Methyl ({[(4E)-1,3-dimethyl-2,6-di­phenyl­piperidin-4-yl­idene]amino}­oxy)acetate

T Mohandas; M Velayutham Pillai; T Vidhyasagar; A Pasupathy; P Sakthivel

doi:10.1107/S1600536814006667

. 2014 Apr 2;70(Pt 5):o513. doi: 10.1107/S1600536814006667

Methyl ({[(4E)-1,3-dimethyl-2,6-diphenylpiperidin-4-ylidene]amino}oxy)acetate

T Mohandas ^a, M Velayutham Pillai ^b, T Vidhyasagar ^b, A Pasupathy ^c, P Sakthivel ^d,^*

PMCID: PMC4011218 PMID: 24860328

Abstract

In the title compound, C₂₂H₂₆N₂O₃, the piperidine ring exhibits a chair conformation. The phenyl rings attached to the piperidine at the 2- and 6-positions have axial orientations. These rings make a dihedral angle of 49.75 (11)°. The aminooxy acetate group attached at the 4-position has an equatorial orientation. In the crystal, inversion dimers linked by pairs of C—H⋯π interactions occur.

Related literature

For background and the importance of oxime ethers, see: Crichlow et al. (2007 ▶). For a study of the in vitro antiproliferative activity of oxyme ether derivatives, see: Parthiban et al. (2011 ▶). For their effects on the senescence of cut carnation flowers, see: Zeng et al. (2012 ▶). For ring conformations, see: Cremer & Pople (1975 ▶). For related structures, see: Park et al. (2012a ▶,b ▶).

Experimental

Crystal data

C₂₂H₂₆N₂O₃
M _r = 366.45
Monoclinic,
a = 8.1662 (9) Å
b = 15.0229 (16) Å
c = 16.2889 (19) Å
β = 93.903 (6)°
V = 1993.7 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 295 K
0.35 × 0.35 × 0.30 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.972, T _max = 0.976
17582 measured reflections
17582 independent reflections
12046 reflections with I > 2σ(I)

Refinement

R[F ² > 2σ(F ²)] = 0.071
wR(F ²) = 0.214
S = 1.06
17582 reflections
249 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: APEX2 and 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: PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814006667/rk2422sup1.cif

e-70-0o513-sup1.cif^{(28.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814006667/rk2422Isup2.hkl

e-70-0o513-Isup2.hkl^{(842KB, hkl)}

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

Supporting information file. DOI: 10.1107/S1600536814006667/rk2422Isup3.cml

CCDC reference: 993682

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

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

Cg2 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C22—H22B⋯Cg2ⁱ	0.96	2.76	3.525 (3)	138.00

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

The auther thank Dr Babu Varghese, Senior Scientific Officer, SAIF, IIT Madras, India, for carrying out the data collection.

supplementary crystallographic information

1. Comment

Oxime ethers are serving as important synthetic intermediate and have been employed as starting materials for both synthetic and medicinal chemistry (Crichlow et al., 2007).

Oxime ether derivatives of 2,6-diphenyl-piperidine–4-one with N-methyl substituent enhanced the efficacy of the in vitro antiproliferative activity against human cervical carcinoma cell lines (Parthiban et al., 2011). Recently oxime ether derivatives of aminooxy acetic acid were synthesized and studied for their effects on the senescence of cut carnation flowers (Zeng et al., 2012). Due to the above importance, the crystal data for the title compound was carried out by X–ray diffraction.

Piperidine ring (C7–C11/N1) exists in a chair conformation with the puckering parameter Q = 0.5566Å, θ = 1.70 (19)°, φ= 23 (7)° (syn periplanar).

The bond distances and bond angles in the title compound agree very well with the corresponding values reported in closely related compound (Park et al., 2012a; 2012b).

The main plane of piperidine ring makes the dihedral angle of 81.82° and 86.73° with the phenyl rings at the 2 and 6 positions respectively. The dihedral angle between the two phenyl rings is 49.75°. The crystal is stabilized by C—H···O interactions. The packing is further stabilized by C—H···π and C22—H22B···Cg2ⁱ interactions, where Cg2 is the centroid of (C1–C6) ring. Symmetry code: (i) 1-x, 1-y, 1-z.

2. Experimental

To a stirred mixture of 1,3-dimethyl-2,6-diphenylpiperidin-4-one oxime (0.88 g, 3 mmol) and K₂CO₃ (0.42 g, 1 eq.) in acetonitrile (15 ml) at 353 K, methyl chloroacetate (0.25 ml, 1 eq) was added dropwise over a period of 5 min and stirring continued for 7.5 hrs at the same condition. The progress of the reaction was monitored by TLC. After completion of the reaction K₂CO₃ was removed by filtration and the solvent was evaporated to getcrude product. Pure product was obtained by coloumn chromotography using petroleum ether/ethyl acetate (9.5/0.5) mixture as the eluent. Yield: 0.77 g (70%).