1,1′-(p-Phenyl­enedimethyl­ene)dipiperidin-4-one

Vijayakumar, V.; Rajesh, K.; Suresh, J.; Narasimhamurthy, T.; Lakshman, P.L.N.

doi:10.1107/S1600536809052908

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o170

doi:10.1107/S1600536809052908

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1,1′-(p-Phenylenedimethylene)dipiperidin-4-one

V. Vijayakumar,^a K. Rajesh,^a J. Suresh,^b T. Narasimhamurthy ^c and P. L. Nilantha Lakshman ^d ^*

^aOrganic Chemistry Division, School of Advanced Sciences, VIT University, Vellore 632 014, India, ^bDepartment of Physics, The Madura College, Madurai 625 011, India, ^cMaterials Research Centre, Indian Institute of Science, Bangalore 560 012, India, and ^dDepartment of Food Science and Technology, Faculty of Agriculture, University of Ruhuna, Mapalana, Kamburupitiya 81100, Sri Lanka
^*Correspondence e-mail: nilanthalakshman@yahoo.co.uk

(Received 5 December 2009; accepted 9 December 2009; online 16 December 2009)

In the molecule of the title compound, C₁₈H₂₄N₂O₂, the piperidine rings are in chair conformations. The crystal structure is stabilized by intermolecular C—H⋯O hydrogen bonding. There are neither C—H⋯π nor π–π interactions in the structure.

Related literature

For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For ring puckering parameters, see Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₈H₂₄N₂O₂
M_r = 300.39
Monoclinic, P 2₁ /n
a = 6.2701 (5) Å
b = 8.0990 (6) Å
c = 15.8978 (13) Å
β = 98.275 (2)°
V = 798.91 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.19 × 0.17 × 0.15 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.984, T_max = 0.987
4782 measured reflections
1826 independent reflections
1424 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.123
S = 1.05
1826 reflections
100 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7B⋯O1ⁱ	0.97	2.56	3.2235 (17)	126
Symmetry code: (i) x, y-1, z.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809052908/bt5127sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809052908/bt5127Isup2.hkl

checkCIF report

Comment top

The configuration and conformation of the title compound, (I) and the atom numbering scheme are shown in the ORTEP drawing (Fig. 1). The piperidone ring exibits chair conformation as evident from the puckering parameters (Q)=0.549 (1) Å, θ = 173.4 (2) °, ψ = 181.9 (1) ° (Cremer & Pople, 1975).

In the crystal structure, an intermolecular C—H···O bond is found generating R22(24) motif (Bernstein et al., 1995).

Related literature top

For hydrogen-bond motifs, see: Bernstein et al. (1995). For ring puckering parameters, see Cremer & Pople (1975).

Experimental top

A mixture of 4-piperidone monohydrate hydrochloride (2 mol), 1,4-bis(bromomethyl)benzene (1 mol) and potassium carbonate (6 mol) in anhydrous benzene was refluxed for 7 h. The completion of reaction was monitored by TLC. Potassium carbonate was filtered off and the excess solvent was removed under reduced pressure. The solid obtained was purified over a column of silica gel (60–120 mesh size) using benzene-ethyl acetate (60–80 °C) in the ratio of 20:80. Yield: 40% m.p. 289°C.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of title compound with atom numbering scheme and 50% probability displacement ellipsoids.

1,1'-(p-Phenylenedimethylene)dipiperidin-4-one top

Crystal data top

C₁₈H₂₄N₂O₂	F(000) = 324
M_r = 300.39	D_x = 1.249 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2500 reflections
a = 6.2701 (5) Å	θ = 2–30°
b = 8.0990 (6) Å	µ = 0.08 mm⁻¹
c = 15.8978 (13) Å	T = 293 K
β = 98.275 (2)°	Block, colourless
V = 798.91 (11) Å³	0.19 × 0.17 × 0.15 mm
Z = 2

Data collection top

Bruker SMART APEX CCD diffractometer	1826 independent reflections
Radiation source: fine-focus sealed tube	1424 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.014
ω scans	θ_max = 27.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −8→4
T_min = 0.984, T_max = 0.987	k = −10→10
4782 measured reflections	l = −20→19

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0639P)² + 0.1074P] where P = (F_o² + 2F_c²)/3
1826 reflections	(Δ/σ)_max < 0.001
100 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₁₈H₂₄N₂O₂	V = 798.91 (11) Å³
M_r = 300.39	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.2701 (5) Å	µ = 0.08 mm⁻¹
b = 8.0990 (6) Å	T = 293 K
c = 15.8978 (13) Å	0.19 × 0.17 × 0.15 mm
β = 98.275 (2)°

Data collection top

Bruker SMART APEX CCD diffractometer	1826 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	1424 reflections with I > 2σ(I)
T_min = 0.984, T_max = 0.987	R_int = 0.014
4782 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 1.05	Δρ_max = 0.20 e Å⁻³
1826 reflections	Δρ_min = −0.14 e Å⁻³
100 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C2	0.2931 (2)	0.43945 (15)	0.38729 (9)	0.0451 (3)
H2A	0.3278	0.4330	0.3299	0.054*
H2B	0.4196	0.4060	0.4260	0.054*
C3	0.2358 (2)	0.61783 (16)	0.40660 (10)	0.0544 (4)
H3A	0.2191	0.6276	0.4661	0.065*
H3B	0.3519	0.6905	0.3959	0.065*
C4	0.0312 (2)	0.66908 (16)	0.35253 (8)	0.0440 (3)
C5	−0.1488 (2)	0.54905 (18)	0.35354 (11)	0.0584 (4)
H5A	−0.2680	0.5796	0.3105	0.070*
H5B	−0.1991	0.5528	0.4084	0.070*
C6	−0.0757 (2)	0.37490 (18)	0.33662 (10)	0.0544 (4)
H6A	−0.1918	0.2982	0.3419	0.065*
H6B	−0.0434	0.3682	0.2789	0.065*
C7	0.1742 (2)	0.15730 (16)	0.37561 (9)	0.0493 (4)
H7A	0.2250	0.1575	0.3208	0.059*
H7B	0.0458	0.0891	0.3705	0.059*
C8	0.3452 (2)	0.07991 (14)	0.44028 (8)	0.0405 (3)
C9	0.3083 (2)	0.05404 (16)	0.52331 (8)	0.0450 (3)
H9	0.1799	0.0900	0.5400	0.054*
C10	0.5395 (2)	0.02482 (16)	0.41824 (8)	0.0444 (3)
H10	0.5682	0.0411	0.3631	0.053*
N1	0.11571 (16)	0.32682 (12)	0.39582 (7)	0.0395 (3)
O1	0.01374 (19)	0.79483 (13)	0.31091 (7)	0.0657 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C2	0.0372 (6)	0.0349 (7)	0.0605 (8)	−0.0033 (5)	−0.0021 (5)	0.0041 (6)
C3	0.0595 (8)	0.0329 (7)	0.0659 (9)	−0.0062 (6)	−0.0079 (7)	0.0018 (6)
C4	0.0549 (8)	0.0322 (6)	0.0448 (7)	0.0048 (5)	0.0072 (6)	0.0015 (5)
C5	0.0415 (7)	0.0509 (9)	0.0821 (10)	0.0057 (6)	0.0064 (7)	0.0227 (7)
C6	0.0423 (7)	0.0422 (8)	0.0731 (10)	−0.0085 (6)	−0.0107 (7)	0.0130 (7)
C7	0.0586 (8)	0.0308 (7)	0.0540 (8)	−0.0024 (6)	−0.0075 (6)	−0.0006 (6)
C8	0.0502 (7)	0.0233 (5)	0.0464 (7)	−0.0019 (5)	0.0015 (5)	−0.0002 (5)
C9	0.0462 (7)	0.0374 (7)	0.0528 (8)	0.0024 (5)	0.0113 (6)	−0.0021 (5)
C10	0.0573 (8)	0.0368 (7)	0.0401 (6)	−0.0039 (6)	0.0106 (6)	0.0016 (5)
N1	0.0389 (5)	0.0288 (5)	0.0484 (6)	−0.0026 (4)	−0.0022 (4)	0.0059 (4)
O1	0.0827 (8)	0.0385 (6)	0.0723 (7)	−0.0004 (5)	−0.0012 (6)	0.0175 (5)

Geometric parameters (Å, º) top

C2—N1	1.4598 (16)	C6—H6A	0.9700
C2—C3	1.5304 (18)	C6—H6B	0.9700
C2—H2A	0.9700	C7—N1	1.4685 (17)
C2—H2B	0.9700	C7—C8	1.5104 (18)
C3—C4	1.4964 (19)	C7—H7A	0.9700
C3—H3A	0.9700	C7—H7B	0.9700
C3—H3B	0.9700	C8—C9	1.3884 (18)
C4—O1	1.2109 (16)	C8—C10	1.3888 (19)
C4—C5	1.492 (2)	C9—C10ⁱ	1.3882 (18)
C5—C6	1.519 (2)	C9—H9	0.9300
C5—H5A	0.9700	C10—C9ⁱ	1.3882 (18)
C5—H5B	0.9700	C10—H10	0.9300
C6—N1	1.4670 (16)

N1—C2—C3	111.55 (11)	C5—C6—H6A	109.2
N1—C2—H2A	109.3	N1—C6—H6B	109.2
C3—C2—H2A	109.3	C5—C6—H6B	109.2
N1—C2—H2B	109.3	H6A—C6—H6B	107.9
C3—C2—H2B	109.3	N1—C7—C8	114.47 (10)
H2A—C2—H2B	108.0	N1—C7—H7A	108.6
C4—C3—C2	110.67 (11)	C8—C7—H7A	108.6
C4—C3—H3A	109.5	N1—C7—H7B	108.6
C2—C3—H3A	109.5	C8—C7—H7B	108.6
C4—C3—H3B	109.5	H7A—C7—H7B	107.6
C2—C3—H3B	109.5	C9—C8—C10	117.61 (11)
H3A—C3—H3B	108.1	C9—C8—C7	120.72 (12)
O1—C4—C5	123.01 (13)	C10—C8—C7	121.59 (12)
O1—C4—C3	123.37 (13)	C10ⁱ—C9—C8	120.89 (12)
C5—C4—C3	113.62 (11)	C10ⁱ—C9—H9	119.6
C4—C5—C6	110.77 (12)	C8—C9—H9	119.6
C4—C5—H5A	109.5	C9ⁱ—C10—C8	121.50 (12)
C6—C5—H5A	109.5	C9ⁱ—C10—H10	119.3
C4—C5—H5B	109.5	C8—C10—H10	119.3
C6—C5—H5B	109.5	C2—N1—C6	109.77 (10)
H5A—C5—H5B	108.1	C2—N1—C7	110.25 (11)
N1—C6—C5	111.90 (12)	C6—N1—C7	108.36 (10)
N1—C6—H6A	109.2

N1—C2—C3—C4	−54.57 (16)	C7—C8—C9—C10ⁱ	176.62 (11)
C2—C3—C4—O1	−129.37 (15)	C9—C8—C10—C9ⁱ	0.3 (2)
C2—C3—C4—C5	49.69 (17)	C7—C8—C10—C9ⁱ	−176.59 (12)
O1—C4—C5—C6	129.33 (15)	C3—C2—N1—C6	59.82 (15)
C3—C4—C5—C6	−49.73 (18)	C3—C2—N1—C7	179.12 (11)
C4—C5—C6—N1	54.57 (17)	C5—C6—N1—C2	−60.02 (16)
N1—C7—C8—C9	62.64 (17)	C5—C6—N1—C7	179.53 (12)
N1—C7—C8—C10	−120.58 (14)	C8—C7—N1—C2	69.70 (15)
C10—C8—C9—C10ⁱ	−0.3 (2)	C8—C7—N1—C6	−170.15 (12)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···O1ⁱⁱ	0.97	2.56	3.2235 (17)	126

Symmetry code: (ii) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₁₈H₂₄N₂O₂
M_r	300.39
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	6.2701 (5), 8.0990 (6), 15.8978 (13)
β (°)	98.275 (2)
V (Å³)	798.91 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.19 × 0.17 × 0.15

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.984, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	4782, 1826, 1424
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.123, 1.05
No. of reflections	1826
No. of parameters	100
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.14

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···O1ⁱ	0.97	2.56	3.2235 (17)	125.5

Symmetry code: (i) x, y−1, z.

Acknowledgements

VV thanks the DST-India for funding through the Young Scientist-Fast Track Proposal.

References

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