Crystal structure of (Z)-3-{3-(4-chloro­phen­yl)-2-[(4-chloro­phen­yl)imino]-2,3-di­hydro­thia­zol-4-yl}-2H-chromen-2-one

M Kayalvizhi; G Vasuki; R Raj Kumar; V Rajeswar Rao

doi:10.1107/S1600536814024775

. 2014 Nov 19;70(Pt 12):o1268–o1269. doi: 10.1107/S1600536814024775

Crystal structure of (Z)-3-{3-(4-chlorophenyl)-2-[(4-chlorophenyl)imino]-2,3-dihydrothiazol-4-yl}-2H-chromen-2-one

M Kayalvizhi ^a, G Vasuki ^a,^*, R Raj Kumar ^b, V Rajeswar Rao ^b

PMCID: PMC4257461 PMID: 25553038

Abstract

In the title compound, C₂₄H₁₄Cl₂N₂O₂S, the 2H-chromene ring system is approximately planar, with a maximum deviation of 0.025 (2) Å. The thiazole ring is almost planar, with an r.m.s. deviation of 0.0022 Å, and makes a dihedral angle of 58.52 (7)° with the chromene ring system. The chromene ring system is inclined at angles of 58.3 (1) and 55.39 (9)° with respect to the two chlorophenyl rings. The two chlorophenyl rings show significant deviation from coplanarity, with a dihedral angle between them of 47.69 (8)°. The crystal structure features C—H⋯Cl interactions extending in (100) and propagating along the a-axis direction and weak π–π interactions [centroid–centroid separation = 3.867 (2) Å].

Keywords: crystal structure, 2H-chromen-2-one, bioactivity, hydrogen bonding, π–π interactions

Related literature

For the bioactivity of coumarin, see: Yusufzai et al. (2012 ▶). For related structures, see: Arshad, Osman, Chan et al. (2010 ▶); Arshad, Osman, Lam et al. (2010a ▶,b ▶). For synthetic chemistry, medicinal chemistry, photochemistry and solid-state chemistry applications of coumarin derivatives, see: Chopra et al. (2009 ▶). For the synthesis, see: Raj Kumar & Rajeswar Rao (2014 ▶).

Experimental

Crystal data

C₂₄H₁₄Cl₂N₂O₂S
M _r = 465.33
Monoclinic,
a = 9.1491 (7) Å
b = 10.3099 (8) Å
c = 11.9347 (10) Å
β = 111.587 (2)°
V = 1046.80 (14) Å³
Z = 2
Mo Kα radiation
μ = 0.44 mm⁻¹
T = 296 K
0.35 × 0.30 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T _min = 0.897, T _max = 1.000
15409 measured reflections
5549 independent reflections
4070 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.075
S = 1.03
5549 reflections
280 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.20 e Å⁻³
Absolute structure: Flack x determined using 1604 quotients [(I ⁺)−(I ⁻)]/[(I ⁺)+(I ⁻)] (Parsons et al., 2013 ▶)
Absolute structure parameter: −0.004 (19)

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global, 206R. DOI: 10.1107/S1600536814024775/zs2320sup1.cif

e-70-o1268-sup1.cif^{(464.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814024775/zs2320Isup2.hkl

e-70-o1268-Isup2.hkl^{(304.1KB, hkl)}

Click here for additional data file.^{(4.6KB, cdx)}

Supporting information file. DOI: 10.1107/S1600536814024775/zs2320Isup3.cdx

Click here for additional data file.^{(7.5KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814024775/zs2320Isup4.cml

Click here for additional data file.^{(1.2MB, tif)}

. DOI: 10.1107/S1600536814024775/zs2320fig1.tif

The molecular structure of the title compound showing atom numbering, with displacement ellipsoids drawn at the 50% probability level.

Click here for additional data file.^{(1.8MB, tif)}

a . DOI: 10.1107/S1600536814024775/zs2320fig2.tif

Crystal packing of the title compound in the unit cell, viewed along the a axis, showing C—H⋯Cl interactions as dashed lines.

Click here for additional data file.^{(1.1MB, tif)}

. DOI: 10.1107/S1600536814024775/zs2320fig3.tif

The partial packing of the title compound, showing the π–π interactions.

CCDC reference: 1027667

Additional supporting information: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the Sophisticated Analytical Instrument Facility, IITM, Chennai 600 036, Tamilnadu, India, for the data collection.

supplementary crystallographic information

S1. Comment

Compounds containing the coumarin moiety exhibit useful and diverse biological activities (Yusufzai et al., 2012). Coumarins are an important class of organic compounds and have been extensively studied. Such molecules of vast structural diversity find useful applications in several areas of synthetic chemistry, medicinal chemistry and photochemistry. The formation of [2 + 2] cycloaddition products upon irradiation of coumarin and its derivatives has contributed immensely to the area of solid-state chemistry. Several substituted coumarin derivatives find applications in the dye industry and in the area of laser dyes based on the fact that such compounds show state dependent variations in their static dipole moments. The geometry and molecular packing patterns of several coumarins derivatives have been studied to evaluate the features of non-covalent interactions (Chopra et al., 2009). Some of the coumarin derivatives have been found to be useful in photochemotherapy, antitumour, anti-HIV therapy, anti-bacterial, anticoagulant, anti-fungal, cytotoxic activities, free radical scavengers and enzyme inhibiting agents. The related compounds whose structures have been solved by X-ray are 3-{2-[2-(diphenylmethylene)hydrazinyl]thiazol-4-yl}-2H-chromen-2-one (Arshad, Osman, Chan et al., 2010), (Z)-3-(2-{2-[1-(4-hydroxyphenyl)ethylidene]hydrazin-1-yl}-1,3-thiazol-4-yl)-2H-chromen-2-one (Arshad, Osman, Lam et al., 2010a) and 3-{2-[2-(2-fluororbenzylidene)hydrazinyl]-1,3-thiazol-4-yl}-2H-chromen-2-one (Arshad, Osman, Lam et al., 2010b). The title compound, C₂₄H₁₄Cl₂N₂O₂S, (Fig. 1), is a new derivative of dihydrothiazoyl coumarin. We present herein its crystal structure.

The 2H-chromene (O1/C1–C9/O2) ring system is approximately planar, with the maximum deviation of -0.025 (2) Å at atom O1. The thiazole ring (S1/N1/C10–C12) is almost planar with a r.m.s. deviation of 0.0022 Å and makes a dihedral angle of 58.52 (7)° with the chromene ring. The chromene ring system is inclined at angles of 58.3 (1)° and 55.39 (9)° with respect to the two chlorophenyl rings (C13–C18/Cl1) and (C19–C24/Cl2), respectively. The two chlorophenyl rings show significant deviation from coplanarity, with a dihedral angle between the two planes of 47.69 (8)°. The sum of bond angles around N1 [359.79 (5)°] indicates that atom N exhibits sp² hybridization. Torsion angles C1—C2—C10—N1 = -58.5 (4)° and C10—N1—C22—C23 = -51.8 (4)° indicate that the chromene ring and the chlorophenyl ring are substituted synclinally to the thiazole ring at atoms C2 and C22, respectively. The torsion angle C22—N1—C12—N2 [6.4 (4)°] indicates that the two chlorophenyl rings have a Z-configuration across the N1—C12 bond. In the crystal, a short intermolecular C3—H···Clⁱ contact is observed [3.282 (3) Å] [symmetry code: (i) x, y - 1, z] together with second longer C23—H···Cl1ⁱⁱ contact is observed between C23 and Cl1ⁱⁱ [3.547 (3) Å] [symmetry code: x + 1, y, z + 1] (Fig. 2). Inter-ring π—π stacking interactions between the symmetry related C4–C9 ring (centroid Cg3) and the C13–C18ⁱⁱⁱ ring (centroid Cg4), with Cg3···Cg4 = 3.867 (2) Å (symmetry code: (iii) x + 1, y, z + 1) further stabilize the crystal structure (Fig. 3).

S2. Experimental

The compound was synthesized according to the published procedure (Raj Kumar & Rajeswar Rao, 2014).