(3E,5E)-1-Acryloyl-3,5-bis­(2-chloro­benzyl­idene)piperidin-4-one

Alireza Basiri; Vikneswaran Murugaiyah; Hasnah Osman; Madhukar Hemamalini; Hoong-Kun Fun

doi:10.1107/S1600536811015042

. 2011 Apr 29;67(Pt 5):o1228–o1229. doi: 10.1107/S1600536811015042

(3E,5E)-1-Acryloyl-3,5-bis(2-chlorobenzylidene)piperidin-4-one

Alireza Basiri ^a, Vikneswaran Murugaiyah ^a, Hasnah Osman ^b,^‡, Madhukar Hemamalini ^c, Hoong-Kun Fun ^c,^*,^§

PMCID: PMC3089119 PMID: 21754526

Abstract

In the title compound, C₂₂H₁₇Cl₂NO₂, the asymmetric unit consists of two crystallographically independent molecules and each piperidinone ring adopts an envelope conformation. The dihedral angles between the two chlorobenzene rings are 24.81 (10) and 19.15 (8)° in the two molecules. In the crystal, molecules are connected via weak intermolecular C—H⋯O hydrogen bonds forming layers perpendicular to the a axis.

Related literature

For details and applications of α,β-unsaturated ketones, see: Anke et al. (1981 ▶); Khodair et al. (1997 ▶); El-Subbagh et al. (2000 ▶); Al-Obaid et al. (1996 ▶); El-Barbary et al. (1994 ▶); Rungeler et al. (1999 ▶); Dimmock et al. (1983 ▶). For preparation details of 3,5-bis(2-chlorobenzylidene)piperidin-4-one, see: Dimmock et al. (2000 ▶). For ring conformations, see: Cremer & Pople (1975 ▶). For bond-length data, see: Allen et al. (1987 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₂₂H₁₇Cl₂NO₂
M _r = 398.27
Triclinic,
a = 9.1426 (5) Å
b = 14.3459 (8) Å
c = 16.6637 (9) Å
α = 108.348 (1)°
β = 102.695 (1)°
γ = 103.649 (1)°
V = 1910.71 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 100 K
0.44 × 0.40 × 0.16 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.858, T _max = 0.947
30297 measured reflections
11008 independent reflections
8952 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.132
S = 1.03
11008 reflections
503 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.11 e Å⁻³
Δρ_min = −0.65 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811015042/rz2586sup1.cif

e-67-o1228-sup1.cif^{(32KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811015042/rz2586Isup2.hkl

e-67-o1228-Isup2.hkl^{(527.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811015042/rz2586Isup3.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
C2A—H2AA⋯O2Aⁱ	0.93	2.44	3.146 (2)	133
C2B—H2BA⋯O2Bⁱⁱ	0.93	2.49	3.385 (2)	161
C21A—H21A⋯O2Bⁱⁱⁱ	0.93	2.47	3.180 (2)	133
C22A—H22A⋯O1Bⁱ	0.96 (3)	2.59 (3)	3.455 (3)	151 (2)
C22B—H22C⋯O1A^iv	0.94 (3)	2.40 (3)	3.191 (3)	141 (3)

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

Acknowledgments

AB, VM and HO thank the Malaysian Government and Universiti Sains Malaysia (USM) for providing financial support and the USM Graduate Scheme. HKF and MH thank the Malaysian Government and Universiti Sains Malaysia for the Research University grant No. 1001/PFIZIK/811160. MH thanks Universiti Sains Malaysia for a post-doctoral research fellowship.

supplementary crystallographic information

Comment

α,β-Unsaturated ketones are a biologically active group of chemicals which are produced by reaction of aldehydes and ketones through Claisen-Schmidt condensation. This class of compounds shows diverse biological activities such as cytotoxic (Anke et al., 1981; Khodair et al., 1997), antitumoral (El-Subbagh et al., 2000; Al-Obaid et al., 1996) and antiviral (El-Barbary et al., 1994) properties. The title compound, (I), includes a conjugated system as the fundamental part in determining the bioactivity of this type of compounds (Rungeler et al., 1999) as well as a β-amino ketone in the structure. These compounds proved to have cytotoxic activities without any mutagenic and carcinogenic side effects (Dimmock et al., 1983).

The asymmetric unit of the title compound consists of two crystallographically independent (3E,5E)-1-acryloyl- 3,5-bis(2-chlorobenzylidene)piperidin-4-one molecules, (A & B), as shown in Fig. 1. The bond lengths and angles of molecules A and B agree with each other and are within normal ranges (Allen et al., 1987). The two chlorobenzene rings are inclined to each other forming dihedral angles of 24.81 (10)° (C1A–C6A:C14A–C19A) in molecule A and 19.15 (8)° (C1B–C6B:C14B–C19B) in molecule B.

The piperidine rings (N1A/C8A–C12A and N1B/C8B–C12B) adopt envelope conformations [puckering parameters (Cremer & Pople, 1975): Q = 0.5071 (18) Å, θ = 126.1 (2)° and φ = 178.5 (3) °; Q = 0.567 (18) Å, θ = 65.89 (18)° and φ = 356.4 (2)°, respectively] with atoms N1A and N1B displaced by 0.6754 (16) and 0.7378 (14) Å from the least-squares plane defined by the remaining atoms (C8A–C12A and C8B–C12B) in the rings.

In the crystal structure (Fig. 2), the molecules are connected via weak intermolecular C2A—H2AA···O2A, C21A—H21A···O2B, C22A—H22A···O1B, C2B—H2BA···O2B and C22B—H22C···O1A hydrogen bonds forming layers perpendicular to the a axis.

Experimental

3,5-Bis(2-chlorobenzylidene)piperidin-4-one was synthesized by the method described by Dimmock et al. (2000). Briefly, the title compound (I) was prepared by dropwise addition of an acryloyl chloride solution (8.7 mmol) to a stirred mixture of 3,5-bis(2,4-dichlorobenzylidene)piperidin-4-one (5.8 mmol) and acetone (10 ml) in presence of sodium carbonate (29 mmol) at room temperature. After completion of the reaction (through TLC monitoring), the mixture was poured into ice. The precipitate which formed was filtered and washed with water. The pure solid was then recrystallised from ethanol to afford the title compound as yellow crystals.