2-Chloro-N-{5-[(4R,5R,10S)-dehydro­abiet-4-yl]-1,3,4-thia­diazol-2-yl}benzamide

Qijin Mo; Wengui Duan; Xianli Ma; Jianxin Huang; Zhen Ma

doi:10.1107/S1600536811007665

. 2011 Mar 9;67(Pt 4):o816–o817. doi: 10.1107/S1600536811007665

2-Chloro-N-{5-[(4R,5R,10S)-dehydroabiet-4-yl]-1,3,4-thiadiazol-2-yl}benzamide

Qijin Mo ^a, Wengui Duan ^a,^*, Xianli Ma ^b, Jianxin Huang ^a, Zhen Ma ^a

PMCID: PMC3100015 PMID: 21754102

Abstract

There are two independent molecules in the asymmetric unit of the title compound, C₂₈H₃₂ClN₃OS (systematic name: 2-chloro-N-{5-[(1R,4aS,10aR)-7-isopropyl-1,4a-dimethyl-1,2,3,4,4a,9,10,10a-octahydrophenanthren-1-yl]-1,3,4-thiadiazol-2-yl}benzamide). In each molecule, the cyclohexyl ring attached to the thiadiazole fragment adopts a classic chair conformation with two of its two methyl groups in the axial positions. In the crystal, pairs of intermolecular N—H⋯N hydrogen bonds link the molecules into centrosymmetric dimers, which are further linked via C—H⋯π interactions.

Related literature

For background to the uses of rosin, see: Song (2004 ▶). For the isolation of dehydroabietic acid, the major component of disproportionated rosin, see: Xu et al. (2009 ▶). For the biological activity of dehydroabietic derivatives, see: Sepulveda et al. (2005 ▶). For the synthesis of the title compound, see: Liu et al. (2009 ▶). For related structures, see: Rao et al. (2007 ▶); Gu & Wang (2009 ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₂₈H₃₂ClN₃OS
M _r = 494.08
Monoclinic,
a = 7.9707 (16) Å
b = 31.874 (6) Å
c = 10.863 (2) Å
β = 107.24 (3)°
V = 2635.7 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 293 K
0.43 × 0.38 × 0.32 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.898, T _max = 0.923
16616 measured reflections
10596 independent reflections
6952 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.105
S = 1.01
10596 reflections
613 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.23 e Å⁻³
Absolute structure: Flack (1983 ▶), 4741 Friedel pairs
Flack parameter: 0.03 (5)

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXS97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811007665/lx2187sup1.cif

e-67-0o816-sup1.cif^{(40.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811007665/lx2187Isup2.hkl

e-67-0o816-Isup2.hkl^{(518.1KB, hkl)}

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

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

Cg is the centroid of the C23–C28 2-chlorophenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N5	0.86	2.03	2.882 (3)	172
N6—H6A⋯N2	0.86	2.14	2.982 (3)	166
C42—H42B⋯Cgⁱ	0.97	2.65	3.462 (3)	141

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the National Natural Science Foundation of China (No. 31060100) and the Key Project of the Natural Science Foundation of Guangxi, China (No. 2010GXNSFD013013).

supplementary crystallographic information

Comment

Rosin, known as an important chemical raw material, is widely used in papermaking, adhesives, paint, printing ink, rubber, food, and other industries (Song, 2004). Dehydroabietic acid is the dominant component of disproportionated rosin produced by catalytic disproportionation of rosin. Therefore, the search for novel bioactive compounds and the study of their pharmacological properties constitute a matter of current interest. Hence, a series of dehydroabietic acid derivatives bearing heterocyclic ring were synthesized and their properties in many fileds have been researched. Herein, we report the crystal structure of the title compound.

The asymmetric unit of the title compound is shown in Fig. 1. There are two independent molecules [A and B] and all bond lengths and angles are within normal ranges (Allen et al., 1987). In each molecule, the cyclohexyl ring having the thiadiazole fragment adopts a classic chair conformation with two methyl groups in the axial positions. The crystal packing (Fig. 2) is stabilized by intermolecular N—H···N hydrogen bonds between the hydrogen of the amide group and the thiadiazole N atom (see; Table 1). The crystal packing (Fig. 2) is further stabilized by intermolecular C—H···π interactions between a cyclohexyl H atom and the 2-chlorophenyl ring (Table 1; Cg is the centroid of the C23–C28 2-chlorophenyl ring).

Experimental

2-Amino-5-dehydroabietyl-1,3,4-thiadiazole was synthesized from dehydroabietic acid at first. Then a solution of the o-chlorobenzoyl chloride (8 mmol) in methylene chloride (5 ml) was added dropwise to a mixture of 2-amino-5-dehydroabietyl-1,3,4-thiadiazole (2.84 g, 8 mmol), triethylamine (1.16 ml, 10 mmol) and methylene chloride (15 ml) with constant stirring at 0–5°C. The reaction mixture was stirred for 45 min at this temperature, then for 5 h at room temperature, followed by evaporation of the mixture in vacuo to afford a yellowish solid, which was washed with water and recrystalized to give the title compound, 2-(2-chlorobenzamido)-5-[(4R,5R,10S)dehydroabietyl]-1,3,4-thiadiazole. Single crystals of the title compound suitable for an X-ray diffraction study were obtained by slow evaporation of an acetone solution at room temperature over a period of 10 d.