t-3-Ethyl-r-2,c-6-bis­(4-methoxy­phen­yl)-1-nitro­sopiperidin-4-one

T Kavitha; M Thenmozhi; S Ponnuswamy; P Sakthivel; M N Ponnuswamy

doi:10.1107/S1600536809024878

. 2009 Jul 4;65(Pt 8):o1765. doi: 10.1107/S1600536809024878

t-3-Ethyl-r-2,c-6-bis(4-methoxyphenyl)-1-nitrosopiperidin-4-one

T Kavitha ^a, M Thenmozhi ^a, S Ponnuswamy ^b, P Sakthivel ^b, M N Ponnuswamy ^a,^*

PMCID: PMC2977124 PMID: 21583475

Abstract

In the title molecule, C₂₁H₂₄N₂O₄, the piperidine ring adopts a distorted boat conformation with the ethyl substituent in the axial position. The dihedral angle between the two benzene rings is 70.25 (9)°. An intramolecular C—H⋯O interaction is observed. In the crystal, molecules are linked into a chain along the c axis by C—H⋯O hydrogen bonds and the chains are linked via weak C—H⋯π interactions.

Related literature

For general background to 4-piperidones, see: Wang et al. (1992 ▶); Grishina et al. (1994 ▶). For ring conformational analysis, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₂₁H₂₄N₂O₄
M _r = 368.42
Orthorhombic,
a = 7.2742 (4) Å
b = 15.8459 (7) Å
c = 16.4800 (7) Å
V = 1899.59 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.25 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T _min = 0.978, T _max = 0.982
15051 measured reflections
3334 independent reflections
2550 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.107
S = 1.02
3334 reflections
244 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809024878/ci2810sup1.cif

e-65-o1765-sup1.cif^{(21.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809024878/ci2810Isup2.hkl

e-65-o1765-Isup2.hkl^{(160.2KB, hkl)}

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
C15—H15C⋯O1	0.96	2.56	3.163 (4)	121
C18—H18⋯O1ⁱ	0.93	2.56	3.472 (3)	167
C23—H23B⋯Cg1ⁱⁱ	0.96	2.89	3.718 (2)	144

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Symmetry codes: (i) Inline graphic ; (ii) . Cg1 is the centroid of the C16–C21 ring.

Acknowledgments

TK thanks Dr Babu Varghese, SAIF, IIT-Madras, Chennai, India, for his help with the data collection. SP thanks the UGC, India, for financial support.

supplementary crystallographic information

Comment

Piperidine derivatives, namely 4-piperidones, are synthetic intermediates in the preparation of various alkaloids and pharmaceutical products (Wang et al., 1992; Grishina et al., 1994).

The piperidine ring adopts a distorted boat conformation, with the ethyl substituent at C3 position in the axial orientation. The puckering parameters for the piperidine ring are q2 = 0.591 (2) Å, q3 = 0.097 (2) Å, Q_T = 0.599 (2) Å and φ2 = 73.2 (2)° (Cremer & Pople, 1975). The dihedral angle between the two benzene rings is 70.25 (9)°. The sum of the bond angles around N1 (359°) indicates sp² hybridization. An intramolecular C—H···O interaction is observed.

The crystal structure is stabilized by intermolecular C—H···O hydrogen bonds (Table 1) which link the molecules into a chain along the c axis. The chains are linked via C—H···π interactions involving the C16-C21 ring.

Experimental

To a solution of t-3-ethyl-r-2,c-6-bis(4-methoxyphenyl)piperidin-4-one (1.69 g, 5 mmol) in chloroform (10 ml) was added conc. HCl (1.5 ml) and water (1.5 ml) and while stirring, solid NaNO₂ (0.84 g,12 mmol) was added in portions during 0.5 h. The solution was stirred at room temperature for another 0.5 h. The organic layer was washed with water, saturated aqueous NaHCO₃ and dried over anhydrous Na₂SO₄. The resulting solution was concentrated and the residue was crystallized from ethanol.