r-2,c-6-Bis(4-chloro­phen­yl)-t-3-isopropyl-1-nitro­sopiperidin-4-one

P Gayathri; A Thiruvalluvar; A Manimekalai; S Sivakumar; R J Butcher

doi:10.1107/S1600536808029723

. 2008 Sep 20;64(Pt 10):o1973. doi: 10.1107/S1600536808029723

r-2,c-6-Bis(4-chlorophenyl)-t-3-isopropyl-1-nitrosopiperidin-4-one

P Gayathri ^a, A Thiruvalluvar ^a,^*, A Manimekalai ^b, S Sivakumar ^b, R J Butcher ^c

PMCID: PMC2959467 PMID: 21201173

Abstract

In the title molecule, C₂₀H₂₀Cl₂N₂O₂, the piperidine ring adopts a chair conformation and the nitroso group at position 1 has a bisectional orientation. The two benzene rings and the isopropyl group attached to the piperidine ring in positions 2, 6 and 3, respectively, have axial orientations. The dihedral angle between the two benzene rings is 21.56 (13)°. One of the Cl atoms is disordered over two positions in a 0.281 (5):0.719 (5) ratio. In the crystal structure, molecules are linked by C—H⋯O hydrogen bonds and a short C—H⋯O contact occurs within the molecule.

Related literature

For related crystal structures, see: Balamurugan et al. (2006 ▶, 2007 ▶); Thiruvalluvar, Balamurugan, Jayabharathi & Manimekalai (2007 ▶); Thiruvalluvar, Balamurugan, Jayabharathi, Manimekalai & Rajarajan (2007 ▶).

Experimental

Crystal data

C₂₀H₂₀Cl₂N₂O₂
M _r = 391.28
Triclinic,
a = 8.2771 (2) Å
b = 11.1921 (4) Å
c = 11.2351 (4) Å
α = 93.375 (3)°
β = 106.924 (3)°
γ = 104.549 (3)°
V = 953.95 (6) Å³
Z = 2
Cu Kα radiation
μ = 3.20 mm⁻¹
T = 200 (2) K
0.54 × 0.47 × 0.41 mm

Data collection

Oxford Diffraction R Gemini diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 ▶) T _min = 0.269, T _max = 1.000 (expected range = 0.073–0.270)
8014 measured reflections
3752 independent reflections
3506 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.056
wR(F ²) = 0.155
S = 1.02
3752 reflections
239 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 ▶); data reduction: CrysAlis RED; 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: PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808029723/hb2797sup1.cif

e-64-o1973-sup1.cif^{(21.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808029723/hb2797Isup2.hkl

e-64-o1973-Isup2.hkl^{(180.2KB, 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
C2—H2⋯O11	1.00	2.24	2.676 (2)	105
C5—H5B⋯O4ⁱ	0.99	2.55	3.530 (3)	171
C32—H32C⋯O4ⁱⁱ	0.98	2.59	3.532 (3)	162

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

Acknowledgments

AT thanks the UGC, India, for the award of a Minor Research Project [File No. MRP-2355/06(UGC-SERO), Link No. 2355, 10/01/2007]. RJB acknowledges the NSF–MRI program for funding to purchase the diffractometer.

supplementary crystallographic information

Comment

Various crystal structures of di-2-furylpiperidin-4-one derivatives have been reported, wherein the piperidine ring adopts a chair (Balamurugan et al., 2006), a twist-boat (Balamurugan et al., 2007) and a chair conformation (Thiruvalluvar, Balamurugan, Jayabharathi & Manimekalai, 2007). Thiruvalluvar, Balamurugan, Jayabharathi, Manimekalai & Rajarajan (2007) have reported the crystal structure of a diphenylpiperidin-4-ol derivative, wherein the piperidine ring adopts a chair conformation.

In the title molecule, C₂₀H₂₀Cl₂N₂O₂ (Fig. 1), the piperidine ring adopts a chair conformation. The nitroso group at position 1 has a bisectional orientation. The two phenyl rings and the isopropyl group attached to the piperidine ring in positions 2, 6 and 3, respectively, have axial orientations. The dihedral angle between the two phenyl rings is 21.56 (13)°. Compound (I) is chiral: in the arbitrarily chosen asymmetric molecule, C2, C3 and C6 have S, R, and R conformations respectively, but crystal symmetry generates a racemic mixture. In the crystal, the molecules are linked by C—H···O hydrogen bonds (Fig. 2, Table 1).

Experimental

To a solution of t3-isopropyl-r2,c6-bis(4-chlorophenyl) piperidin-4-one (1.81 g, 0.005 mol) in chloroform (10 ml), concentrated HCl (1.5 ml) and water (1.5 ml) were added. While stirring, solid NaNO₂ (3 g, 0.012 mol) was added in small portions to the reaction mixture over a period of 30 minutes. The stirring was continued for another 30 minutes. The organic layer was washed with water and saturated NaHCO₃ and dried over anhydrous Na₂SO₄. After the removal of chloroform, the crude solid was recrystallized from distilled ethanol, to yield 1.5 g of colourless chunks of (I) (yield = 76%).