3-[Bis(p-tolyl­sulfon­yl)amino]-N-(4-chloro­benz­yl)-6-(3,4-dichloro­phen­yl)thieno[2,3-b]pyridine-2-carboxamide

Hai-Yun He; Hong-Ze Li; Li Yang

doi:10.1107/S160053681100290X

. 2011 Jan 26;67(Pt 2):o499. doi: 10.1107/S160053681100290X

3-[Bis(p-tolylsulfonyl)amino]-N-(4-chlorobenzyl)-6-(3,4-dichlorophenyl)thieno[2,3-b]pyridine-2-carboxamide

Hai-Yun He ^a, Hong-Ze Li ^b, Li Yang ^a,^*

PMCID: PMC3051570 PMID: 21523153

Abstract

In the title compound, C₃₅H₂₆Cl₃N₃O₅S₃, the dihedral angle between the mean plane through the thieno[2,3-b]pyridine ring system and the attached benzene ring is 3.89 (6)°. The molecular conformation is stabilized by an intramolecular N—H⋯O hydrogen bond. In the crystal, molecules are linked by intermolecular C—H⋯O hydrogen bonds, forming chains parallel to [100].

Related literature

For general background to the biological properties of thieno[2,3-b]pyridine derivatives, see: Litvinov et al. (2005 ▶).

Experimental

Crystal data

C₃₅H₂₆Cl₃N₃O₅S₃
M _r = 771.15
Monoclinic,
a = 25.8238 (8) Å
b = 9.1634 (2) Å
c = 14.8366 (5) Å
β = 102.314 (3)°
V = 3430.07 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.50 mm⁻¹
T = 294 K
0.36 × 0.28 × 0.16 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T _min = 0.695, T _max = 1.0
14766 measured reflections
7014 independent reflections
4515 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.105
S = 1.03
7014 reflections
444 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); 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: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶) and OLEX2.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681100290X/rz2547sup1.cif

e-67-0o499-sup1.cif^{(29KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053681100290X/rz2547Isup2.hkl

e-67-0o499-Isup2.hkl^{(343.2KB, 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
N3—H3⋯O2	0.86	2.11	2.945 (3)	162
C34—H34⋯S1ⁱ	0.93	2.79	3.714 (2)	172

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Symmetry code: (i) Inline graphic .

supplementary crystallographic information

Comment

Thieno[2,3-b]pyridine derivatives are of great importance owing to their wide biological properties (Litvinov et al., 2005). The title compound is one of the key intermediates in our synthetic investigations of anticancer drugs. We report here its crystal structure.

In the tile compound (Fig. 1), the thieno[2,3-b]pyridine ring system is approximately planar (maximum deviation 0.048 (2) Å for atom C8) and forms a dihedral angle of 3.89 (6)° with the attached benzene ring. The molecular conformation is stabilized by an intramolecular N—H···O hydrogen bond (Table 1). In the crystal structure (Fig. 2), the molecules are linked into chains parallel to the [100] direction by C···H···O hydrogen bonds.

Experimental

To a solution of 3-amino-N-(4-chlorobenzyl)-6-(3,4-dichlorophenyl)thieno[2,3-b]pyridine-2-carboxamide (1.39 g, 3 mmol) in tetrahydrofuran (10 ml) and triethylamine (0.63 ml) was added p-toluenesulfonyl chloride (1.14 g, 6 mmol). After stirring for 5 minutes, N,N-4-dimethylaminopyridine (48 mg, 0.39 mmol) was added and the mixture was stirred at room temperature until the reaction was completed (as monitored by TLC). The reaction mixture was concentrated in vacuo and the resulting residue was treated with a dilute HCl solution and extracted with ethyl acetate. The organic phase was dried over MgSO₄ and then was evaporated under reduced pressure. The residue was chromatographed on silica gel using petroleum ether-ethyl acetate (9:1 v/v) as eluent. The product was recrystallized from ethanol to afford the title compound as an off-white solid (yield: 60%). Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethyl acetate solution.