1-Benzyl-3,5-bis­(4-chloro­benzyl­idene)piperidin-4-one

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

doi:10.1107/S1600536811018587

. 2011 May 25;67(Pt 6):o1505–o1506. doi: 10.1107/S1600536811018587

1-Benzyl-3,5-bis(4-chlorobenzylidene)piperidin-4-one

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

PMCID: PMC3120573 PMID: 21754872

Abstract

The title compound, C₂₆H₂₁Cl₂NO, crystallizes with two symmetry-independent molecules (A and B) in the asymmetric unit. In both molecules, the central heterocyclic ring adopts a sofa conformation. The dihedral angles between the planar part of this central heterocyclic ring [maximum deviations of 0.011 (1) and 0.036 (1) Å in molecules A and B, respectively] and the two almost planar [maximum deviations of 0.020 (1) and 0.008 (1) Å in A and 0.007 (1) and 0.011 (1) in B] side-chain fragments that include the aromatic ring and bridging atoms are 20.1 (1) and 31.2 (1)° in molecule A, and 26.4 (1) and 19.6 (1)° in molecule B. The dihedral angles between the planar part of the heterocyclic ring and the benzyl substituent are 79.7 (1) and 53.2 (1)° in molecules A and B, respectively. In the crystal, weak intermolecular C—H⋯O hydrogen bonds link the two independent molecules into dimers.

Related literature

For non-linear optical organic compounds with two-photon absorption properties and potential biophotonic materials, see: Nesterov et al. (2003 ▶, 2007 ▶); Sarkisov et al. (2005 ▶). For the biological importance of 4-piperidone, see: Jia et al. (1988 ▶); Dimmock et al. (2001 ▶). For the synthesis of the title compound, see: Dimmock et al. (2001 ▶). For related structures, see: Nesterov et al. (2003 ▶, 2007 ▶, 2011 ▶). For details concerning weak hydrogen bonds, see: Desiraju & Steiner (1999 ▶). For van der Waals radii, see: Rowland & Taylor (1996 ▶).

Experimental

Crystal data

C₂₆H₂₁Cl₂NO
M _r = 434.34
Triclinic,
a = 12.504 (2) Å
b = 13.414 (4) Å
c = 14.763 (2) Å
α = 102.736 (3)°
β = 111.676 (2)°
γ = 104.066 (3)°
V = 2095.7 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 100 K
0.25 × 0.20 × 0.12 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.922, T _max = 0.962
24542 measured reflections
8251 independent reflections
7049 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.108
S = 1.02
8251 reflections
541 parameters
H-atom parameters constrained
Δρ_max = 0.79 e Å⁻³
Δρ_min = −0.48 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/S1600536811018587/fl2348sup1.cif

e-67-o1505-sup1.cif^{(34.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811018587/fl2348Isup2.hkl

e-67-o1505-Isup2.hkl^{(403.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811018587/fl2348Isup3.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
C16B—H16B⋯O1A	0.95	2.42	3.334 (2)	160
C14A—H14A⋯O1B	0.95	2.52	3.309 (2)	141
C16A—H16A⋯O1B	0.95	2.48	3.099 (2)	122

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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 et al. 2007; Nesterov et al., 2011; 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; Dimmock et al., 2001). It may also find application as an agent for locating cancer cells with two photon excited fluorescence and as a potential agent for a photodynamic treatment of cancer (Nesterov et al., 2003; Sarkisov et al., 2005).

The molecular structure of the title compound is illustrated in Fig. 1. The central heterocycle adopts a sofa conformation: atom N1A lies -0.721 (2) Å in (IA) and N1B lies 0.725 (2) Å in (IB) out of the central C₅ plane [planar within 0.011 (1) and 0.036 (1) Å, respectively]. Dihedral angles between the flat part of the heterocycle (atoms C2A,C3A,C4A,C5A,C6A in (IA) and C2B,C3B,C4B,C5B,C6B in (IB) and the two almost planar fragments that include the Ph-ring and the bridging atoms are 20.1 (1) and 31.2 (1)° in (IA) for (C7A-C13A) and (C14A-C20A), respectively and 26.4 (1) and 19.6 (1)° for (C7B-C13B) and (C14B-C20B), respectively. Such nonplanarity might partly be caused by the presence of short intramolecular contacts H2AA···H13A and H6AB···H20A in (IA) and H2BB···H13B and H6BA···H20B in (IB) with distances 2.19 and 2.18 Å in (IA) and 2.14 and 2.22 Å in (IB), that are somewhat shorter than the doubled van der Waals radii of the H atom (Rowland & Taylor, 1996). Atoms N1A and N1B in the piperidone rings have a pyramidal coordination with the sum of bond angles equal to 331.4 (1) and 335.8 (1)°, while the methylene substituent connected to it occupies an equatorial position. The mutual orientations of the benzyl substituents and flat part of the heterocycles in both molecules are more different (dihedral angles are 79.7 (1) and 53.2 (1)°, respectively).

In the crystal there are several weak intermolecular C—H···O contacts (Table 1) that could be considered as weak hydrogen bonds (Desiraju & Steiner, 1999) that link (IA) and (IB) molecules into dimers (Fig. 2).

Experimental

The title compound was obtained according to the literature procedure (Dimmock et al., 2001) by the reaction of p-chlorobenzaldehyde with 1-benzyl-4-piperidone. The precipitate obtained was isolated and recrystallized from ethanol/acetonitrile [v/v = 50/50]; Mp. 424 K, yield 86%). The title compound was characterized by ¹H and ¹³C NMR spectroscopy.