1-(2,6-Dichloro­benzo­yl)-3-(3-methoxy­phen­yl)thio­urea

M Khawar Rauf; Michael Bolte; Amin Badshah

doi:10.1107/S1600536808041263

. 2008 Dec 17;65(Pt 1):o142. doi: 10.1107/S1600536808041263

1-(2,6-Dichlorobenzoyl)-3-(3-methoxyphenyl)thiourea

M Khawar Rauf ^a, Michael Bolte ^b, Amin Badshah ^a,^*

PMCID: PMC2968058 PMID: 21581601

Abstract

The two aromatic rings in the title compound, C₁₅H₁₂Cl₂N₂O₂S, enclose a dihedral angle of 37.49 (6)°. The molecule exists in the solid state in its thione form with typical thiourea C—S and C—O bonds lengths, as well as shortened C—N bonds. An intramolecular N—H⋯O hydrogen bond stabilizes the molecular conformation. In the crystal, molecules are connected by N—H⋯O and N—H⋯S hydrogen bonds, forming chains running along the a axis.

Related literature

For general background, see: Darlington et al. (1996 ▶); Dowding & Leeds (1971 ▶); Sasse et al. (1969 ▶); Khawar Rauf et al., (2006a ▶,b ▶,c ▶, 2007 ▶); Santrucek & Krepelka (1988 ▶); Teruhisa et al. (1972 ▶). For related structures, see: Khawar Rauf et al. (2006a ▶,b ▶,c ▶, 2007 ▶). For a description of the Cambridge Database, see: Allen, (2002 ▶).

Experimental

Crystal data

C₁₅H₁₂Cl₂N₂O₂S
M _r = 355.23
Monoclinic,
a = 10.7215 (6) Å
b = 11.2370 (8) Å
c = 13.8065 (8) Å
β = 104.447 (4)°
V = 1610.77 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.54 mm⁻¹
T = 173 (2) K
0.47 × 0.47 × 0.44 mm

Data collection

STOE IPDS II two-circle-diffractometer
Absorption correction: multi-scan (MULABS; Spek, 2003 ▶; Blessing, 1995 ▶) T _min = 0.786, T _max = 0.797
19919 measured reflections
4113 independent reflections
3704 reflections with I > 2σ(I)
R _int = 0.060

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.087
S = 1.07
4113 reflections
218 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2001 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808041263/dn2414sup1.cif

e-65-0o142-sup1.cif^{(19KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808041263/dn2414Isup2.hkl

e-65-0o142-Isup2.hkl^{(201.6KB, 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—H2⋯O1	0.89 (2)	1.97 (2)	2.7007 (15)	137.9 (18)
N2—H2⋯O1ⁱ	0.89 (2)	2.38 (2)	3.1015 (16)	137.8 (18)
N1—H1⋯S1ⁱⁱ	0.852 (18)	2.479 (19)	3.3141 (12)	166.7 (16)

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

Acknowledgments

MKR is grateful to the Higher Education Commission of Pakistan for financial support for the PhD program under scholarship No. ILC–0363104.

supplementary crystallographic information

Comment

Thiourea and Urea derivatives have played an important role in developing agrochemicals and pharmacological agents, for example. Ureidothiazoles are effective herbicides for a broad spectrum of weeds (Dowding & Leeds, 1971). N-Methylfurfurylurea herbicides gave selective weed control in cereals, as well as cotton and beans (Sasse et al., 1969). N-Methyl-N-(2-thiazolyl)-N'-alkyl substituted thioureas are plant growth regulators that inhibit stem alongation of rice and kidney bean plants without phytotoxity (Teruhisa et al., 1972). 4-Aminomethyl derivatives of 2-methyl-5-hydroxybenzimidazole have been reported as an antioxidants and stimmulators of plant growth of dicotyledons under drought conditions (Santrucek & Krepelka, 1988; Darlington et al., 1996). As part of interest in N,N'-disubstituted thioureas, we now report the crystal structure of the title compound (I).

A view of compound (I), is shown in Fig 1. The N—C bonds differ significantly from one another but are short in comparison with the typical value for an N—C single bond (1.479 A°), and the C1—S1 bond is slightly shorter than a C—S double bond (1.681 A°), indicating partial electron delocalization in the N—C(S)—N(H)—C(O) structural segment. These distances are similar to those usually found in other substituted thioureas [Khawar Rauf et al., 2006a, 2006b, 2006c, 2007; Cambridge Structural Database, Version 5.28 (Allen, 2002)]. The dihedral angle between the aromatic rings is 37.49 (6)°, and the corresponding angles with the thiourea plane are 81.41 (7)° for the C11–C16 ring and 44.12 (7)° for the C21–C26 ring. The thiocarbonyl and carbonyl groups are almost coplanar, as reflected by the O1—C2—N2—C1 and C2—N2— C1—N1 torsion angles. This is associated with the intramolecular N—H···O hydrogen bond (Table 1), forming a six-membered ring commonly observed in this class of compounds. In the crystal packing of (I), intermolecular N—H···S and N-H···O hydrogen bonds link the molecules into chains running along the a axis (Table 1, Fig. 2).

Experimental

Freshly prepared 2,6-Dichlorobenzoylisothiocyanate (2.32 g, 10 mmol) was added in acetone (30 ml) and stirred for 10 minutes. Afterwards neat 3-methoxyaniline (1.23 g, 10 mmol) was added and the resulting mixture was stirred for 1 h.The reaction mixture was then poured into acidified (pH 4) water and stirred well. The solid product was separated and washed with deionized water and purified by recrystallization from methanol/ 1,1-dichloromethane (1:1 v/v) to give fine crystals of the title compound (I), with an overall yield of 88%. Full spectroscopic and physical characterization will be reported elsewhere.