Ethyl 2-[2-(2,4-diphenyl-3-aza­bicyclo­[3.3.1]nonan-9-yl­idene)hydrazin-1-yl]-4-methyl-1,3-thia­zole-5-carboxyl­ate di­methyl­formamide monosolvate

S Jothivel; S Kabilan

doi:10.1107/S1600536813033540

. 2013 Dec 18;70(Pt 1):o68–o69. doi: 10.1107/S1600536813033540

Ethyl 2-[2-(2,4-diphenyl-3-azabicyclo[3.3.1]nonan-9-ylidene)hydrazin-1-yl]-4-methyl-1,3-thiazole-5-carboxylate dimethylformamide monosolvate

S Jothivel ^a, S Kabilan ^a,^*

PMCID: PMC3914099 PMID: 24527004

Abstract

In the title molecule, C₂₇H₃₀N₄O₂S·C₃H₇NO, the fused piperidine and cyclohexane rings adopt a twin chair conformation and the phenyl groups occupy equatorial sites. The phenyl rings make a dihedral angle of 40.74 (2)°. In the crystal, the dimethylformamide solvent molecule is connected to the main molecule by an N—H⋯O hydrogen bond. An additional N—H⋯O hydrogen bond connects molecules into chains along [100]. Pairs of weak C—H⋯O hydrogen bonds connect inversion-related chains. The ethyl group was refined as disordered over two sets of sites with an occupancy ratio of 0.660 (17):0.340 (17).

Related literature

For the biological activity of related structures, see: Ramachandran et al. (2009 ▶); Hutchinson et al. (2002 ▶); Bondock et al. (2007 ▶). For bicyclic compounds, see: Jeyaraman & Avila (1981 ▶). graphic file with name e-70-00o68-scheme1.jpg

Experimental

Crystal data

C₂₇H₃₀N₄O₂S·C₃H₇NO
M _r = 547.71
Monoclinic,
a = 12.700 (5) Å
b = 19.427 (5) Å
c = 13.203 (5) Å
β = 115.249 (5)°
V = 2946.3 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.15 mm⁻¹
T = 293 K
0.35 × 0.35 × 0.30 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T _min = 0.937, T _max = 0.965
25815 measured reflections
5179 independent reflections
3606 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.055
wR(F ²) = 0.154
S = 1.01
5179 reflections
379 parameters
40 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.37 e Å⁻³

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: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, 1. DOI: 10.1107/S1600536813033540/lh5671sup1.cif

e-70-00o68-sup1.cif^{(37KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813033540/lh5671Isup2.hkl

e-70-00o68-Isup2.hkl^{(253.6KB, hkl)}

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

Supporting information file. DOI: 10.1107/S1600536813033540/lh5671Isup3.cdx

Click here for additional data file.^{(11.2KB, cml)}

Supporting information file. DOI: 10.1107/S1600536813033540/lh5671Isup4.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14⋯O1ⁱ	0.93	2.41	3.284 (4)	156
N1—H1A⋯O1ⁱⁱ	0.84 (2)	2.59 (2)	3.380 (4)	157 (2)
N3—H3A⋯O3	0.85 (2)	1.99 (2)	2.843 (4)	173 (3)

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

Acknowledgments

SJ is thankful to the Council of Scientific and Industrial Research (CSIR), New Delhi, India, for the award of a Senior Research Fellowship through research grant No. 01/2454/11/EMR-II. The authors are thankful to the SAIF, IIT Madras, for the data collection.

supplementary crystallographic information

1. Comment

Thiazoles are an interesting unit in medicinal chemistry and are responsible for numerous pharmacological and biological properties (Hutchinson et al. 2002; Bondock et al., 2007; Ramachandran et al., 2009). This has piqued our interest in the synthesis of thiazole containing compounds. The importance of bicyclic compounds as intermediates in the synthesis of a several physiologically active compounds have been reviewed by Jeyaraman & Avila (1981). Moreover, these bridged bicyclic compounds exhibit twin chair, chair–boat or twin boat conformations and possess interesting stereochemistries. In order to investigate the change in molecular conformation of the piperidine and cyclohexane rings, the X-ray structure determination of the title compound was carried out. The six–membered heterocyclic piperidine ring (Fig. 1) adopts the expected chair conformation. The two phenyl rings form a dihedral angle of 40.74 (2)°. In the crystal the dimethylformamide solvent molecule is connected to the main molecule by an N—H···O hydrogen bond. An additional N—H···O hydrogen bond connects molecules into chains along [100] (Fig. 2). Weak C—H···O hydrogen bonds connect pairs of inversion related chains. The ethyl group was refined as disordered over two sets of sites with a 0.660 (17): 0.340 (17) ratio of occupancies.

2. Experimental

To a boiling solution of the bicyclic thiosemicarbazone (0.01 mol) in ethanolic–chloroform (1:1 / v:v), ethyl-2-chloroacetoacetate(0.01 mol), sodium acetate trihydrate (0.02 mol) and a few drops of acetic acid 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 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 dimethylformamide as the solvent.