1-Dichloro­acetyl-3,3-dimethyl-2,6-diphenyl­piperidin-4-one

T Kavitha; S Ponnuswamy; M Jamesh; J Umamaheshwari; M N Ponnuswamy

doi:10.1107/S1600536808040051

. 2008 Dec 3;65(Pt 1):o10. doi: 10.1107/S1600536808040051

1-Dichloroacetyl-3,3-dimethyl-2,6-diphenylpiperidin-4-one

T Kavitha ^a, S Ponnuswamy ^b, M Jamesh ^b, J Umamaheshwari ^b, M N Ponnuswamy ^a,^*

PMCID: PMC2967931 PMID: 21581563

Abstract

In the title compound, C₂₁H₂₁Cl₂NO₂, the piperidine ring adopts a distorted boat conformation. The two phenyl rings are approximately perpendicular to each other, with a dihedral angle of 86.12 (7)°. Molecules are linked into centrosymmetric dimers by pairs of bifurcated C—H⋯O hydrogen bonds, forming R ₂ ²(10) and R ₂ ²(14) ring motifs, and an intramolecular C—H⋯O link also occurs.

Related literature

For general backround, see: Ponnuswamy et al. (2002 ▶). For details of hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For ring puckering and asymmetry parameters, see: Cremer & Pople (1975 ▶); Nardelli (1983 ▶). For hybridization, see: Beddoes et al. (1986 ▶).

Experimental

Crystal data

C₂₁H₂₁Cl₂NO₂
M _r = 390.29
Triclinic,
a = 9.1084 (2) Å
b = 10.8992 (3) Å
c = 10.9918 (3) Å
α = 63.879 (1)°
β = 85.343 (2)°
γ = 79.029 (1)°
V = 961.84 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 293 (2) K
0.30 × 0.26 × 0.20 mm

Data collection

Bruker Kappa APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T _min = 0.902, T _max = 0.933
26977 measured reflections
7709 independent reflections
5516 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.057
wR(F ²) = 0.180
S = 1.03
7709 reflections
235 parameters
H-atom parameters constrained
Δρ_max = 0.80 e Å⁻³
Δρ_min = −0.73 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808040051/ci2724sup1.cif

e-65-00o10-sup1.cif^{(21.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808040051/ci2724Isup2.hkl

e-65-00o10-Isup2.hkl^{(369.5KB, 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
C14—H14⋯O2	0.93	2.57	3.250 (2)	130
C2—H2⋯O2ⁱ	0.98	2.50	3.4264 (18)	158
C16—H16A⋯O2ⁱ	0.96	2.54	3.413 (2)	151

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Symmetry code: (i) Inline graphic .

Acknowledgments

TK thanks Dr Babu Varghese, SAIF, IIT–Madras, Chennai, India, for his help with the data collection. SP thanks the UGC, India, for financial support.

supplementary crystallographic information

Comment

The design and synthesis of conformationally anchored molecules are important due its potency and selectivity for designing drugs. The piperidin-4-ones are one such class of compounds to be investigated to understand the stereodynamics and other structural features (Ponnuswamy et al., 2002).

The sum of bond angles around atom N1 (359.6°) indicates sp² hybridization (Beddoes et al., 1986). The N1—C7 [1.3564 (16) Å] and C7—O2 [1.2149 (17) Å] distances indicate electron delocalization. The piperidine ring adopts a distorted boat conformation, with puckering parameters (Cremer & Pople, 1975) q2 = 0.638 (1) Å, q3 = -0.067 (2) Å and φ₂ = 253.4 (1)°, and the asymmetry parameters ΔC_s(C2)= 14.4 (1)° (Nardelli, 1983). The best plane through the piperidine ring, N1/C3/C4/C6, forms dihedral angles of 89.31 (6)° and 63.47 (7)°, respectively, with the C9—C4 and C17—C22 phenyl rings. The two phenyl rings are approximately perpendicular to each other, with a dihedral angle of 86.12 (7)°.

The crystal structure is stabilized by intermolecular C—H···O hydrogen bonds. Each atoms C2 and C16 at (x, y, z) donate one proton to bifurcated acceptor O2 at (-x, 1 - y, 1 - z), forming a centrosymmetric dimer (Fig. 2) with R₂²(10) and R₂²(14) ring motifs (Bernstein et al., 1995).

Experimental

A mixture of 3,3-dimethyl-cis-2,6-diphenylpiperidin-4-one (1.4 g, 5 mmol), dichloroacetylchloride (1 ml, 10 mmol) and triethylamine (2 ml, 14.4 mmol) in anhydrous benzene (20 ml) was stirred at room temperature for 7 h. The benzene solution was dried over anhydrous Na₂SO₄ and concentrated. The pasty mass obtained was purified by crystallization from benzene-petroleum ether (333–353 K) in the ratio of 95:5.