3-Isopropyl-1-{2-[(1-methyl-1H-tetra­zol-5-yl)sulfan­yl]acet­yl}-2,6-di­phenyl­piperidin-4-one hemihydrate

S Ganesan; P Sugumar; S Ananthan; M N Ponnuswamy

doi:10.1107/S1600536813026500

. 2013 Oct 2;69(Pt 11):o1598. doi: 10.1107/S1600536813026500

3-Isopropyl-1-{2-[(1-methyl-1H-tetrazol-5-yl)sulfanyl]acetyl}-2,6-diphenylpiperidin-4-one hemihydrate

S Ganesan ^a,^b, P Sugumar ^c, S Ananthan ^b, M N Ponnuswamy ^c,^*

PMCID: PMC3884276 PMID: 24454052

Abstract

In the title compound, C₂₄H₂₇N₅O₂S·0.5H₂O, the piperidine ring adopts a distorted boat conformation. The phenyl rings subtend dihedral angles of 69.7 (1) and 88.7 (1)° with the best plane through the piperidine moiety. In the crystal, symmetry-related molecules are linked through a network of C—H⋯O and C—H⋯N interactions, the former connecting them into zigzag chains along the c-axis direction and the latter forming an R ² ₂(4)motif. The dimer formation (C—H⋯N) and the repetition of symmetry-related molecules (C—H⋯O) along the b-axis direction stabilize the packing mode. The water molecule is located on a twofold rotation axis.

Related literature

For the biological activity of piperidine derivatives, see: Aridoss et al. (2009 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For asymmetry parameters, see: Nardelli (1983 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). graphic file with name e-69-o1598-scheme1.jpg

Experimental

Crystal data

C₂₄H₂₇N₅O₂S·0.5H₂O
M _r = 458.57
Monoclinic,
a = 28.7522 (9) Å
b = 11.1809 (4) Å
c = 16.5584 (5) Å
β = 115.303 (2)°
V = 4812.4 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.17 mm⁻¹
T = 293 K
0.22 × 0.19 × 0.17 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.964, T _max = 0.972
22058 measured reflections
6013 independent reflections
4157 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.146
S = 1.04
6013 reflections
297 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; 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: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813026500/bt6930sup1.cif

e-69-o1598-sup1.cif^{(24.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813026500/bt6930Isup2.hkl

e-69-o1598-Isup2.hkl^{(294.4KB, hkl)}

Click here for additional data file.^{(9.1KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813026500/bt6930Isup3.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
C25—H25C⋯O1ⁱ	0.96	2.47	3.406 (3)	166
C18—H18⋯O1ⁱⁱ	0.93	2.54	3.312 (2)	140
C25—H25B⋯N4ⁱⁱⁱ	0.96	2.54	3.472 (3)	165

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

Acknowledgments

SG wishes to thank Orchid Chemicals and Pharmaceuticals Limited (www.orchidpharma.com), Chennai, India, for consent to perform the research. PS thanks the UGC, New Delhi, for financial support in the form of a Research Fellowship in Science for Meritorious Students.

supplementary crystallographic information

1. Comment

In a way to find piperidin-4-one based lead drug molecules for the antimicrobial therapy, various piperidin-4-ones were prepared by condensing N-chloroacetyl-2,6-diphenylpiperidin-4-one with 5-mercapto-(1-methyltetrazole) (Aridoss et al., 2009). 5-Mercapto-(1-methyl tetrazole) is the active part of a number of cephalosporanic drugs like Cefamandole, Cefoperazone, Cefmetazole sodium & Cefotetan and responsible for its activity. The present investigation was undertaken to establish the structure and conformation of the title compound by X-ray crystallographic methods.

The ORTEP plot of the molecule is shown in Fig. 1. The piperidine ring adopts a distorted boat conformation with the puckering parameters (Cremer & Pople, 1975) and the asymmetry parameters (Nardelli, 1983): q₂=0.662 (2) Å, q₃ = 0.079 (2) Å, φ₂ = 76.86 (2)° and Δ_s(N1 & C4)= 74.11 (2)°.

The methyltetrazol ring is planar with the maximum deviation -0.003 (2) Å for N4 atom. The endocyclic bond lengths of N2–N3=1.362 (4)°, N3–N4= 1.278 (4) Å & N4–N5 = 1.348 (3) Å, clearly indicate that they are alternate single and double bonds.

The carbonyl group is almost anti-periplanar to C2 and C6, [C2—C3—C4—O1 = 155.9 (2)°; C6—C5—C4—O1= 151.1 (2)°]. The dihedral angles between the best plane through the piperidine ring and the phenyl rings are 69.7 (1)° & 88.7 (1)°. The two phenyl rings are oriented to each other with a dihedral angle of 70.5 (1)°.

Symmetry related molecules are linked through a network of intermolecular C—H···O and C—H···N interactions. C18–H18···O1 and C25–H25B···O1 connect the molecules to zigzag chains. Another motif R²₂(4), involving the weak interaction C25—H25A···N4 is shown in Fig. 2 (Bernstein et al., 1995).

2. Experimental

To anhydrous DMF(10 ml), N-Chloroacetyl-3-isopropyl-2,6-diphenylpiperidin-4-one (1 mole), 5-Mercapto-1-methyltetrazole(1 mole) followed by potassium carbonate (1.5 mole) was added and stirred for 1 hr at room temperature. The reaction mass was heated to 60°C and stirred and monitored using TLC. After completion of reaction, the reaction mass was quenched into water and the product was extracted with dichloromethane. The dichloromethane layer distilled completely and to the residue methanol was added and kept in overnight. The solid obtained was filtered and dried at 60° C under vacuum. Single crystals were obtained by re-crystallization using ethanol.