Crystal structure of 2-chloro-1-(3-methyl-2,6-di­phenyl­piperidin-1-yl)ethanone

V Shreevidhyaa Suressh; K Prathebha; S Abdul Basheer; S Ponnuswamy; G Usha

doi:10.1107/S205698901500122X

. 2015 Jan 28;71(Pt 2):o135–o136. doi: 10.1107/S205698901500122X

Crystal structure of 2-chloro-1-(3-methyl-2,6-diphenylpiperidin-1-yl)ethanone

V Shreevidhyaa Suressh ^a, K Prathebha ^b, S Abdul Basheer ^c, S Ponnuswamy ^c, G Usha ^b,^*

PMCID: PMC4384538 PMID: 25878870

Abstract

In the title compound, C₂₀H₂₂ClNO, the piperidine ring has a twist-boat conformation. There is an intramolecular C—H⋯π interaction involving the two phenyl rings which are inclined to one another by 84.91 (7)°. In the crystal, molecules are linked via C—H⋯O hydrogen bonds, forming helical chains along [010]. The chains are linked by C—H⋯π interactions, forming sheets parallel to (100).

Keywords: crystal structure, piperidine, diphenylpiperidine, 2-chloro-ethanone, hydrogen bonding, C—H⋯π interactions

Related literature

For the biological activity of piperidines and their derivatives, see: Aridoss et al. (2007 ▸); Jain et al. (2005 ▸); Mobio et al. (1989 ▸); Palani et al. (2002 ▸). For the crystal structure of a very similar compound, 2-chloro-1-(3,3-dimethyl-2,6-diphenylpiperidin-1-yl)ethanone, see: Prathebha et al. (2013 ▸).

Experimental

Crystal data

C₂₀H₂₂ClNO
M _r = 327.84
Monoclinic,
a = 8.7146 (3) Å
b = 12.3963 (4) Å
c = 16.6117 (6) Å
β = 101.523 (2)°
V = 1758.37 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 293 K
0.25 × 0.23 × 0.23 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▸) T _min = 0.946, T _max = 0.950
16473 measured reflections
4353 independent reflections
3075 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.236
S = 0.92
4353 reflections
208 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▸); cell refinement: SAINT (Bruker, 2008 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S205698901500122X/su5068sup1.cif

e-71-0o135-sup1.cif^{(26.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901500122X/su5068Isup2.hkl

e-71-0o135-Isup2.hkl^{(208.1KB, hkl)}

Click here for additional data file.^{(6.5KB, cml)}

Supporting information file. DOI: 10.1107/S205698901500122X/su5068Isup3.cml

Click here for additional data file.^{(2MB, tif)}

. DOI: 10.1107/S205698901500122X/su5068fig1.tif

The molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level. The intramolecular C—H⋯π interaction is shown as a dashed line (see Table 1 for details).

Click here for additional data file.^{(1.2MB, tif)}

a . DOI: 10.1107/S205698901500122X/su5068fig2.tif

A view along the a axis of the crystal packing of the title compound. The dashed lines indicate the hydrogen bonds (see Table 1 for details).

CCDC reference: 1044361

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

Cg1 is the centroid of the C5C10 ring.

DHA	DH	HA	D A	DHA
C17H17Cg1	0.93	2.98	3.879(2)	164
C21H21O1ⁱ	0.93	2.57	3.472(3)	165
C14H14bCg1ⁱⁱ	0.98	2.84	3.751(2)	156

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

Acknowledgments

The authors thank Professor D. Velmurugan, Centre for Advanced Study in Crystallography and Biophysics, University of Madras, for providing data-collection facilities.

supplementary crystallographic information

S1. Structural commentary

Piperidine and their derivatives are significant heterocyclic compounds found in natural substances (Jain et al., 2005). They have been observed to exhibit a wide range of biological activities, such as anti-fungal, anti-malarial, anti-bacterial and anti-viral activities (Aridoss et al., 2007; Mobio et al., 1989). They also show a highly favourable antiviral activity against a range of primary HIV-1 isolates (Palani et al., 2002).

The molecular structure of the title compound is illustrated in Fig. 1. The sum of the bond angles around atom N1 is 359.85 (1) °, indicating sp² hybridization. The dihedral angle between the phenyl rings (C5—C10 and C16—C21) is 84.91 (7) °. They are linked by an intramolecular C—H···π interaction (Table 1). The piperidine ring adopts a twist-boat conformation.

In the crystal, molecules are linked via C—H···O hydrogen bonds forming helical chains along [010], see Table 1 and Fig. 2. The chains are linked by C—H···π interactions forming sheets parallel to (100), see Table 1.

S2. Synthesis and crystallization

A mixture of t-3-methyl-r-2,c-6-diphenylpiperidine (5 mmol), chloroacetyl chloride (20 mmol) and triethylamine (20 mmol) in anhydrous benzene (20 ml) was stirred at rt. The precipitated ammonium salt was filtered and the resulting solution was washed with water and bicarbonate solution (4 × 10 ml). Finally, the benzene solution was dried over anhydrous sodium sulfate and concentrated. The pasty mass was purified by crystallization from pet-ether (333-353 K) and ethyl acetate in the ratio of 95: 5, and yielded colourless block-like crystals.

S3. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were positioned geometrically and treated as riding on their parent atoms: C—H = 0.93 - 0.98 Å, with U_iso(H)= 1.5 U_eq(C) for methyl H atoms and = 1.2U_eq(C) for other H atoms.