1-Benzoyl-3-(4-hy­droxy­phen­yl)thio­urea

Aisha A Al-abbasi; Siew San Tan; Mohammad B Kassim

doi:10.1107/S1600536810045988

. 2010 Nov 13;66(Pt 12):o3181. doi: 10.1107/S1600536810045988

1-Benzoyl-3-(4-hydroxyphenyl)thiourea

Aisha A Al-abbasi ^a, Siew San Tan ^a, Mohammad B Kassim ^a,^*

PMCID: PMC3011591 PMID: 21589476

Abstract

In the title compound, C₁₄H₁₂N₂O₂S, the aminophenol and the benzoyl groups adopt a syn–anti configuration with respect to the thiono C=S group across the thiourea C—N. The dihedral angle between the mean planes of the benzoyl and hydroxyphenyl rings is 36.77 (8)°. The molecules are stabilized by intramolecular N—H⋯O hydrogen bonds. In the crystal, weak intermolecular C—H⋯O, O—H⋯S and N—H⋯O hydrogen bonds link the molecules into a chain along the c axis.

Related literature

For the preparation and chemical properties of related compounds, see: Zhang et al. (2001 ▶). For related structures, see: Abosadiya et al. (2007 ▶); Hung et al. (2010 ▶); Yamin & Yusof (2003 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₄H₁₂N₂O₂S
M _r = 272.33
Orthorhombic,
a = 5.5865 (10) Å
b = 14.451 (2) Å
c = 16.462 (3) Å
V = 1329.0 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 298 K
0.50 × 0.48 × 0.35 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.886, T _max = 0.919
7608 measured reflections
2351 independent reflections
2143 reflections with I > 2σ(I)
R _int = 0.018

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.085
S = 1.05
2351 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.14 e Å⁻³
Absolute structure: Flack (1983 ▶), 958 Friedel pairs
Flack parameter: 0.09 (9)

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); 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, PARST (Nardelli, 1995 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810045988/jj2068sup1.cif

e-66-o3181-sup1.cif^{(17.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810045988/jj2068Isup2.hkl

e-66-o3181-Isup2.hkl^{(115.6KB, 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—H2B⋯O1	0.86	1.95	2.631 (2)	135
N1—H1B⋯O2ⁱ	0.86	2.29	3.109 (2)	158
O2—H2C⋯S1ⁱⁱ	0.82	2.53	3.1533 (18)	134
C1—H1A⋯O2ⁱ	0.93	2.51	3.429 (3)	172
C11—H11A⋯O1ⁱⁱⁱ	0.93	2.43	3.262 (2)	149

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

Acknowledgments

The authors thank Universiti Kebangsaan Malaysia for providing facilities and grants UKM-GUP-BTT-07–30-190 and UKM-OUP-TK-16–73/2010, the Libyan Government for providing a scholarship for AA and J.-C. Daran for his advice.

supplementary crystallographic information

Comment

The title compound, I, is closely related to the previously reported N-benzoyl-N'-(3-hydroxyphenyl)thiourea (II) (Abosadiya et al., 2007) compound. As in most benzoylthiourea derivatives of the type R₁C(O)NHC(S)NHR₂, the title compound has a syn–anti configuration for the hydroxyphenyl and benzoyl groups with respect to the thiono C=S bond across the thiourea C—N bond (Fig 1). The bond lengths and angles in the molecules are in normal ranges (Allen et al., 1987) and comparable to those in (II). All C—N bond lengths are shorter than the normal value for C—N single bond, and the bond lengths C7—O1 and C8—S1 become longer than normal values for a double bond, which suggests the presence of delocalized π-electrons. For example, the C=S bond (1.671 (2) Å) and C—N bond lengths (C8—N1 = 1.388 (2) Å, C8—N2 = 1.328 (2) Å and C9—N2 = 1.428 (2) Å) in the title compound are longer than that observed in an unsubsituted phenyl ring (III - Yamin et al., 2003) in which the C=S bond length (1.6567 (15) Å) and C—N bond lengths are 1.393 (2), 1.326 (2) and 1.408 (2) Å, respectively. This is due to donating effect of OH group in the para position, which contributes to an increase in the bond length.

The benzoyl ring [C1/C2/C3/C4/C5/C6/C7/O1] (A), hydroxyphenyl ring [N2/C9/C10/C11/C12/C13/C14/O2] (B) and thiourea [(S1/N1/N2/C8/] (C) fragments are essentially planar with maximum deviations from their mean planes of 0.045 (2) Å for atom O1 (A), 0.010 (2) Å for atom C10 (B) and 0.008 (2)Å for atom C8 (C), respectively. The dihedral angle between the mean planes of A and B is 36.77 (8)°. The crytal structure is stabilized by an intramolecular N2—H2B···O1 hydrogen bond which forms a six-membered ring (N2/H2B/O1/C7/N1/C8) commonly observed in this class of ligands. In addition, the molecules are linked by weak intermolecular C11—H···O1, C1—H···O2, O2—H···S1 and N1—H···O2 hydrogen bonds (Table 2), resulting in a one-dimensional chain along the c-axis (Fig 2).

Experimental

The title compound was first synthesized by (Zhang et al., 2001) under the condition of solid-liquid phase transfer catalysis using polyethylene glycol as catalyst, however, a much simpler method was used to synthesize the title compound. The reaction scheme involved a reaction of benzoyl chloride (10 mmol) with ammonium thiocyanate (10 mmol) in dry acetone. The product, benzoyl isothiocyanate was reacted with 4-hydroxy aniline (10 mmol) to give the title compound with a 56% yield. A slow evaporation of ethanolic solution of the compound gave light brawn crystals suitable for X-ray diffraction.