4-(4-Bromo­phen­yl)-5-oxo-1,2,3,4,5,6,7,8-octa­hydro­quinazoline-2-thione

Min Xie; Changquan Deng; Jie Zheng; Yulin Zhu

doi:10.1107/S1600536809028761

. 2009 Jul 25;65(Pt 8):o1980. doi: 10.1107/S1600536809028761

4-(4-Bromophenyl)-5-oxo-1,2,3,4,5,6,7,8-octahydroquinazoline-2-thione

Min Xie ^a, Changquan Deng ^a, Jie Zheng ^a, Yulin Zhu ^a,^*

PMCID: PMC2977462 PMID: 21583656

Abstract

The title compound, C₁₄H₁₃BrN₂OS, was synthesized from the multicomponent reaction between thiourea, 4-bromobenzaldehyde and cyclohexane-1,3-dione. The crystal packing is stabilized by intermolecular N—H⋯O, N—H⋯S, C—H⋯O and C—H⋯S hydrogen bonds. Br⋯O interactions [3.183 (3) Å] are also observed in the crystal structure.

Related literature

For the pharmaceutical applications of 4-aryl-5-oxo-1,2,3,4,5,6,7,8-octahydroquinazoline-2-thiones, see: Kappe & Stadler (2004 ▶); Sarac et al. (1997 ▶, 1999 ▶); Yarima et al., (2003 ▶). For background information on halogen bonding, see: Damodharana et al. (2004 ▶); Sureshan et al. (2001 ▶); Yang et al. (2008 ▶).

Experimental

Crystal data

C₁₄H₁₃BrN₂OS
M _r = 337.23
Triclinic,
a = 7.0395 (11) Å
b = 8.1859 (13) Å
c = 13.286 (2) Å
α = 105.329 (2)°
β = 91.279 (2)°
γ = 103.854 (2)°
V = 713.9 (2) Å³
Z = 2
Mo Kα radiation
μ = 3.02 mm⁻¹
T = 293 K
0.25 × 0.25 × 0.20 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.429, T _max = 0.547
3953 measured reflections
2744 independent reflections
1880 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.117
S = 1.04
2744 reflections
174 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809028761/zl2225sup1.cif

e-65-o1980-sup1.cif^{(18.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809028761/zl2225Isup2.hkl

e-65-o1980-Isup2.hkl^{(134.7KB, 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
C2—H2A⋯S1ⁱ	0.97	2.98	3.781 (4)	140
N2—H2⋯S1ⁱⁱ	0.86	2.55	3.380 (3)	161
N1—H1⋯O1ⁱⁱⁱ	0.86	2.00	2.832 (4)	164
C4—H4A⋯O1ⁱⁱⁱ	0.97	2.59	3.361 (4)	137

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

Acknowledgments

The authors thank South China Normal University for financial support (grant Nos. SCNU033038 and SCNU524002).

supplementary crystallographic information

Comment

4-Aryl-5-oxo-1,2,3,4,5,6,7,8-octahydroquinazoline-2-thiones have received much attention recently because of their pharmaceutical applications. (Kappe & Stadler, 2004; Sarac et al., 1997; Sarac et al., 1999). For example, the calcium antagonist activity of the compounds was tested in vitro on isolated rat ileum and lamb carotid artery. (Yarima et al., 2003). As part of our on going studies on the synthesis of quinazolinethiones, the title compound was isolated under Biginelli reaction conditions (Figure 1).

The reaction between thiourea, 4-bromobenzaldehyde, and 1,3-cyclohexanedione instead of an open-chain dicarbonyl compound in the presence of palladium(II) 2,4-pentanedionate as catalyst proceeded to give the title compound in excellent yield. A representation of the title compound is given in Figure 2. There are no unusual bond lengths and angles in the compound. The molecules in the structure are linked via N1—H1···O1 and paired N2—H2···S1 intermolecular hydrogen bonds. The bromine atom Br1 exhibits a Br···O halogen bond with oxygen atom O1 (Figure 3). (Damodharana et al., 2004; Sureshan et al., 2001; Yang et al., 2008). The Br1···O1 distance of this interaction is 3.182 Å, which is less than the sum of their van der Waals radii.

Experimental

A mixture of thiourea (0.91 g, 12 mmol), 4-bromobenzaldehyde (1.84 g, 10 mmol), 1,3-cyclohexanedione (1.12 g, 10 mmol), and palladium(II) 2,4-pentanedionate (0.0020 mg) was refluxed in acetonitrile (12 ml) at 353 K for 4 h. After being cooled to room temperature, the reaction mixture was poured into water. The white precipitate was filtered off with a silica pad, washed twice with water, and the filtrate was then dried under vacuum to yield the product. Single crystals of the title compound were obtained by slow evaporation from ethanol at room temperature to yield colourless, block-shaped crystal.