N,N-Diethyl-N′-phenyl­acetyl­thio­urea

Liang Xian

doi:10.1107/S1600536808035290

. 2008 Nov 8;64(Pt 12):o2256. doi: 10.1107/S1600536808035290

N,N-Diethyl-N′-phenylacetylthiourea

Liang Xian ^a,^*

PMCID: PMC2959839 PMID: 21581237

Abstract

The title thiourea molecule, C₁₃H₁₈N₂OS, adopts a folded conformation due to the steric hindrance of the two ethyl groups and the acetyl group. In the crystal structure, the acetyl O atom is not involved in hydrogen bonding, but intermolecular N—H⋯S hydrogen bonds link the molecules into centrosymmetric dimers.

Related literature

For general background on the chemistry of thiourea derivatives, see: Choi et al. (2008 ▶); Jones et al. (2008 ▶); Kushwaha et al. (2008 ▶); Su et al. (2006 ▶). For related structures, see: Su (2005 ▶, 2007 ▶); Xian et al. (2004 ▶); Xian (2008 ▶).

Experimental

Crystal data

C₁₃H₁₈N₂OS
M _r = 250.35
Monoclinic,
a = 11.578 (7) Å
b = 12.804 (8) Å
c = 9.176 (6) Å
β = 103.842 (10)°
V = 1320.8 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 296 (2) K
0.30 × 0.29 × 0.25 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ▶) T _min = 0.933, T _max = 0.944
7619 measured reflections
3080 independent reflections
2484 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.124
S = 1.05
3080 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Data collection: APEX2 (Bruker, 2001 ▶); cell refinement: APEX2 and SAINT (Bruker, 2001 ▶); data reduction: SAINT; 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: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808035290/cv2467sup1.cif

e-64-o2256-sup1.cif^{(16.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808035290/cv2467Isup2.hkl

e-64-o2256-Isup2.hkl^{(151.1KB, 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—H1′⋯S1ⁱ	0.86	2.69	3.404 (3)	141

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Symmetry code: (i) Inline graphic .

Acknowledgments

Financial support of this work by the Foundation of Northwest University for Nationalities are acknowledged.

supplementary crystallographic information

Comment

Thiourea and its derivatives attract special attention in recent years because of their broad applications, such as anion recognition, nonlinear optical material, catalysis etc., and also due to high bioactivity and good coordination ability (Choi et al., 2008; Kushwaha et al., 2008; Jones et al. 2008; Su et al., 2006). For a long time, we have being interested in the influence of non-covalent interactions related to the substituted groups on the conformations of thiourea derivatives as well as their coordination abilities. Thiourea derivatives with different substituted groups coordinate different transition metal ions providing various structures. One of the key influence factors in coordination reactions is non-covalent interaction. However, the central ion also plays and important role. Triangle conformation is commonly observed in the coordination compound of benzoylthiourea with Cu(I) (Xian et al., 2004). However, Cu₆ cluster structure was also obtained (Su et al., 2005). Herewith we present the crystal structure of the title compound, (I).

The conformation and the packing diagram of (I) are shown in Figures 1 and 2, respectively. It can be seen that the title compound has a folded conformation which is similar to the structure we obtained before (CCDC No. 699688). The dihedral angle between the benzene ring and the plane O1/ N1/C7/C8 is 69.12 (6)°, and the dihedral angle between the benzene ring and the plane S1/C9/N1/N2 is 67.19 (6)°. Apparently, stereo-hindrance effect of two ethyl groups and acetyl group is the main influence factor to the folded conformation. Because of the absence of hydrogen atom on N2, the acetyl oxygen atom does not take part in hydrogen bonding interactions. This is different from the other carbonylthiourea derivatives (Su et al., 2006; Xian, 2008), in which the carbonyl oxygen atom often forms a six-membered hydrogen bonding ring. However, thiocarbonyl sulfur atom is involved in an intermolecular N—H···S hydrogen bond (Table 1), linking two molecules into centrosymmetric dimer, that was eralier observed in related structures (Su, 2007; Xian, 2008).

Experimental

All reagents and organic solvents were of analytical reagent grade and commercially available. Phenylacetyl chloride (1.55 g) was treated with ammonium thiocyanate (1.20 g) in CH₂Cl₂ under solid-liquid phase transfer catalysis conditions, using 3% polyethylene glycol-400 as catalyst, to give the corresponding phenylacetyl isothiocyanate, which was reacted with diethylamine (0.73 g) to give the title compound. The solid was separated from the liquid phase by filtration, washed with CH₂Cl₂ and then dried in air. Colorless single crystals suitable for X-ray analysis were obtained after one week by slow evaporation of an chloroform solution. The infrared spectrum was recorded in the range of 4000–400 cm^-1 on a Nicolet NEXUS 670 F T—IR spectrometer, using KBr pellets. ¹H NMR spectrum was obtained on an INOVA-400 MHz superconduction spectrometer, acetone_d6 was used as solvent and TMS as internal standard, and the chemical shifts are expressed as delta. Elemental analyses were carried out on a PE-2400 elemental analysis instrument. Melting point determination was performed in YRT-3 melting point instrument (Tianjin) and was uncorrected. Melting Point: 92–94 °C. Elemental analysis (%) found (calcd.): C, 62.3(60.5); H, 7.2(6.9); N, 11.2(13.6); S, 12.8(10.9). IR (KBr, cm^-1): 3190 (N—H), 3079, 1711 (C=O), 1548(C=C), 1233(C=S), 1121. ¹H NMR(delta, p.p.m.): 2.06 (m, 3H, CH₃); 2.85 (m, 3H, CH₃);3.70 (m, 6H, 3CH₂); 7.22–7.38 (m, 5H, C₆H₅); 9.25 (s, 1H, NH).