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

Abstract

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,

• a = 6.2701 (5) Å

• b = 8.0990 (6) Å

• c = 15.8978 (13) Å

• β = 98.275 (2)°

• V = 798.91 (11) ų

• 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[F ² > 2σ(F ²)] = 0.043

• wR(F ²) = 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

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.

Supplementary Material

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
C7—H7B⋯O1i	0.97	2.56	3.2235 (17)	126

Symmetry code: (i) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

The H atoms were placed in calculated positions and allowed to ride on their carrier atoms with C—H = 0.93–0.97 Å.U_iso = 1.2U_eq(C) for CH and CH₂ groups.

Figures

Fig. 1.

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

Crystal data

C18H24N2O2	F(000) = 324
Mr = 300.39	Dx = 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

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

Refinement

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(Fo2) + (0.0639P)2 + 0.1074P] where P = (Fo2 + 2Fc2)/3
1826 reflections	(Δ/σ)max < 0.001
100 parameters	Δρmax = 0.20 e Å−3
0 restraints	Δρmin = −0.14 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, °)

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

Symmetry codes: (ii) x, y−1, z.