3-{(E)-[1-(2-Hy­droxy­phen­yl)ethyl­idene]amino}-1-(2-methyl­phen­yl)thio­urea

Md Abdus Salam; Md Abu Affan; Mohd Razip Asaruddin; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S1600536811013729

. 2011 Apr 16;67(Pt 5):o1164. doi: 10.1107/S1600536811013729

3-{(E)-[1-(2-Hydroxyphenyl)ethylidene]amino}-1-(2-methylphenyl)thiourea

Md Abdus Salam ^a, Md Abu Affan ^a,^‡, Mohd Razip Asaruddin ^a, Seik Weng Ng ^b, Edward R T Tiekink ^b,^*

PMCID: PMC3089068 PMID: 21754471

Abstract

In the title thiourea derivative, C₁₆H₁₇N₃OS, the hydroxy- and methyl-substituted benzene rings form dihedral angles of 9.62 (12) and 55.69 (6)°, respectively, with the central CN₃S chromophore (r.m.s. deviation = 0.0117 Å). An intramolecular O—H⋯N hydrogen bond ensures the coplanarity of the central atoms. The H atoms of the NH groups are syn and the conformation about the N=C double bond [1.295 (4) Å] is E. In the crystal, helical supramolecular chains sustained primarily by N—H⋯S hydrogen bonds are found. Additional stabilization is provided by C—H⋯π and π–π [ring centroid(hydroxybenzene)⋯ring centroid(methylbenzene) = 3.8524 (18) Å] interactions.

Related literature

For pharmaceutical applications of thioruea derivatives, see: Venkatachalam et al. (2004 ▶); Bruce et al. (2007 ▶). For related thiourea structures, see: Normaya et al. (2011 ▶); Salam et al. (2011 ▶); Dzulkifli et al. (2011 ▶).

Experimental

Crystal data

C₁₆H₁₇N₃OS
M _r = 299.39
Monoclinic,
a = 14.6966 (8) Å
b = 7.3586 (4) Å
c = 14.0926 (8) Å
β = 94.358 (5)°
V = 1519.66 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 100 K
0.30 × 0.10 × 0.05 mm

Data collection

Agilent Supernova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.419, T _max = 1.000
7614 measured reflections
3375 independent reflections
2094 reflections with I > 2σ(I)
R _int = 0.066

Refinement

R[F ² > 2σ(F ²)] = 0.060
wR(F ²) = 0.174
S = 1.00
3375 reflections
201 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2010 ▶); 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: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811013729/hg5025sup1.cif

e-67-o1164-sup1.cif^{(18.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811013729/hg5025Isup2.hkl

e-67-o1164-Isup2.hkl^{(162.2KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 is the centroid of the C10–C15 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1o⋯N1	0.84 (1)	1.81 (2)	2.551 (3)	145 (3)
N2—H2n⋯S1ⁱ	0.88 (1)	2.51 (2)	3.323 (2)	154 (3)
N3—H3n⋯S1ⁱ	0.88 (1)	2.49 (2)	3.286 (3)	151 (2)
C8—H8b⋯Cg1ⁱ	0.98	2.59	3.501 (3)	155

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was financially supported by the Ministry of Science Technology and Innovation (MOSTI) under a research grant (No. 06–01-09-SF0046). The authors would like to thank Universiti Malaysia Sarawak (UNIMAS) for the facilities to carry out the research work. The authors also thank the University of Malaya for support of the crystallographic facility.

supplementary crystallographic information

Comment

In continuation of structural investigations into the conformation and hydrogen bonding patterns in thiourea derivatives (Normaya et al. 2011; Salam et al., 2011; Dzulkifli et al., 2011), and also motivated by their pharmacological potential (Venkatachalam et al. 2004; Bruce et al., 2007), the title compound, (I), was investigated.

With respect to the planar (r.m.s. = 0.0117 Å) central CN₃S chromophore in (I), Fig. 1, the OH– and Me-benzene rings are twisted as seen in the respective dihedral angles of 9.62 (12) and 55.69 (6) °. The almost co-planarity of the central atoms is ascribed to the formation of an intramolecular hydroxyl-O—H···N-imine hydrogen bond, Table 1. The H atoms of the NH groups are syn, and the conformation about the N1═C7 double bond [1.295 (4) Å] is E. The syn arrangement in (I) contrast the anti arrangement often seen in such derivatives but is readily explained in terms of the intramolecular O—H···N-imine hydrogen bond in (I) by contrast to the normally observed intramolecular N—H···N-imine hydrogen bond (Normaya et al. 2011; Salam et al., 2011; Dzulkifli et al., 2011).

Helical supramolecular chains along the b axis dominate the crystal packing, Fig. 2 and Table 1. These arise as a result of the thione-S interacting with both N—H atoms of a neighbouring molecule thereby forming six-membered hydrogen bond mediated rings. Chains are stabilized by C—H..π, Table 1, and π–π [ring centroid(C1···C6)···ring centroid(C10···C15)ⁱ = 3.8524 (18) Å, dihedral angle = 2.37 (15) ° for i: 1 - x, -1/2 + y, 1/2 - z] interactions, Fig. 3.

Experimental

2-Methylphenylisothiocyanate (0.746 g, 5 mmol) and hydrazine hydrate (0.253 g, 5 mmol), each dissolved in 10 ml e thanol, were mixed with constant stirring. The stirring was continued for 30 min and the white product formed was washed with ethanol and dried in vacuo. A solution of the isolated 2-methylphenylthiosemicarbazide (0.540 g, 3 mmol) in 10 ml me thanol was then refluxed with a methanolic solution of 2-hydroxyacetophenone (0.408 g, 3 mmol) for 5 h after adding 1–2 drops of glacial acetic acid. On cooling, the solution to room temperature, a light-yellow powder separated and washed with methanol. The powder was recrystallized from methanol and dried in vacuo over silica gel. (M.pt. 451–453 K. Yield 0.740 g (78%). Elemental analysis: Calc. for C₁₆H₁₇N₃OS: C, 64.21; H, 5.73; N, 14.04%. Found: C, 64.17; H, 5.67; N, 14.01%. FT—IR (KBr, cm^-1) ν_max: 3175 (m, OH), 3000 (s, NH), 1583 (w, C═N), 943 (m, N—N), 1371, 861 (w, C═S).