1-(2,2-Di­chloro­acet­yl)-3-ethyl-2,6-di­phenyl­piperidin-4-one

P Sugumar; R Kayalvizhi; P Nirmala; S Ponnuswamy; M N Ponnuswamy

doi:10.1107/S1600536813010957

. 2013 Apr 27;69(Pt 5):o800. doi: 10.1107/S1600536813010957

1-(2,2-Dichloroacetyl)-3-ethyl-2,6-diphenylpiperidin-4-one

P Sugumar ^a, R Kayalvizhi ^b, P Nirmala ^b, S Ponnuswamy ^b, M N Ponnuswamy ^a,^*

PMCID: PMC3648321 PMID: 23723941

Abstract

The asymmetric unit of the title compound, C₂₁H₂₁Cl₂NO₂, contains two independent molecules that show similar geometrical features. The piperidine ring adopts a distorted boat conformation. The phenyl rings substituted at the 2- and 6-positions of the piperidine ring are oriented at angles of 65.4 (1) [64.7 (2)°] and 89.2 (1)° [86.3 (2)°] with respect to the least-squares plane of the piperidine ring. In the crystal, adjacent molecules are linked by a network of C—H⋯O interactions, forming a C(6) chain along the c-axis direction.

Related literature

For the biological activity of piperidine derivatives, see: Aridoss et al. (2009 ▶); Nalanishi et al. (1974 ▶); Michael (2001 ▶); Pinder (1992 ▶); Rubiralta et al. (1991 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For asymmetry parameters, see: Nardelli (1983 ▶). graphic file with name e-69-0o800-scheme1.jpg

Experimental

Crystal data

C₂₁H₂₁Cl₂NO₂
M _r = 390.29
Monoclinic,
a = 17.4615 (13) Å
b = 19.0291 (15) Å
c = 11.9501 (9) Å
β = 91.825 (5)°
V = 3968.7 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 293 K
0.22 × 0.20 × 0.18 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.928, T _max = 0.940
36640 measured reflections
9905 independent reflections
5029 reflections with I > 2σ(I)
R _int = 0.058

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.175
S = 1.00
9905 reflections
471 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.44 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

Click here for additional data file.^{(32KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813010957/ng5321sup1.cif

e-69-0o800-sup1.cif^{(32KB, cif)}

Click here for additional data file.^{(484.4KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813010957/ng5321Isup2.hkl

e-69-0o800-Isup2.hkl^{(484.4KB, hkl)}

Click here for additional data file.^{(6.9KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813010957/ng5321Isup3.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
C2—H2⋯O1ⁱ	0.98	2.49	3.435 (3)	161
C20′—H20F⋯O1ⁱⁱ	0.96	2.48	3.415 (4)	164
C6′—H6′⋯O2′ⁱⁱⁱ	0.98	2.51	3.292 (3)	137

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

Acknowledgments

PS thanks the UGC, New Delhi, for financial support in the form of a Research Fellowship in Science for Meritorious Students. SP thanks the UGC, New Delhi, for financial assistance in the form of a major research project.

supplementary crystallographic information

Comment

Piperidine derivatives are the valued heterocyclic compounds in the field of medicinal chemistry. The compounds possessing an amide bond linkage have a wide range of biological activities such as antimicrobial, anti-inflammatory, antiviral, antimalarial and general anesthetics (Aridoss et al., 2009). Functionalized piperidines are familiar substructures found in biologically active natural products and synthetic pharmaceuticals (Michael, 2001; Pinder, 1992; Rubiralta et al., 1991). Piperidines have been found to exhibit blood cholesterol-lowering activities (Nalanishi et al., 1974). Against this background and to ascertain the molecular structure and conformation, crystallographic study of the title compound has been carried out.

The ORTEP plot of the molecule is shown in Fig. 1. The chloro substituted piperidine derivative crystallizes in monoclinic space group P2₁/c. The piperidine ring adopts distorted boat conformation with the puckering parameters (Cremer & Pople, 1975) and the asymmetry parameters (Nardelli, 1983) are: q₂=0.651 (3) Å, q₃ = -0.078 (3) Å, φ₂ = 77.0 (2)° and Δ_s(C2 & C5)= 19.1 (2)°. The sum of the bond angles around N1 [359°] is in accordance with sp² hybridization.

The planar phenyl rings [C7—C12 & C13—C18] substituted at 2,6-positions of the piperidine ring subtend angles of 65.4 (1)° [64.7 (2)°] & 89.2 (1)° [86.3 (2)°] in both the molecules with the best plane of the piperidine ring. The two phenyl rings are approximately perpendicular to each other with a dihedral angle of 86.5 (1)° [82.8 (2)°].

The dichloroacetyl groups substituted at the N^th-position of the piperidine ring are axial and equatorial orientation for the both molecules which can be seen from the torsion angles of [N1—C21—C22—Cl2=] 88.5 (2)° [-97.0 (2)°] & [N1—C21—C22—Cl1=] -150.5 (2)° [142.5 (2)°], respectively.

The crystal packing reveals that the symmetry related molecules are linked through a network of C—H···O type of intermolecular interactions.

Experimental

3-Ethyl-2,6-diphenylpiperidin-4-one (5 mmol) was dissolved in 60 ml of anhydrous benzene. To this solution, dichloroacetylchloride (20 mmol) and triethylamine (20 mmol) were added and the reaction mixture was allowed to stirr for 8 h. The course of the reaction was monitored by TLC. The organic layer was dried over anhydrous Na₂SO₄ and the resulting pasty mass was purified by recrystallization from ethyl acetate. Yield: 74%, Melting point: 140–142°C