Ethyl 4-(3-butyrylthio­ureido)benzoate

Sohail Saeed; Moazzam Hussain Bhatti; Muhammad Kalim Tahir; Peter G Jones

doi:10.1107/S1600536808017868

. 2008 Jun 28;64(Pt 7):o1369. doi: 10.1107/S1600536808017868

Ethyl 4-(3-butyrylthioureido)benzoate

Sohail Saeed ^a,^*, Moazzam Hussain Bhatti ^a, Muhammad Kalim Tahir ^a, Peter G Jones ^b

PMCID: PMC2961839 PMID: 21202987

Abstract

The title compound, C₁₄H₁₈N₂O₃S, crystallizes in the thioamide form with an intramolecular N—H⋯O hydrogen bond associated with the thiourea unit. With the benzoic acid and the butyrylthioureido units, the molecule consists of two planar building blocks connected by the common NH function adjacent to the aromatic ring. The interplanar angle is 33.38 (3)°. Molecules are connected in chains parallel to [110] by classical hydrogen bonds of the N—H⋯O type from the other NH group to the benzoate C=O of a neighboring molecule.

Related literature

For related literature, see: del Campo et al. (2002 ▶); D’hooghe et al. (2005 ▶); Dušek (1985 ▶); Huebner et al. (1953 ▶); Rodriguez-Fernandez et al. (2005 ▶); Xu et al. (2004 ▶); Zeng et al. (2003 ▶).

Experimental

Crystal data

C₁₄H₁₈N₂O₃S
M _r = 294.36
Triclinic,
a = 7.9817 (4) Å
b = 9.8843 (6) Å
c = 11.0759 (6) Å
α = 114.472 (6)°
β = 101.156 (4)°
γ = 102.277 (5)°
V = 737.15 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 100 (2) K
0.28 × 0.18 × 0.12 mm

Data collection

Oxford Diffraction Xcalibur S diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 ▶) T _min = 0.944, T _max = 1.000 (expected range = 0.918–0.973)
15025 measured reflections
4104 independent reflections
3045 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.096
S = 0.96
4104 reflections
191 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2008 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP (Siemens, 1994 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808017868/im2072sup1.cif

e-64-o1369-sup1.cif^{(19.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808017868/im2072Isup2.hkl

e-64-o1369-Isup2.hkl^{(201.1KB, 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
N2—H02⋯O1	0.82 (2)	1.92 (2)	2.653 (1)	148 (2)
N1—H01⋯O2ⁱ	0.79 (1)	2.20 (1)	2.957 (1)	160 (2)
C13—H13A⋯O1ⁱⁱ	0.99	2.58	3.363 (2)	136
C1—H1B⋯Sⁱⁱⁱ	0.98	3.00	3.854 (2)	147
C13—H13B⋯S^iv	0.99	2.96	3.577 (1)	122
C14—H14C⋯S^v	0.98	2.98	3.821 (2)	144

Open in a new tab

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

supplementary crystallographic information

Comment

Epoxy resins have the combination of good thermal and dimensional stability, excellent chemical and corrosion resistance, high tensile strength and modulus, and ease of handling and processability, ensuring their wide application in the aerospace and electronic industries in the form of structural adhesives, advanced composite matrices, and packaging materials (Dušek, 1985). The properties of cured epoxy polymers largely depend on the nature of chemical structure of the starting resins and curing agents. The title compound (I) is a precursor in an attempt to synthesize imidazole derivatives and transition metal complexes as epoxy resin curing agents and accelerators. Substituted thioureas are an important class of compounds, precursors or intermediates towards the synthesis of a variety of heterocyclic systems such as imidazole-2-thiones (Zeng et al., 2003), 2-imino-1,3-thiazolines (D'hooghe et al., 2005), pyrimidine-2-thiones and (benzothiazolyl)-4-quinazolinones. Thioureas are also known to exhibit a wide range of biological activities including antiviral, antibacterial, antifungal, antitubercular, antithyroidal, herbicidal and insecticidal activities (Huebner et al., 1953) and as agrochemicals (Xu et al., 2004). Among thiourea derivatives, acylthioureas, with O and S as potential donor sites, have been found to display a remarkably rich coordination chemistry. Such coordination compounds of thiourea have been studied for various biological systems (Rodriguez-Fernandez et al., 2005). In recent years some attention has also been paid to the potential use of acylthioureas as highly selective reagents for the enrichment and separation of metal cations (del Campo et al.,2002).

The title compound crystallizes in the thioamide form with an intramolecular hydrogen bond N2—H02···O1. Bond lengths and angles (cf. Supplementary Material) may be regarded as normal. The molecule consists of two planar building blocks: the butyrylthioureido group (S, C1–5, O1, N1, N2) and the benzoic acid moiety (C6–14, N2, O2, O3). Mean deviations from planarity for these moieties are 0.12 and 0.13 Å, respectively, and the interplanar angle is 33.38 (3)°. Molecules are connected to give infinite chains parallel to [110] by classical hydrogen bonds N1—H01···O2. These are in turn connected to antiparallel chains by the weak hydrogen bonds C13—H13A···O1. Additionally, there are three C—H···S contacts that may be borderline weak H bonds (Table 1, Fig. 2).

Experimental

A mixture of ammonium thiocyanate (26 mmol) and butanoyl chloride (26 mmol) in anhydrous acetone (70 ml) was stirred for 35 min. Then p-aminobenzoic acid ethyl ester (26 mmol) was added dropwise and the reaction mixture was refluxed for 2 h. After cooling, the reaction mixture was poured in acidified cold water. The resulting light green solid was filtered and washed with cold acetone.The product was recrystallized from ethanol as light greenish crystals (3.62 g, 91%), m.p. 412 K.