3,5-Bis(4-chloro­benzyl­idene)-1-methyl­piperidin-4-one

Volodymyr V Nesterov; Sergey S Sarkisov; Vladimir Shulaev; Vladimir N Nesterov

doi:10.1107/S1600536811006994

. 2011 Mar 2;67(Pt 4):o760–o761. doi: 10.1107/S1600536811006994

3,5-Bis(4-chlorobenzylidene)-1-methylpiperidin-4-one

Volodymyr V Nesterov ^a,^*, Sergey S Sarkisov ^b, Vladimir Shulaev ^c,^*, Vladimir N Nesterov ^d

PMCID: PMC3099892 PMID: 21754057

Abstract

In the title molecule, C₂₀H₁₇Cl₂NO, the central heterocyclic ring adopts a flattened boat conformation. The dihedral angles between the planar part of this central heterocyclic ring [maximum deviation = 0.004 (1) Å] and the two almost planar side-chain fragments [maximum deviations = 0.015 (1) and 0.019 (1) Å], that include the aromatic ring and bridging atoms, are 18.1 (1) and 18.0 (1)°. In the crystal, pairs of weak intermolecular C—H⋯O hydrogen bonds link molecules into inversion dimers that form stacks along the a axis. The structure is further stabilized by weak intermolecular C—H⋯π interactions involving the benzene rings.

Related literature

For non-linear optical organic compounds with two-photon absorption properties and potential biophotonic materials, see: Nesterov et al. (2003 ▶); Nesterov (2004 ▶); Sarkisov et al. (2005 ▶). For the biological importance of 4-piperidone, see: Jia et al. (1988 ▶, 1989 ▶); Dimmock et al. (2001 ▶). For the synthesis of the title compound, see: Dimmock et al. (2001 ▶). For related structures, see: Nesterov (2004 ▶); Nesterov et al. (2003 ▶, 2007a ▶,b ▶,c ▶, 2008 ▶). For weak hydrogen bonds, see: Desiraju & Steiner (1999 ▶). For the van der Waals radius of the H atom, see: Rowland & Taylor (1996 ▶).

Experimental

Crystal data

C₂₀H₁₇Cl₂NO
M _r = 358.25
Monoclinic,
a = 5.4568 (11) Å
b = 13.916 (3) Å
c = 22.289 (4) Å
β = 90.847 (3)°
V = 1692.4 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.39 mm⁻¹
T = 100 K
0.23 × 0.18 × 0.08 mm

Data collection

Bruker SMART APEX II CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.916, T _max = 0.970
14890 measured reflections
3461 independent reflections
2830 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.080
S = 1.03
3461 reflections
218 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811006994/su2255sup1.cif

e-67-0o760-sup1.cif^{(17.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811006994/su2255Isup2.hkl

e-67-0o760-Isup2.hkl^{(169.8KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 and Cg2 are the centroids of the C15–C20 and C8–C13 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9A⋯O1ⁱ	0.95	2.47	3.210 (2)	135
C12—H12A⋯Cg1ⁱⁱ	0.95	2.72	3.439 (2)	133
C19—H19A⋯Cg2ⁱⁱⁱ	0.95	2.73	3.432 (2)	131

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

Acknowledgments

We appreciate financial support from DoD Grant W911NF-05–1–0456, and in part by the NIH (National Institutes of Health) NCI (National Cancer Institute) grant R01CA120170.

supplementary crystallographic information

Comment

Continuing our work on the synthesis and structural investigations of nonlinear optical organic compounds with two-photon absorption properties and potential biophotonic materials (Nesterov et al., 2003; Nesterov, 2004; Nesterov et al., 2007a-c; Nesterov et al., 2008; Sarkisov et al., 2005), we investigated the crystal structure of the title compound. This compound belongs to a group that has shown anticancer activity (Jia et al., 1988; Jia et al., 1989; Dimmock et al., 2001). It may also find application as an agent for locating cancer cells with two photon excited fluorescence and as potential agent for a photodynamic treatment of cancer (Nesterov et al., 2003; Sarkisov et al., 2005).

The molecular structure of the title molecule is illustrated in Fig. 1. The central heterocycle adopts a flattened boat conformation: atoms N1 and C4 lie -0.723 (1) and -0.205 (1) Å, respectively, out of the central C₄ plane [planar within 0.004 (1) Å]. Dihedral angles between the flat part of the heterocycle (atoms C2,C3,C5,C6) and the two almost planar fragments that include the Ph-ring and the bridging atoms are 18.1 (1) and 18.0 (1)° for (C7-C13) and (C14-C20), respectively. Such nonplanarity might partly be caused by the presence of short intramolecular contacts H2B···H13A and H6A···H20A with distances 2.16 and 2.15 Å, that are somewhat shorter than the doubled van der Waals radii of the H atom (Rowland & Taylor, 1996). Atom N1 in the piperidone ring has a pyramidal coordination with the sum of bond angles equal to 329.8 (1)°, while the methyl substituent connected to it occupies an equatorial position.

In the crystal there are weak intermolecular C—H···O (H9A···O1 2.47 Å) contacts (Table 1) that could be considered as weak hydrogen bonds (Desiraju & Steiner, 1999). Such H-bonds link the molecules into dimers, centered about an inversion center, that form stacks along the a-axis (Fig. 2). The structure of the molecule is further stabilized by weak intermolecular C-H···π-interactions involving the benzene rings (Table 1).

Experimental

The title compound was obtained according to the literature procedure (Dimmock et al., 2001) by the reaction of p-chlorobenzaldehyde with 1-methyl-4-piperidone. The precipitate obtained was isolated and recrystallized from ethanol/acetonitrile [v/v = 50/50]; Mp. 442 K, yield 87%). The title compound was characterized by ¹H and ¹³C NMR spectroscopy.