar with maximum deviation of 0.011 (1) Å at atom C5. The intramolecular N1—H1N1···O1 hydrogen bond (Table 1) generates S(6) ring motifs (Berstein et al., 1995). The bond lengths and angles are within normal ranges and are comparable to the related structures (Khawar Rauf et al., 2006; Yusof et al., 2007).

The crystal packing is shown in Fig. 2. R¹₂(6), R²₂(8), R²₂(12) ring motifs (Berstein et al. 1995) are formed by intermolecular N2—H1N2···S1, N1—H1N1···O1 and C9—H9A···S1 (Table 1) hydrogen bonds, respectively. Intermolecular C2—H2A···Cl1 and C3—H3A···F1 (Table 1) interactions linked the molecules into three-dimensional network. π–π interaction [Cg1···Cg1 (-1 - x, 1 - y, 1 - z) = 3.7098 (6) Å;] are also observed [Cg1: C1–C6].

Experimental

An equimolar amount of 2-(trifluoromethyl)aniline (1.14 g, 7.09 mmol) in 20 ml acetone was added drop-wise into a stirring acetone solution (75 ml) containing 4-chlorobutanoylchloride (1.00 g, 7.09 mmol) and ammonium thiocyanate (0.54 g, 7.09 mmol). The mixture was refluxed for 1 h. Then, the solution was filtered-off and left to evaporate at room temperature to yield colourless needles.