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

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

doi:10.1107/S1600536811016023

. 2011 May 7;67(Pt 6):o1301–o1302. doi: 10.1107/S1600536811016023

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

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

PMCID: PMC3120482 PMID: 21754705

Abstract

The asymmetric unit of the title compound, C₂₂H₁₅Cl₄NO₂·0.5H₂O, consists of a (3E,5E)-1-acryloyl-3,5-bis(2,4-dichlorobenzylidene)piperidin-4-one molecule and a half-molecule of water (the O atom of the water molecule lies on a twofold axis). The piperidin-4-one ring adopts an envelope conformation. The dihedral angle between the two terminal benzene rings is 8.84 (11)°. In the crystal, molecules are connected by C—H⋯O hydrogen bonds forming supramolecular chains along the c axis. Furthermore, adjacent chains are interconnected by the water molecules via O—H⋯O hydrogen bonds.

Related literature

For details and applications of α,β-unsaturated carbonyl compounds, see: Oh et al. (2006 ▶); El-Subbagh et al. (2000 ▶); Husain et al. (2006 ▶); Favier et al. (2005 ▶). For details of the preparation, see: Dimmock et al. (2000 ▶). For ring conformations, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

2C₂₂H₁₅Cl₄NO₂·H₂O
M _r = 952.32
Monoclinic,
a = 27.0296 (12) Å
b = 11.3031 (5) Å
c = 18.9580 (14) Å
β = 133.807 (2)°
V = 4180.0 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.59 mm⁻¹
T = 296 K
0.41 × 0.22 × 0.09 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.794, T _max = 0.947
22264 measured reflections
6084 independent reflections
3314 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.140
S = 1.04
6084 reflections
273 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.30 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/S1600536811016023/sj5130sup1.cif

e-67-o1301-sup1.cif^{(21.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811016023/sj5130Isup2.hkl

e-67-o1301-Isup2.hkl^{(291.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811016023/sj5130Isup3.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
O1W—H1W1⋯O2ⁱ	1.05	2.19	3.180 (3)	157
C4—H4A⋯O1ⁱⁱ	0.93	2.29	3.186 (3)	162

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

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 also thanks Universiti Sains Malaysia for a post-doctoral research fellowship.

supplementary crystallographic information

Comment

The α,β-unsaturated carbonyl moiety is present in a large number of natural and synthetic products which are products of the Claisen-Schmidt condensation reaction. They exhibit wide variety of biological activities such as cytotoxicity (Oh et al., 2006), antitumor (El-Subbagh et al., 2000) and antimicrobial (Husain et al., 2006) properties. Furthermore, it has been shown that the conjugated system plays a fundamental role in determining the bioactivity, due to its ability to act as a Michael acceptor for the addition of protein functional groups (Favier et al., 2005). The title compound (I), is a new piperidin-4-one derivative.

The asymmetric unit of the title compound consists of a (3E,5E)-1-acryloyl-3,5-bis(2,4-dichlorobenzylidene) piperidin-4-one molecule and a half-molecule of water (the O atom of the water molecule lies on a twofold axis), as shown in Fig. 1. The dihedral angle between the two terminal phenyl (C1–C6:C15–C20) rings is 8.84 (11)°. The piperidine (N12/C8–C11/C13) ring adopts an envelope conformation [puckering parameters: Q = 0.508 (3) Å, θ = 122.4 (3)° and φ = 182.1 (4)°; (Cremer & Pople, 1975)] with atoms C11 and C13 deviating by 0.233 (2) and 0.217 (3) Å from the least-squares plane defined by the remaining atoms (N12/C8–C10) in the ring.

In the crystal structure, (Fig. 2), the molecules are connected by intermolecular C4—H4A···O1 hydrogen bonds forming one-dimensional supramolecular chains along the c-axis. Furthermore, adjacent chains are inter-connected by water molecules via O1W—H1W1···O2 hydrogen bonds.

Experimental

3,5-bis(2,4-dichlorobenzylidene)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 acryloyl chloride solution (7.24 mmol) to stirring mixture of 3,5-bis(2,4-dichlorobenzylidene) piperidin-4-one (4.82 mmol) and acetone (10 ml) in presence of weak base at room temperature. After completion of the reaction (through TLC monitoring), the mixture was poured into ice. The precipitate was filtered and washed with water. The pure solid was then recrystallized from ethanol to afford the title compound as yellow crystals.