2-Anilino-4-(1,3-benzothia­zol-2-yl)-5-(4-chloro­benzo­yl)thio­phene-3-carbonitrile

Hoong-Kun Fun; Tze Shyang Chia; Hatem A Abdel-Aziz

doi:10.1107/S1600536812032588

. 2012 Jul 25;68(Pt 8):o2529. doi: 10.1107/S1600536812032588

2-Anilino-4-(1,3-benzothiazol-2-yl)-5-(4-chlorobenzoyl)thiophene-3-carbonitrile

Hoong-Kun Fun ^a,^*,^‡, Tze Shyang Chia ^a, Hatem A Abdel-Aziz ^b

PMCID: PMC3414976 PMID: 22904963

Abstract

In the title compound, C₂₅H₁₄ClN₃OS₂, the central thiophene ring [maximum deviation = 0.011 (1) Å] makes dihedral angles of 55.72 (5), 13.36 (5) and 46.77 (4)° with the adjacent chloro-substituted benzene ring, the benzene ring and the 1,3-benzothiazole ring system [maximum deviation = 0.012 (1) Å], respectively. An intramolecular C—H⋯S(thienyl) hydrogen bond generates an S(6) ring motif in the molecule. In the crystal, molecules are linked by pairs of N—H⋯N hydrogen bonds into inversion dimers and the dimers are further connected by C—H⋯O hydrogen bonds into tapes running along [100]. Aromatic π–π stacking interactions are also observed [centroid-to-centroid distances = 3.6116 (6) and 3.7081 (6) Å].

Related literature

For background to the chemistry and biological activity of thiophenes, see: Fun et al. (2012 ▶); Abdel-Aziz et al. (2012 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₂₅H₁₄ClN₃OS₂
M _r = 471.96
Triclinic,
a = 6.9469 (2) Å
b = 7.6722 (3) Å
c = 20.9874 (7) Å
α = 91.519 (1)°
β = 97.577 (1)°
γ = 107.791 (1)°
V = 1053.15 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 100 K
0.31 × 0.27 × 0.19 mm

Data collection

Bruker APEX DUO CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.884, T _max = 0.929
27413 measured reflections
7637 independent reflections
6820 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.083
S = 1.04
7637 reflections
293 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812032588/hb6899sup1.cif

e-68-o2529-sup1.cif^{(29.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812032588/hb6899Isup2.hkl

e-68-o2529-Isup2.hkl^{(373.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812032588/hb6899Isup3.cml

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—H1N3⋯N2ⁱ	0.862 (15)	2.163 (15)	2.9558 (12)	152.7 (13)
C17—H17A⋯O1ⁱⁱ	0.95	2.60	3.3496 (14)	136
C24—H24A⋯S2	0.95	2.49	3.1719 (9)	128

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

Acknowledgments

HKF and TSC thank Universiti Sains Malaysia (USM) for a Research University Grant (No. 1001/PFIZIK/811160). TSC thanks the Malaysian government and USM for the award of a Research Fellowship. The authors thank the Deanship of Scientific Research and the Research Center, College of Pharmacy, King Saud University, for funding and facilities.

supplementary crystallographic information

Comment

In continuation to our interest in the chemistry of thiophenes (Fun et al., 2012; Abdel-Aziz et al., 2012), we report herein the crystal structure of the title compound.

The asymmetric unit of the title compound is shown in Fig. 1. The molecule consists of a thiophene ring (A) [S2/C8–C11; maximum deviation = 0.011 (1) Å at atoms S2 and C11], a chloro-substituted benzene ring (B) [C13–C18], a benzene ring (C) [C19–C24] and a benzo[d]thiazole ring system (D) [S1/N1/C1–C7; maximum deviation = 0.012 (1) Å at atom C7]. The dihedral angles between the mean planes of the rings are A/B = 55.72 (5)°, A/C = 13.36 (5)°, A/D = 46.77 (4)°, B/C = 67.90 (5)°, B/D = 23.99 (4)° and C/D = 60.11 (4)°. An intramolecular C24—H24A···S2 hydrogen bond generates an S(6) ring motif (Bernstein et al., 1995) in the molecule.

In the crystal (Fig. 2), molecules are linked by pairs of N3—H1N3···N2 hydrogen bonds into inversion dimers and the dimers are further connected by C17—H17A···O1 hydrogen bond into tapes, running along the a-axis. π–π interactions are also observed with Cg1···Cg3 = 3.6116 (6) Å [symmetry code = x, y, z] and Cg2···Cg4 = 3.7081 (6) Å [symmetry code = -x, -y, -z], where Cg1, Cg2, Cg3 and Cg4 are the centroids of S1/C6/C1/N1/C7, S2/C8–C11, C13–C18 and C19–C24 rings, respectively.

Experimental

To a stirred solution of potassium hydroxide (0.56 g, 10 mmol) in dimethylformamide (20 ml), 3-(benzo[d]thiazol-2-yl)-3-oxopropanenitrile (0.2 g, 1 mmol) was added. After heating at 100°C for 10 min, phenyl isothiocyanate (0.135 g, 1 mmol) was added to the resulting mixture and the heating was continued for another 10 min, then 2-chloro-1-(4-chlorophenyl)ethanone (0.189 g, 1 mmol) was added. After the addition, the reaction mixture was heated at 100°C for 15 min. The precipitated product was filtered off, washed with water and dried. Crystallization from DMF afforded the title compound. Colourless blocks were formed after slow evaporation of DMF after one month.