1-Dichloro­acetyl-t-3,t-5-dimethyl-r-2,c-6-diphenyl­piperidin-4-one

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

doi:10.1107/S1600536813007927

. 2013 Mar 28;69(Pt 4):o609. doi: 10.1107/S1600536813007927

1-Dichloroacetyl-t-3,t-5-dimethyl-r-2,c-6-diphenylpiperidin-4-one

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

PMCID: PMC3629647 PMID: 23634134

Abstract

In the title compound, C₂₁H₂₁Cl₂NO₂, the piperidine ring adopts a distorted boat conformation. The phenyl rings substituted at the 2- and 6-positions of the piperidine ring subtend angles of 87.9 (7) and 70.8 (9)°, respectively, with the best plane through the piperidine ring. In the crystal, molecules are connected by C—H⋯O and C—H⋯Cl interactions into layers in the ab plane.

Related literature

For the biological activity of piperidine derivatives, see: Aridoss et al. (2009 ▶); Michael (2001 ▶); Pinder (1992 ▶); Rubiralta et al. (1991 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For asymmetry parameters, see: Nardelli (1983 ▶). For hydrogen-bond motifs, see: Bernstein et al.(1995 ▶).

Experimental

Crystal data

C₂₁H₂₁Cl₂NO₂
M _r = 390.29
Monoclinic,
a = 8.278 (2) Å
b = 9.714 (3) Å
c = 11.847 (3) Å
β = 90.578 (9)°
V = 952.5 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 293 K
0.20 × 0.18 × 0.17 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.931, T _max = 0.944
8874 measured reflections
4241 independent reflections
3962 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.088
S = 1.03
4241 reflections
235 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.31 e Å⁻³
Absolute structure: Flack (1983 ▶), 1745 Friedel pairs
Flack parameter: 0.01 (5)

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.^{(21.5KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813007927/bt6893sup1.cif

e-69-0o609-sup1.cif^{(21.5KB, cif)}

Click here for additional data file.^{(207.8KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813007927/bt6893Isup2.hkl

e-69-0o609-Isup2.hkl^{(207.8KB, hkl)}

Click here for additional data file.^{(7KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813007927/bt6893Isup3.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	2.45	3.379 (2)	159
C20—H20⋯O1ⁱ	0.98	2.53	3.273 (2)	132
C21—H21C⋯Cl1ⁱⁱ	0.96	2.81	3.702 (2)	155

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

Acknowledgments

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

supplementary crystallographic information

Comment

Piperidine derivatives are the valuable 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). Against this background and to ascertain the molecular structure and conformation, the X-ray crystal structure determination of the title compound has been carried out.

The ORTEP plot of the molecule is shown in Fig. 1. The title compound crystallizes in the monoclinic space group P2₁. The piperidine ring adopts a distorted boat conformation. The puckering parameters (Cremer & Pople, 1975) and the asymmetry parameters (Nardelli, 1983) are: q₂=0.7556 (2) Å, q₃ = -0.010 (2) Å, φ₂ = 287.05 (1)° and Δ_s(C3 & C6)= 17.08 (1)°. The sum of the bond angles around N1 (359.1°) is in accordance with sp² hybridization.

The carbonyl group is oriented syn to C2 [C2—N1—C7—O1=] -6.5 (2)° and anti to C6 [C6—N1—C7—O1=] -176.7 (1)°. The best plane of the piperidine ring and the attached phenyl rings [C7—C12 and C13—C18] enclose dihedral angles of 87.9 (7)° and 70.8 (9)°. The two phenyl rings are oriented to each other with a dihedral angle of 54.01 (1)°.

The crystal packing reveals that the molecules are linked through a network of C—H···O and C—H···Cl intermolecular interactions. Atoms C2 and C20 of the molecule at (x, y, z) donate a proton to bifurcated acceptor atom O1 of the molecule at (1 - x,-1/2 + y,-z), which form two different C(5) and C(8) chains (Bernstein et al., 1995) forming layers in the ab plane as shown in Fig. 2.

Experimental

t-3,t-5-Dimethyl-r-2,c-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: 70%, Melting point: 190–92°C