3-Benzoyl-1-(2-meth­oxy­phen­yl)thio­urea

N Selvakumaran; M Mary Sheeba; R Karvembu; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S160053681204456X

. 2012 Nov 3;68(Pt 12):o3259. doi: 10.1107/S160053681204456X

3-Benzoyl-1-(2-methoxyphenyl)thiourea

N Selvakumaran ^a, M Mary Sheeba ^a, R Karvembu ^a,^‡, Seik Weng Ng ^b,^c, Edward R T Tiekink ^b,^*

PMCID: PMC3588812 PMID: 23468777

Abstract

In the title compound, C₁₅H₁₄N₂O₂S, the central C₂N₂OS moiety is planar (r.m.s. deviation of fitted atoms = 0.0336 Å). This is ascribed to the formation of an S(6) loop stabilized by an intramolecular N—H⋯O hydrogen bond; additional intramolecular N—H⋯O and C—H⋯S contacts are also noted. The dihedral angles between the central unit and the phenyl and benzene rings are 23.79 (7) and 29.52 (5)°, respectively. The thione S and ketone O atoms are mutually anti, as are the N—H H atoms; the O atoms lie to the same side of the molecule. Centrosymmetric eight-membered {⋯HNC=S}₂ synthons feature in the crystal packing. The resulting inversion dimers stack along the a axis and are connected into a three-dimensional structure by C—H⋯O and C—H⋯π interactions.

Related literature

For complexation of N-benzoyl-N′-arylthiourea derivatives to transition metals, see: Selvakumaran et al. (2011 ▶). For the structure of the unsubstituted parent compound, see: Yamin & Yusof (2003 ▶).

Experimental

Crystal data

C₁₅H₁₄N₂O₂S
M _r = 286.34
Monoclinic,
a = 5.9358 (1) Å
b = 25.6916 (4) Å
c = 9.0535 (1) Å
β = 92.065 (1)°
V = 1379.76 (4) Å³
Z = 4
Cu Kα radiation
μ = 2.11 mm⁻¹
T = 100 K
0.30 × 0.25 × 0.20 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ▶) T _min = 0.467, T _max = 1.000
5143 measured reflections
2721 independent reflections
2505 reflections with I > 2σ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.097
S = 1.04
2721 reflections
189 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012 ▶); 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 for Windows (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Click here for additional data file.^{(18.6KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681204456X/su2519sup1.cif

e-68-o3259-sup1.cif^{(18.6KB, cif)}

Click here for additional data file.^{(133.6KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681204456X/su2519Isup2.hkl

e-68-o3259-Isup2.hkl^{(133.6KB, hkl)}

Click here for additional data file.^{(5.3KB, cml)}

Supplementary material file. DOI: 10.1107/S160053681204456X/su2519Isup3.cml

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

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

Cg1 is the centroid of the C9–C14 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2n⋯O1	0.905 (18)	1.867 (18)	2.6316 (15)	141.0 (16)
C10—H10⋯S1	0.95	2.68	3.2241 (13)	117
N2—H2n⋯O2	0.90 (2)	2.231 (19)	2.5819 (15)	102.5 (14)
N1—H1n⋯S1ⁱ	0.902 (18)	2.636 (18)	3.4976 (12)	160.1 (15)
C15—H15B⋯O1ⁱⁱ	0.98	2.57	3.4273 (19)	146
C15—H15C⋯Cg1ⁱⁱⁱ	0.98	2.81	3.6248 (17)	141

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

Acknowledgments

NS thanks NITT for a fellowship. The authors also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR-MOHE/SC/12).

supplementary crystallographic information

Comment

N-Benzoyl-N'-arylthiourea derivatives, of which the title compound is an example are versatile ligands with coordination possible via the S, O or N atom, and various combinations of these. The title compound was prepared in connection with on-going studies involving complexation of N-benzoyl-N'-arylthiourea derivatives to transition metals, e.g. Pd^II (Selvakumaran et al., 2011).

In the title compound, Fig. 1, the thione and ketone atoms are anti with respect to each other. Similarly, the N—H H-atoms are anti to each other, and the oxygen atoms lie to the same side of the molecule. The central chromophore is planar with a r.m.s. deviation of 0.0336 Å [maximum deviations of 0.0449 (5) Å for S1, and -0.0460 (9) Å for N1] owing to the presence of an intramolecular N—H···O hydrogen bond which closes an S(6) loop (Table 1). Weaker intramolecular N—H···O and C—H···S contacts are also noted (Table 1). Despite this, a significant twist is evident in the molecule as manifested in the dihedral angle of 53.06 (5)° between the six-membered rings. The relative orientation of the atoms and deviations from planarity described above mimic those reported for the unsubstituted parent compound, PhC(═ O)N(H)C(═ S)N(H)Ph where the dihedral angle between the phenyl rings is 33.26 (6)° (Yamin & Yusof, 2003).

The most significant interaction in the crystal packing is the formation of centrosymmetric eight-membered {···HNC=S}₂ synthons owing to the presence of N—H···S hydrogen bonds (Table ). These inversion dimers stack along the a axis and are connected into a three-dimensional architecture by C—H···O and C—H···π interactions (Fig. 2 and Table 1).

Experimental

A solution of benzoyl chloride (0.005 mol, 0.7029 g) in acetone (30 ml) was added drop wise to a suspension of potassium thiocyanate (0.005 mol, 0.4859 g) in anhydrous acetone (30 ml). The reaction mixture was heated under reflux for 45 minutes and then cooled to room temperature. A solution of substituted 2-methoxyaniline (0.005 mol, 0.6158 g). in acetone (30 ml) was added and the resulting mixture was stirred for 2 h. Hydrochloric acid (0.1 N, 300 ml) was added and resulting solid was filtered, washed with water and dried in vacuo. The resulting solid product was recrystallized from ethanol/dichloromethane (1:2 ratio) solution. Yield: 87%, M. pt: 409 K. Anal. Calcd. for C₁₅H₁₄N₂O₂S (%): C, 62.9; H, 4.9; N, 9.8; Found: C, 63.1; H, 5.1; N, 9.6. Spectroscopic data for the title compound are given in the archived CIF.