Crystal structure of 1-cyclo­propane­carbon­yl-3-methyl-2,6-di-p-tolyl­piperidin-4-one

A Kamaraj; S Ranjith; R Rajkumar; G Mohanraj; K Krishnasamy

doi:10.1107/S1600536814018546

. 2014 Aug 30;70(Pt 9):o1056–o1057. doi: 10.1107/S1600536814018546

Crystal structure of 1-cyclopropanecarbonyl-3-methyl-2,6-di-p-tolylpiperidin-4-one

A Kamaraj ^a, S Ranjith ^b, R Rajkumar ^a, G Mohanraj ^c, K Krishnasamy ^a,^*

PMCID: PMC4186191 PMID: 25309223

Abstract

The title compound, C₂₄H₂₇NO₂, crystallizes with two independent molecules (A and B) in the asymmetric unit. The two molecules have very similar conformations and each exhibits an intramolecular C—H⋯π interaction. The central piperidine rings adopt boat conformations and the p-tolyl rings are inclined to the mean plane of the piperidine ring by 71.21 (11) and 89.86 (12)° in molecule A and by 68.01 (12) and 89.33 (12)° in molecule B. The cyclopropanecarbonyl group is oriented at an angle of 68.5 (2)° with respect to the mean plane of the piperidine ring in molecule A and 66.2 (2)° in molecule B. In the crystal, the A and B molecules are linked by C—H⋯O hydrogen bonds, enclosing R ₂ ¹(6) ring motifs, forming ribbons running along the a-axis direction.

Keywords: crystal structure, cyclopropanecarbonyl, p-tolylpiperidin-4-one, C—H⋯π interaction

Related literature

For the biological activity of piperidine derivatives, see: Aridoss et al. (2009 ▶); Nalanishi et al. (1974 ▶); Michael (2001 ▶); Pinder (1992 ▶); Rubiralta et al. (1991 ▶). For the crystal structure of the related compound, 2,2-dichloro-1-(4-ethoxyphenyl)cyclopropanylpiperidin-1-yl ketone, see: Sun et al. (2006 ▶).

Experimental

Crystal data

C₂₄H₂₇NO₂
M _r = 361.47
Triclinic,
a = 10.494 (3) Å
b = 11.464 (2) Å
c = 17.425 (3) Å
α = 80.265 (15)°
β = 86.064 (17)°
γ = 89.877 (18)°
V = 2061.1 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 293 K
0.25 × 0.22 × 0.19 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.982, T _max = 0.986
13683 measured reflections
7267 independent reflections
4028 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.156
S = 0.95
7276 reflections
493 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.14 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, 2008 ▶); 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) global, I. DOI: 10.1107/S1600536814018546/su2765sup1.cif

e-70-o1056-sup1.cif^{(35.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814018546/su2765Isup2.hkl

e-70-o1056-Isup2.hkl^{(348.4KB, hkl)}

Click here for additional data file.^{(7.8KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814018546/su2765Isup3.cml

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

. DOI: 10.1107/S1600536814018546/su2765fig1.tif

The molecular structure of the two independent molecules of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

Click here for additional data file.^{(1.5MB, tif)}

b a . DOI: 10.1107/S1600536814018546/su2765fig2.tif

The crystal packing of the title compound, viewed along the b axis, in which hydrogen bonds form Inline graphic (6) bifurcated ring motifs forming ribbons running along a axis. For the sake of clarity, H atoms not involved in hydrogen bonds have been omitted.

CCDC reference: 922988

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

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

Cg1 and Cg2 are the centroids of the C7A–C12A and C7B–C12B rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C23A—H23A⋯Cg1	0.93	2.86	3.787 (3)	173
C23B—H23B⋯Cg2	0.93	2.85	3.777 (3)	173
C5A—H5A⋯O2B ⁱ	0.98	2.41	3.366 (3)	166
C5B—H5B⋯O2A	0.98	2.42	3.381 (3)	166
C19A—H19A⋯O2B ⁱ	0.93	2.59	3.435 (3)	151

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Symmetry code: (i) Inline graphic .

Acknowledgments

KK thanks the University Grant Commission for the financial support (major research project, F. No. 42–342/2013) of this research work. The authors are grateful to the UGC Networking Resource Centre, University of Hyderabad, for providing characterization facilities and Dr R. Nagarajan, School of Chemistry, University of Hyderabad, for providing laboratory facilities.

supplementary crystallographic information

S1. Synthesis and crystallization

To a well stirred solution of 3-methyl-2,6-di-p-tolylpiperidin-4-one (1 equiv) and triethylamine (1 equiv) in 30 ml of dry benzene, cyclopropanecarbonyl chloride (1 equiv) in 20 ml of benzene was added drop wise over a period of 30 min. Stirring was continued with mild heating using a magnetic stirrer. After the completion of reaction, it was poured into water and extracted with ether in three 50 ml portions. The combined ether extract was then washed well with 3% sodium bicarbonate solution and dried over anhydrous sodium sulfate. Crystal were obtained by slow evaporation of a solution of the title compound in ethanol.

S2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were fixed geometrically and allowed to ride on their parent atoms: C—H = 0.93–0.97 Å with U_iso(H) = 1.5U_eq(C-methyl) and = 1.2U_eq(C) for other H atoms.