2-(2,4-Diphenyl-3-aza­bicyclo­[3.3.1]nonan-9-ylidenehydrazono)-1,3-thia­zolidin-4-one

R Ramachandran; M Rani; S Kabilan

doi:10.1107/S1600536809005339

. 2009 Feb 25;65(Pt 3):o584. doi: 10.1107/S1600536809005339

2-(2,4-Diphenyl-3-azabicyclo[3.3.1]nonan-9-ylidenehydrazono)-1,3-thiazolidin-4-one

R Ramachandran ^a, M Rani ^a, S Kabilan ^a,^*

PMCID: PMC2968662 PMID: 21582239

Abstract

In the title compound, C₂₃H₂₄N₄OS, the piperidine and cyclohexane rings adopt twin chair conformations and the phenyl groups occupy equatorial positions. The dihedral angle between the two benzene rings is 10.25 (12)°. The crystal structure is stabilized by intermolecular N—H⋯O hydrogen bonds with the formation of centrosymmetric dimers.

Related literature

For background on the thiazolidinone system, see: Laurent et al. (2004 ▶). For the biological activities of thiazolidinones, see: Shih & Ke (2004 ▶), For bicyclic compounds, see: Jeyaraman & Avila, (1981 ▶). For ring conformational analysis, see: Cremer & Pople, (1975 ▶).

Experimental

Crystal data

C₂₃H₂₄N₄OS
M _r = 404.53
Monoclinic,
a = 8.3183 (3) Å
b = 10.8435 (4) Å
c = 22.7417 (8) Å
β = 92.483 (2)°
V = 2049.36 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 293 K
0.25 × 0.20 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker 1999 ▶) T _min = 0.956, T _max = 0.974
31153 measured reflections
7820 independent reflections
4068 reflections with I > 2σ(I)
R _int = 0.053

Refinement

R[F ² > 2σ(F ²)] = 0.062
wR(F ²) = 0.203
S = 1.04
7820 reflections
270 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809005339/rk2127sup1.cif

e-65-0o584-sup1.cif^{(22.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809005339/rk2127Isup2.hkl

e-65-0o584-Isup2.hkl^{(374.9KB, 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
N4—H4A⋯O1ⁱ	0.83 (2)	2.03 (2)	2.847 (2)	169 (2)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors are grateful to Dr Babu Varghese, Senior Scientist, Indian Institute of Technology Madras, for his valuable suggestions and for the data collection.

supplementary crystallographic information

Comment

Thiazolidinones are an interesting backbone unit in medicinal chemistry and is responsible for numerous pharmacological and biological properties (Shih & Ke, 2004; Laurent et al., 2004), which inspires our research interest in this area towards the synthesis of thiazolidinone unit. The importance of bicyclic compounds as intermediates in the synthesis of a several physiologically active compounds have reviewed by Jeyaraman & Avila, (1981). Moreover, these bridged bicyclic compounds exhibit twin chair, chair–boat or twin boat conformations to be elucidated possessing interesting stereochemistry. In order to investigate the change in molecular conformation of piperidine and cyclohexane ring, the present investigation was made and confirmed by X–ray diffraction study.

We found, that six–membered heterocyclic piperidine ring (Fig. 1) adopt normal chair conformation with the puckering parameters (Cremer & Pople, 1975) being q₁ and q₂ are 0.0714 (19) Å and -0.567 (19) Å, respectively. The total puckering amplitude, Q_T=0.572 (19) Å; θ=173.03 (19)°. Similarly, the cyclohexane ring is also adopt normal chair conformation with the puckering parameters being q₁ and q₂ are 0.121 (2)Å and 0.552 (2) Å, respectively. The puckering amplitude, Q_T=0.562 (2) Å, θ=12.5 (2)°. The planar phenyl rings occupy equatorial orientation of the piperidine ring and its subtending angle between the phenyl ring and the best plane of the piperidine ring is 10.25 (12)°. The crystal structure is stabilized by intermolecular N4—H4A···O1ⁱ hydrogen bonds (Fig. 2) with formation of centrosymmetrical dimers. Symmetry code: (i) -x+1, -y+1, -z+1.

Experimental

To the boiling solution of the bicyclic thiosemicarbazone (0.01 mol) in ethanolic–chloroform (1:1 / v:v), ethylbromoacetate (0.01 mol), sodium acetate trihydrate (0.02 mol) and acetic acid few drops were added and refluxed for about 5–6 h. After the completion of reaction, excess of solvent was removed under reduced pressure and poured into water. After usual work–up, the solid was separated and purified by column chromatography using benzene–ethyl acetate (9:1 / v:v) as eluent on neutral alumina. Colourless crystals were grown by slow evaporation method using ethanol as solvent. ¹H NMR (δ p.p.m.), DMSO–d₆: 4.39 (s, 1H, H2a); 4.26 (s, 1H, H4a); 3.56 (s, 1H, H5e); 2.57 (s, 1H, H1e); 3.74 (s, 2H, S—CH₂); 2.82 (m, 1H, H7a); 1.44 (m, 5H, H6e, H8e, H7e, H6a and H8a); 2.09 (s, 1H, NH at 3); 11.60 (bs, 1H, NH exchangeable); 7.25–7.60 & 7.80 (m, 10H aryl protons): ¹³C NMR (δ p.p.m.) DMSO–d₆: 64.94 (C2); 63.57 (C4); 45.91 (C1); 39.88 (C5); 28.65 (C8); 27.28 (C6); 21.37 (C7); 32.92 (S—CH₂); 173.98 (Cδb O); 163.00 (Cδb N) 142.54 (C2' & C4'); 128.16, 127.02, 126.95, 126.83, 126.77 (other aryl carbons).