1-Formyl-r-2,c-6-bis­(4-methoxy­phen­yl)-c-3,t-3-dimethyl­piperidin-4-one

T Kavitha; S Ponnuswamy; P Sakthivel; K Karthik; M N Ponnuswamy

doi:10.1107/S1600536809010010

. 2009 Mar 25;65(Pt 4):o856. doi: 10.1107/S1600536809010010

1-Formyl-r-2,c-6-bis(4-methoxyphenyl)-c-3,t-3-dimethylpiperidin-4-one

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

PMCID: PMC2968915 PMID: 21582573

Abstract

In the title compound, C₂₂H₂₅NO₄, the piperidine ring adopts a distorted boat conformation. The two benzene rings are approximately perpendicular to each other, making a dihedral angle of 86.2 (8)°. The crystal packing is stabilized by C—H⋯O and C—H⋯π interactions.

Related literature

For details of hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For ring conformational analysis, see: Cremer & Pople (1975 ▶); Nardelli (1983 ▶).

Experimental

Crystal data

C₂₂H₂₅NO₄
M _r = 367.43
Monoclinic,
a = 11.7274 (3) Å
b = 18.8556 (4) Å
c = 9.7178 (3) Å
β = 113.507 (1)°
V = 1970.54 (9) 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 diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T _min = 0.979, T _max = 0.983
26804 measured reflections
6250 independent reflections
4080 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.142
S = 1.03
6250 reflections
244 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.19 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: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1983 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809010010/bt2903sup1.cif

e-65-0o856-sup1.cif^{(22.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809010010/bt2903Isup2.hkl

e-65-0o856-Isup2.hkl^{(299.8KB, 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
C5—H5A⋯O3ⁱ	0.97	2.44	3.3446 (16)	155
C6—H6⋯O2ⁱⁱ	0.98	2.41	3.3708 (16)	168
C18—H18⋯O1ⁱⁱⁱ	0.93	2.53	3.3018 (17)	140
C10—H10⋯Cg1^iv	0.93	2.90	3.6627 (17)	140

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) . Cg(1) 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, a basic component of the piper alkaloid piper nigrum is a monocyclic cyclohexane with a hetero atom affixed in the first position. The skeletal ring of piperidine is contained in the molecules of many synthetic and natural medicaments. A significant industrial application of piperidine is for the production of dipiperidinyl dithiuram tetrasulfide, which can be used as a rubber vulcanization accelerator.

The piperidine ring adopts distorted boat conformation with puckering parameters (Cremer & Pople, 1975) q2 = 0.630 (1) Å, q3 =0.070 (1)Å and φ2= 87.2 (1)° and the asymmetry parameters ΔC₂(N1) and ΔC₂(C4) = 14.78 (12)Å (Nardelli, 1983). The angles between the best plane of the piperidine ring (N1,C3,C4,C6) and the phenyl rings (C8—C13 and C16—C21) are 84.17 (7)° and 80.70 (7)°, respectively. The two phenyl rings are approximately perpendicular to each other as can be seen from the dihedral angle of 86.23 (8)°. The methyl substituents C14 and C15 are oriented equatorially [N1—C2—C3—C14 =] -178.88 (11)° and axially [N1—C2—C3—C15 =] -59.52 (13) ° with respect to the piperidine ring. The sum of the bond angles around N1 atom (359.3°) indicates sp² hybridization.

The packing of the molecules is controlled by C—H···O types of intermolecular interactions. The symmetry related molecules form a dimer with the graph-set motif of R²₂(16) (Bernstein et al., 1995) through hydrogen bonds. Further a C—H··· π interaction also leads to the formation of a dimer [C10—H10 = 0.9301 Å, H10···Cg(1) =2.9035 Å, C10···Cg(1) = 3.6627 (17) Å and C10—H10···Cg(1) = 139.71°, where Cg(1) is the centroid of the ring (C16—C21) at (1 - x,-y,2 - z)] .

Experimental

The ice-cold solution of acetic-formic anhydride was prepared from acetic anhydride (10 ml) and 85% formic acid (5 ml) and was added slowly to a cold solution of r-2, c-6-bis(4-methoxyphenyl)-c-3,t-3-dimethylpiperidine-4-one (1.69 g) in benzene (30 ml). The reaction mixture was stirred at room temperature for 5 hrs. The organic layer was separated, dried over anhydrous Na₂SO₄ and concentrated. The resulting mass was purified by crystallization from benzene-petroleum ether (333–353 K) in the ratio 1:1.