1-(Benzothia­zol-2-yl)-3-(4-nitro­benzo­yl)thio­urea

Sohail Saeed; Naghmana Rashid; Rizwan Hussain; Peter G Jones

doi:10.1107/S1600536809030803

. 2009 Aug 8;65(Pt 9):o2106. doi: 10.1107/S1600536809030803

1-(Benzothiazol-2-yl)-3-(4-nitrobenzoyl)thiourea

Sohail Saeed ^a,^*, Naghmana Rashid ^a, Rizwan Hussain ^b, Peter G Jones ^c

PMCID: PMC2970100 PMID: 21577521

Abstract

The molecule of the title compound, C₁₅H₁₀N₄O₃S₂, is almost planar (r.m.s. deviation = 0.1Å for all non-H atoms). An intramolecular N—H⋯O=C hydrogen bond is observed. In the crystal, molecules are connected into layers parallel to (10 Inline graphic ) by a classical intermolecular hydrogen bond from the second NH group to a nitro O atom and by three weak hydrogen bonds of the C—H⋯X type (X = O or S_thione).

Related literature

For general background to the chemistry of thiourea derivatives, see Choi et al. (2008 ▶); Jones et al. (2008 ▶); Su et al. (2006 ▶). For related structures, see: Saeed et al. (2008a ▶,b ▶,c ▶); Yunus et al. (2008 ▶).

Experimental

Crystal data

C₁₅H₁₀N₄O₃S₂
M _r = 358.39
Monoclinic,
a = 7.1596 (3) Å
b = 17.9071 (5) Å
c = 11.5768 (4) Å
β = 96.446 (4)°
V = 1474.85 (9) Å³
Z = 4
Cu Kα radiation
μ = 3.50 mm⁻¹
T = 100 K
0.20 × 0.10 × 0.05 mm

Data collection

Oxford Diffraction Xcalibur Nova A diffractometer
Absorption correction: multi-scan (CrysAlis Pro; Oxford Diffraction, 2009 ▶) T _min = 0.682, T _max = 1.000 (expected range = 0.573–0.840)
30943 measured reflections
3026 independent reflections
2834 reflections with I > 2σ(I)
R _int = 0.040

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.078
S = 1.06
3026 reflections
225 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: CrysAlis Pro (Oxford Diffraction, 2009 ▶); 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: XP (Siemens, 1994 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809030803/im2131sup1.cif

e-65-o2106-sup1.cif^{(19.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809030803/im2131Isup2.hkl

e-65-o2106-Isup2.hkl^{(148.5KB, 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
N1—H01⋯O1	0.83 (2)	1.92 (2)	2.598 (2)	138 (2)
N2—H02⋯O2ⁱ	0.84 (2)	2.42 (2)	3.261 (2)	175 (2)
C5—H5⋯O1ⁱⁱ	0.95	2.55	3.462 (2)	161
C11—H11⋯O2ⁱ	0.95	2.41	3.318 (2)	159
C12—H12⋯S2ⁱⁱⁱ	0.95	2.73	3.673 (1)	173
C7—H7⋯S2^iv	0.95	2.91	3.563 (1)	127

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

Acknowledgments

The authors are grateful to Allama Iqbal Open University and the National Development Complex, Islamabad, Pakistan for the allocation of research and analytical laboratory facilities.

supplementary crystallographic information

Comment

Thiourea and its derivatives have found extensive applications in the field of medicine, agriculture and analytical chemistry. They are known to exhibit a wide variety of biological activities such as antiviral, anti-bacterial, antifungal, antitubercular, herbicidal, insecticidal and some epoxy resin curing agents containing amino functional groups (Saeedet al., 2008a,b,c). They have found broad areas of application e.g. in anion recognition, nonlinear optics and catalysis, and also display good coordination abilities (Choi et al., 2008; Jones et al., 2008; Su et al., 2006). As part of our research on coordination chemistry of thioureas, we are interested in the study of the influence of non-covalent interactions, especially hydrogen bonds and π-π stacking interactions, on the coordination modes of benzothiazoles bearing the 4- nitrobenzoylthiourea group with transition metal ions. Such coordination compounds of thiourea have been studied for various biological systems like antibactrial, antifungal and anticancer activities (Yunus et al., 2008).The importance of such work lies in the possibility that the next generation of thiourea derivatives might be more efficacious as antimicrobial and anticancer agents. However, a thorough investigation relating structure and activity of thiourea derivatives as well as their stability under biological conditions is required. These detailed investigations could be helpful in designing more potent antimicrobial and anticancer agents for therapeutic use. Condensation of acyl or aroyl thiocyanates with primary amines affords 1, 3-disubstituted thioureas in excellent yields in a single step. In the present paper, the crystal structure of the title compound is reported.

The molecule of the title compound is shown in Fig. 1. The molecule is approximately planar (r.m.s. deviation for all non-H atoms 0.1 Å). The two ring systems (S1–C7A plus N1, C8, N2; C10–C15 plus N4, C9) are essentially parallel (interplanar angle 1.06 (3)°), because non-zero torsion angles such as C11—C10—C9—N2 - 10.7 (2) and N1—C8—N2—C9 7.7 (2)° effectively cancel out.

An intramolecular hydrogen bond N1—H01···O1 is observed. The second classical H bond N2—H02···O2 combines with the three shortest "weak" H bonds H5···O1, H11···O2 and H12···S2 (Table 1) to form layers parallel to (101) (Fig. 2).

Experimental

A mixture of ammonium thiocyanate (0.1 mol) and 4-nitrobenzoyl chloride (0.1 mol) in anhydrous acetone (60 ml) was stirred for 40 min. 2-Aminobenzothiazole (0.1 mol) was added and the reaction mixture was refluxed for 2 h. After cooling, the reaction mixture was poured into 800 ml of acidified cold water (pH = 5). The resulting dark yellow solid was filtered and washed with cold acetone (yield 1.56 g, 87%). The title compound (I) was obtained as suitable crystals for X-ray analysis after recrystallization of the solid from a 1:1 ethanol- dichloromethane mixture.