1-Dichloro­acetyl-r-2,c-6-bis­(4-methoxy­phen­yl)-c-3,t-3-dimethyl­piperidin-4-one

M Thenmozhi; S Ponnuswamy; V Mohanraj; R Vijayalakshmi; M N Ponnuswamy

doi:10.1107/S1600536808040063

. 2008 Dec 3;65(Pt 1):o11. doi: 10.1107/S1600536808040063

1-Dichloroacetyl-r-2,c-6-bis(4-methoxyphenyl)-c-3,t-3-dimethylpiperidin-4-one

M Thenmozhi ^a, S Ponnuswamy ^b, V Mohanraj ^b, R Vijayalakshmi ^c, M N Ponnuswamy ^a,^*

PMCID: PMC2967932 PMID: 21581573

Abstract

In the title compound, C₂₃H₂₅Cl₂NO₄, the piperidine ring adopts a distorted boat conformation. Inversion-related molecules are linked into centrosymmetric R ₂ ²(16) dimers by paired C—H⋯O hydrogen bonds, and the dimers are connected via C—H⋯O hydrogen bonds into a chain running along [101].

Related literature

For general background, see: Eller et al.(2002 ▶); Ribeiro da Silva et al. (2007 ▶). For hybridization, see: Beddoes et al. (1986 ▶) For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For ring conformational analysis, see: Cremer & Pople (1975 ▶); Nardelli (1983 ▶).

Experimental

Crystal data

C₂₃H₂₅Cl₂NO₄
M _r = 450.34
Monoclinic,
a = 23.6295 (9) Å
b = 10.3999 (4) Å
c = 19.2617 (9) Å
β = 107.734 (1)°
V = 4508.5 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 293 (2) K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T _min = 0.911, T _max = 0.939
29354 measured reflections
6905 independent reflections
4138 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.056
wR(F ²) = 0.184
S = 1.00
6905 reflections
275 parameters
H-atom parameters constrained
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.63 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: SHELXS97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808040063/ci2726sup1.cif

e-65-00o11-sup1.cif^{(23.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808040063/ci2726Isup2.hkl

e-65-00o11-Isup2.hkl^{(331.2KB, 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
C6—H6⋯O1ⁱ	0.98	2.30	3.216 (2)	155
C13—H13⋯O3ⁱⁱ	0.93	2.58	3.453 (3)	155

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

Acknowledgments

SP thanks the UGC, India, for financial support.

supplementary crystallographic information

Comment

The piperidine compounds are used in chemical industry for the synthesis of pharmacological drugs, either as reactants, solvents or being units of molecular chemical structure of the final compounds. These compounds have significant biological importance with more environmental impact (Ribeiro da Silva et al., 2007). A significant industrial application of piperidine is for the production of dipiperidinyl dithiuram tetrasulfide, which is used as a rubber vulcanization accelerator (Eller et al., 2002).

The piperidine ring adopts a distorted boat conformation, with puckering parameters (Cremer & Pople, 1975) q₂ = 0.606 (2) Å, q₃ = 0.127 (2) Å, and φ = 77.5 (2)°, and asymmetry parameter Δ_s(C2) = 18.26 (17)° (Nardelli, 1983). The torsion angles C13—C12—O2—C15 [2.6 (3)°] and C20—C21—O4—C24 [-11.7 (3)°] indicate that the methoxy groups are almost coplanar with the attached rings (Fig.1). The sum of the bond angles around atom N1 (359.4°) of the piperidine ring is in accordance with sp² hybridization (Beddoes et al., 1986). The best plane through the piperidine ring (N1/C3/C4/C6) and methoxyphenyl ring (C9—C14) are orthogonal to one another, with a dihedral angle of 87.18 (7)°, whereas, the other methoxyphenyl ring (C18—C23) is oriented at an angle of 54.47 (7)°.

The molecules at positions (x, y, z) and (1 - x, 1 - y, 1 - z) are linked through a pair of C13—H13···O3 hydrogen bonds forming a cyclic centrosymmetric R₂²(16) dimer (Bernstein et al., 1995). The dimers are linked by intermolecular C6—H6···O1 hydrogen bonds (Table 1) into a chain running along the [101] (Fig.2).

Experimental

To the solution of r-2,c-6-bis(4-methoxyphenyl)-c-3,t-3-dimethylpiperidin-4-one (2 g) in benzene (25 ml), triethylamine (2.0 ml) and dichloroacetyl chloride (1.40 ml) were added and allowed to reflux on a water bath for 5 h. The course of the reaction was monitored by TLC. The solution was concentrated and the resulting mass was crystallized from ethanol.