4-{(4-Chloro­phen­yl)[4-(4-methyl­phen­yl)-1,2,3-selenadiazol-5-yl]meth­yl}-4,5,6,7-tetra­hydro-1,2,3-benzoselenadiazole

J Muthukumaran; M Nishandhini; S Chitra; S Muthusubramanian; P Manisankar; Suman Bhattacharya; R Krishna; J Jeyakanthan

doi:10.1107/S160053681101751X

. 2011 May 14;67(Pt 6):o1421–o1422. doi: 10.1107/S160053681101751X

4-{(4-Chlorophenyl)[4-(4-methylphenyl)-1,2,3-selenadiazol-5-yl]methyl}-4,5,6,7-tetrahydro-1,2,3-benzoselenadiazole

J Muthukumaran ^a, M Nishandhini ^b, S Chitra ^c, S Muthusubramanian ^d, P Manisankar ^c, Suman Bhattacharya ^e, R Krishna ^a,^‡, J Jeyakanthan ^b,^*

PMCID: PMC3120601 PMID: 21754802

Abstract

In the title compound, C₂₂H₁₉ClN₄Se₂, the mean plane of the non-fused selenadiazole ring forms dihedral angles of 54.20 (16)° and 70.48 (11)°, respectively, with the essentially planar [maximum deviations of 0.025 (5) and 0.009 (2) Å, respectively] methylphenyl and chlorophenyl substituents. The tetrahydro-1,2,3-benzoselenadiazole group is disordered over two sets of sites with a refined occupancy ratio of 0.802 (5):0.198 (5). In the crystal, weak intermolecular C—H⋯N interactions are observed.

Related literature

For biological applications of 1,2,3-selenadiazole derivatives, see: Kuroda et al. (2001 ▶); El-Bahaie et al. (1990 ▶); El-Kashef et al. (1986 ▶); Plano et al. (2010 ▶); Padmavathi et al. (2002 ▶). For the structures of mono and bis-1,2,3-selenadiazole derivatives, see: Marx et al. (2008 ▶); Boag et al. (2010 ▶). For ring puckering analysis, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₂₂H₁₉ClN₄Se₂
M _r = 532.78
Monoclinic,
a = 9.7226 (18) Å
b = 12.969 (4) Å
c = 17.690 (3) Å
β = 100.959 (19)°
V = 2189.9 (8) Å³
Z = 4
Mo Kα radiation
μ = 3.52 mm⁻¹
T = 293 K
0.4 × 0.3 × 0.2 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.516, T _max = 1.000
8795 measured reflections
3849 independent reflections
2590 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.138
S = 1.04
3849 reflections
255 parameters
293 restraints
H-atom parameters constrained
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.68 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 ▶); data reduction: CrysAlis RED; 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, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681101751X/lh5230sup1.cif

e-67-o1421-sup1.cif^{(27.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053681101751X/lh5230Isup2.hkl

e-67-o1421-Isup2.hkl^{(188.7KB, 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
C6A—H6A⋯N2Aⁱ	0.98	2.57	3.517 (16)	164
C10—H10⋯N4ⁱⁱ	0.93	2.61	3.467 (7)	153
C12—H12⋯N3ⁱⁱⁱ	0.93	2.61	3.470 (7)	153

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

Acknowledgments

RK and JM thank the Centre for Bioinformatics (funded by the Department of Biotechnology and the Department of Information Technology, New Delhi, India), Pondicherry University and JJ thanks the Department of Organic Chemistry, Madurai Kamaraj University, for providing the facilities for the synthesis of the title compound, and the Department of Bioinformatics, Alagappa University for providing the computational facilities to carry out this research work. JJ also thanks Binoy Krishna Saha, Assistant Professor, Department of Chemistry, Pondicherry University, for providing the X-ray facility. JM also thanks the Council for Scientific and Industrial Research (CSIR) for a Senior Research Fellowship (SRF).

supplementary crystallographic information

Comment

Selenium containing compounds like 1,2,3-selenadiazole are of increasing interest because of their unique chemical properties and have several important biological applications such as anti-fungal (Kuroda et al., 2001), anti-bacterial (El-Kashef et al.,1986), anti-microbial (El-Bahaie et al., 1990), anti-cancer (Plano et al., 2010) and insecticidal (Padmavathi et al., 2002) activities. In view of the growing importances of selenium containing compounds, we present herein the single-crystal structure of the title compound (I).

Some mono and bis-1,2,3-selenadiazole derivatives are already reported in the literature (Marx et al., 2008; Boag et al., 2010). The molecular structure of the title compound is shown in Fig. 1. The puckering analysis (Cremer & Pople, 1975) for the atoms C1A/C2A/C3A/C4A/C5A/C6A (belonging to the major component of disorder) of the 4,5,6,7-tetrahydrobenzo[d][1,2,3]selenadiazole group in (I) adopt an envelope conformation (E form) with puckering parameters of Q = 0.536 (8) Å, θ = 56.1 (8)° and Φ = 239.0 (10)°. The tetrahydro-1,2,3-benzoselenadiazole group is disordered with the refined site-occupancy ratios 0.802 (5):0.198 (5). The hetrocyclic ring (Se2/C14/C15/N3/N4) makes dihedral angles of 54.20 (16)° and 70.48 (11)°, respectively with the essentially planar atoms C16-C22 [maximum deviation 0.025 (5) Å for C16] and atoms C8-C13/Cl1 [maximum deviation of 0.009 (2)Å for Cl1]. The crystal packing (Fig. 2) is stabilized by weak intermolecular C—H···N interactions.

Experimental

A mixture of 2-[1-(4-chloro-phenyl)-3-(4-methylphenyl)-3-oxopropyl]-1-cyclohexanone (1 mmol) and semicarbazide hydro-chloride (2.5 mmol) in ethanol (10 mL) was heated under reflux on a water bath for 3 h. After completion of the reaction as evident from TLC, the mixture was poured into ice-water (50 ml) and the resulting semicarbazone solid was filtered off. Then, a mixture of semicarbazone and SeO₂ (3 mmol) in tetrahydrofuran (THF) (10 ml) were refluxed on a water bath for 30 min. After completion of the reaction as monitored by TLC, the reaction mixture was filtered to remove selenium powder, the filtrate was concentrated under vacuum, and the residue was subjected to column chromatography using petroleum ether/ethyl acetate mixture (95:5; v/v) as eluent to afford the pure product. X-ray quality crystals were grown from a solution of the title compound in a 3:1 mixture of dichloromethane:ethylacetate in a partially closed 5ml glass vial over 7-8 days.