2,6-Bis(3-methoxy­phen­yl)-3-methyl­piperidin-4-one

Nithya, P.; Khan, F.N.; Novanna, M.; Hathwar, V.R.; Ng, S.W.

doi:10.1107/S1600536809045346

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o2984

doi:10.1107/S1600536809045346

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2,6-Bis(3-methoxyphenyl)-3-methylpiperidin-4-one

P. Nithya,^a F. Nawaz Khan,^a Motakatla Novanna,^a Venkatesha R. Hathwar ^b and Seik Weng Ng ^c ^*

^aChemistry Division, School of Science and Humanities, VIT University, Vellore 632 014, Tamil Nadu, India, ^bSolid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012, Karnataka, India, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 27 October 2009; accepted 29 October 2009; online 4 November 2009)

In the molecule of the title compound, C₂₀H₂₃NO₃, the bulky methoxyphenyl substituents at the equatorial 2,6-positions crowd the vicinity of the equatorial amino H atom and prevent it from forming intermolecular hydrogen bonds. The piperidine ring adopts a distorted chair conformation.

Related literature

For the crystal structure of a related piperidinone compound, see: Nithya et al. (2009 ).

Experimental

Crystal data

C₂₀H₂₃NO₃
M_r = 325.39
Monoclinic, C 2/c
a = 28.695 (3) Å
b = 10.9717 (12) Å
c = 11.3946 (13) Å
β = 95.078 (2)°
V = 3573.3 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 290 K
0.35 × 0.12 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
12581 measured reflections
3148 independent reflections
1751 reflections with I > 2σ(I)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.154
S = 1.04
3148 reflections
224 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Data collection: SMART (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: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809045346/ci2955sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809045346/ci2955Isup2.hkl

checkCIF report

Related literature top

For the crystal structure of a related piperidinone compound, see: Nithya et al. (2009).

Experimental top

Ammonium acetate (1 mmol), m-methoxybenzaldehyde (2 mmol) and ethylmethyl ketone (1 mmol) was heated until the colour of the solution turned yellow. After the completion of the reaction (as monitored by TLC), the product was dissolved in ether (10 ml). The solution was treated with aqueous hydrochloric acid [20 ml, 1:1 (v/v)]. The hydrochloride salt of the piperidin-4-one was collected and washed with ether. The base was liberated from an alcohol solution of the hydrochloride by the addition of a slight excess of aqueous ammonia at 273 K. The product was collected and recrystallized from ethanol.

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

Fig. 1. Displacement ellipsoid plot (Barbour, 2001) of C₂₀H₂₃NO₃ at the 50% probability level. H atoms are drawn as spheres of arbitrary radius.

2,6-Bis(3-methoxyphenyl)-3-methylpiperidin-4-one top

Crystal data top

C₂₀H₂₃NO₃	F(000) = 1392
M_r = 325.39	D_x = 1.210 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1065 reflections
a = 28.695 (3) Å	θ = 2.0–20.8°
b = 10.9717 (12) Å	µ = 0.08 mm⁻¹
c = 11.3946 (13) Å	T = 290 K
β = 95.078 (2)°	Plate, colourless
V = 3573.3 (7) Å³	0.35 × 0.12 × 0.08 mm
Z = 8

Data collection top

Bruker SMART CCD area-detector diffractometer	1751 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.058
Graphite monochromator	θ_max = 25.0°, θ_min = 1.4°
ϕ and ω scans	h = −33→34
12581 measured reflections	k = −13→11
3148 independent reflections	l = −13→13

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.154	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0658P)² + 0.6442P] where P = (F_o² + 2F_c²)/3
3148 reflections	(Δ/σ)_max = 0.001
224 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₂₀H₂₃NO₃	V = 3573.3 (7) Å³
M_r = 325.39	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 28.695 (3) Å	µ = 0.08 mm⁻¹
b = 10.9717 (12) Å	T = 290 K
c = 11.3946 (13) Å	0.35 × 0.12 × 0.08 mm
β = 95.078 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1751 reflections with I > 2σ(I)
12581 measured reflections	R_int = 0.058
3148 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	0 restraints
wR(F²) = 0.154	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.18 e Å⁻³
3148 reflections	Δρ_min = −0.14 e Å⁻³
224 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.58419 (9)	0.8518 (2)	0.9145 (2)	0.1002 (10)
O2	0.76371 (8)	0.5426 (2)	0.51929 (18)	0.0750 (7)
O3	0.57121 (8)	0.17943 (18)	1.10361 (17)	0.0647 (6)
N1	0.65515 (8)	0.5548 (2)	0.83450 (19)	0.0438 (6)
H1N	0.6737 (9)	0.493 (2)	0.850 (2)	0.042 (8)*
C1	0.68070 (10)	0.6693 (3)	0.8526 (2)	0.0460 (7)
H1	0.6910	0.6772	0.9366	0.055*
C2	0.64767 (11)	0.7743 (3)	0.8172 (3)	0.0585 (9)
H2A	0.6627	0.8505	0.8419	0.070*
H2B	0.6420	0.7760	0.7320	0.070*
C3	0.60185 (12)	0.7651 (3)	0.8696 (3)	0.0588 (9)
C4	0.57864 (10)	0.6416 (3)	0.8627 (2)	0.0488 (8)
H4	0.5697	0.6251	0.7792	0.059*
C5	0.61533 (9)	0.5452 (2)	0.9056 (2)	0.0405 (7)
H5	0.6262	0.5630	0.9878	0.049*
C6	0.59593 (9)	0.4172 (2)	0.8989 (2)	0.0392 (7)
C7	0.59208 (9)	0.3507 (2)	1.0002 (2)	0.0429 (7)
H7	0.6019	0.3850	1.0729	0.051*
C8	0.57388 (10)	0.2338 (3)	0.9957 (2)	0.0456 (7)
C9	0.56020 (11)	0.1801 (3)	0.8898 (3)	0.0573 (8)
H9	0.5487	0.1009	0.8864	0.069*
C10	0.56400 (11)	0.2471 (3)	0.7879 (3)	0.0646 (9)
H10	0.5544	0.2123	0.7153	0.078*
C11	0.58152 (10)	0.3632 (3)	0.7912 (2)	0.0525 (8)
H11	0.5838	0.4061	0.7216	0.063*
C12	0.72330 (10)	0.6733 (3)	0.7837 (2)	0.0445 (7)
C13	0.72600 (10)	0.6065 (3)	0.6817 (2)	0.0500 (8)
H13	0.7013	0.5558	0.6550	0.060*
C14	0.76509 (11)	0.6143 (3)	0.6189 (3)	0.0549 (8)
C15	0.80184 (12)	0.6882 (3)	0.6568 (3)	0.0686 (10)
H15	0.8284	0.6922	0.6155	0.082*
C16	0.79871 (12)	0.7568 (3)	0.7577 (3)	0.0716 (10)
H16	0.8232	0.8085	0.7834	0.086*
C17	0.76009 (11)	0.7498 (3)	0.8206 (3)	0.0597 (9)
H17	0.7587	0.7967	0.8882	0.072*
C18	0.80099 (13)	0.5566 (3)	0.4451 (3)	0.0848 (12)
H18A	0.8021	0.6396	0.4189	0.127*
H18B	0.7958	0.5036	0.3782	0.127*
H18C	0.8301	0.5359	0.4885	0.127*
C19	0.55104 (15)	0.0625 (3)	1.1084 (3)	0.0877 (12)
H19A	0.5192	0.0654	1.0746	0.132*
H19B	0.5518	0.0365	1.1890	0.132*
H19C	0.5684	0.0060	1.0650	0.132*
C20	0.53454 (12)	0.6374 (3)	0.9252 (3)	0.0826 (11)
H20A	0.5421	0.6511	1.0079	0.124*
H20B	0.5201	0.5589	0.9136	0.124*
H20C	0.5134	0.6994	0.8939	0.124*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.119 (2)	0.0536 (16)	0.135 (2)	0.0140 (15)	0.0511 (19)	−0.0246 (15)
O2	0.0798 (17)	0.0788 (16)	0.0713 (14)	−0.0245 (13)	0.0343 (13)	−0.0180 (13)
O3	0.0959 (17)	0.0445 (13)	0.0538 (13)	−0.0223 (12)	0.0074 (11)	0.0049 (10)
N1	0.0422 (15)	0.0342 (15)	0.0560 (15)	0.0009 (13)	0.0100 (12)	0.0041 (12)
C1	0.0515 (19)	0.0455 (18)	0.0403 (15)	−0.0075 (16)	0.0001 (14)	−0.0005 (13)
C2	0.069 (2)	0.0394 (19)	0.068 (2)	−0.0052 (16)	0.0137 (17)	−0.0052 (15)
C3	0.071 (2)	0.042 (2)	0.064 (2)	0.0102 (18)	0.0113 (17)	−0.0019 (15)
C4	0.0485 (19)	0.051 (2)	0.0485 (17)	0.0065 (16)	0.0123 (14)	−0.0005 (14)
C5	0.0421 (17)	0.0418 (17)	0.0381 (14)	−0.0016 (14)	0.0074 (12)	−0.0017 (12)
C6	0.0373 (16)	0.0382 (17)	0.0431 (16)	0.0028 (13)	0.0092 (13)	−0.0022 (13)
C7	0.0485 (18)	0.0393 (18)	0.0410 (16)	−0.0024 (14)	0.0049 (13)	−0.0036 (13)
C8	0.0482 (19)	0.0446 (19)	0.0447 (16)	−0.0016 (15)	0.0075 (13)	−0.0012 (14)
C9	0.068 (2)	0.0440 (19)	0.060 (2)	−0.0164 (16)	0.0096 (16)	−0.0051 (15)
C10	0.086 (3)	0.060 (2)	0.0469 (18)	−0.019 (2)	0.0026 (16)	−0.0138 (16)
C11	0.063 (2)	0.055 (2)	0.0407 (17)	−0.0082 (17)	0.0069 (14)	−0.0025 (14)
C12	0.0453 (18)	0.0438 (17)	0.0438 (16)	−0.0059 (15)	0.0006 (14)	0.0074 (13)
C13	0.0480 (19)	0.0487 (19)	0.0536 (18)	−0.0162 (15)	0.0067 (15)	−0.0026 (14)
C14	0.057 (2)	0.053 (2)	0.0560 (19)	−0.0118 (17)	0.0130 (16)	0.0019 (16)
C15	0.060 (2)	0.077 (2)	0.072 (2)	−0.019 (2)	0.0216 (18)	0.0035 (19)
C16	0.062 (2)	0.077 (2)	0.077 (2)	−0.032 (2)	0.0088 (19)	−0.002 (2)
C17	0.061 (2)	0.064 (2)	0.0535 (18)	−0.0187 (19)	0.0034 (16)	−0.0029 (16)
C18	0.089 (3)	0.094 (3)	0.077 (2)	−0.020 (2)	0.042 (2)	−0.012 (2)
C19	0.140 (4)	0.054 (2)	0.071 (2)	−0.031 (2)	0.021 (2)	0.0032 (18)
C20	0.074 (3)	0.076 (3)	0.103 (3)	0.017 (2)	0.039 (2)	0.011 (2)

Geometric parameters (Å, º) top

O1—C3	1.212 (3)	C9—C10	1.388 (4)
O2—C14	1.379 (3)	C9—H9	0.93
O2—C18	1.429 (3)	C10—C11	1.368 (4)
O3—C8	1.375 (3)	C10—H10	0.93
O3—C19	1.411 (3)	C11—H11	0.93
N1—C1	1.460 (3)	C12—C13	1.382 (4)
N1—C5	1.462 (3)	C12—C17	1.384 (4)
N1—H1N	0.87 (3)	C13—C14	1.385 (4)
C1—C12	1.511 (4)	C13—H13	0.93
C1—C2	1.524 (4)	C14—C15	1.369 (4)
C1—H1	0.98	C15—C16	1.384 (4)
C2—C3	1.495 (4)	C15—H15	0.93
C2—H2A	0.97	C16—C17	1.374 (4)
C2—H2B	0.97	C16—H16	0.93
C3—C4	1.509 (4)	C17—H17	0.93
C4—C20	1.507 (4)	C18—H18A	0.96
C4—C5	1.541 (4)	C18—H18B	0.96
C4—H4	0.98	C18—H18C	0.96
C5—C6	1.511 (3)	C19—H19A	0.96
C5—H5	0.98	C19—H19B	0.96
C6—C7	1.379 (3)	C19—H19C	0.96
C6—C11	1.392 (3)	C20—H20A	0.96
C7—C8	1.384 (4)	C20—H20B	0.96
C7—H7	0.93	C20—H20C	0.96
C8—C9	1.368 (4)

C14—O2—C18	117.2 (2)	C10—C9—H9	120.9
C8—O3—C19	119.0 (2)	C11—C10—C9	121.7 (3)
C1—N1—C5	113.0 (2)	C11—C10—H10	119.2
C1—N1—H1N	110.2 (17)	C9—C10—H10	119.2
C5—N1—H1N	109.0 (16)	C10—C11—C6	120.0 (3)
N1—C1—C12	111.8 (2)	C10—C11—H11	120.0
N1—C1—C2	108.7 (2)	C6—C11—H11	120.0
C12—C1—C2	110.7 (2)	C13—C12—C17	118.6 (3)
N1—C1—H1	108.5	C13—C12—C1	122.0 (3)
C12—C1—H1	108.5	C17—C12—C1	119.4 (3)
C2—C1—H1	108.5	C12—C13—C14	120.6 (3)
C3—C2—C1	113.0 (2)	C12—C13—H13	119.7
C3—C2—H2A	109.0	C14—C13—H13	119.7
C1—C2—H2A	109.0	C15—C14—O2	124.2 (3)
C3—C2—H2B	109.0	C15—C14—C13	120.7 (3)
C1—C2—H2B	109.0	O2—C14—C13	115.1 (3)
H2A—C2—H2B	107.8	C14—C15—C16	118.6 (3)
O1—C3—C2	122.1 (3)	C14—C15—H15	120.7
O1—C3—C4	121.8 (3)	C16—C15—H15	120.7
C2—C3—C4	116.1 (3)	C17—C16—C15	121.2 (3)
C20—C4—C3	112.9 (3)	C17—C16—H16	119.4
C20—C4—C5	114.0 (2)	C15—C16—H16	119.4
C3—C4—C5	108.3 (2)	C16—C17—C12	120.3 (3)
C20—C4—H4	107.1	C16—C17—H17	119.9
C3—C4—H4	107.1	C12—C17—H17	119.9
C5—C4—H4	107.1	O2—C18—H18A	109.5
N1—C5—C6	110.0 (2)	O2—C18—H18B	109.5
N1—C5—C4	108.7 (2)	H18A—C18—H18B	109.5
C6—C5—C4	112.6 (2)	O2—C18—H18C	109.5
N1—C5—H5	108.5	H18A—C18—H18C	109.5
C6—C5—H5	108.5	H18B—C18—H18C	109.5
C4—C5—H5	108.5	O3—C19—H19A	109.5
C7—C6—C11	118.3 (3)	O3—C19—H19B	109.5
C7—C6—C5	120.4 (2)	H19A—C19—H19B	109.5
C11—C6—C5	121.3 (2)	O3—C19—H19C	109.5
C6—C7—C8	121.1 (3)	H19A—C19—H19C	109.5
C6—C7—H7	119.4	H19B—C19—H19C	109.5
C8—C7—H7	119.4	C4—C20—H20A	109.5
C9—C8—O3	124.5 (3)	C4—C20—H20B	109.5
C9—C8—C7	120.7 (3)	H20A—C20—H20B	109.5
O3—C8—C7	114.8 (2)	C4—C20—H20C	109.5
C8—C9—C10	118.2 (3)	H20A—C20—H20C	109.5
C8—C9—H9	120.9	H20B—C20—H20C	109.5

C5—N1—C1—C12	176.5 (2)	C6—C7—C8—C9	1.5 (4)
C5—N1—C1—C2	−61.0 (3)	C6—C7—C8—O3	−178.7 (2)
N1—C1—C2—C3	48.7 (3)	O3—C8—C9—C10	178.6 (3)
C12—C1—C2—C3	171.8 (2)	C7—C8—C9—C10	−1.6 (4)
C1—C2—C3—O1	134.6 (3)	C8—C9—C10—C11	1.0 (5)
C1—C2—C3—C4	−45.8 (4)	C9—C10—C11—C6	−0.2 (5)
O1—C3—C4—C20	−4.6 (4)	C7—C6—C11—C10	0.1 (4)
C2—C3—C4—C20	175.7 (3)	C5—C6—C11—C10	−179.9 (3)
O1—C3—C4—C5	−131.9 (3)	N1—C1—C12—C13	26.1 (4)
C2—C3—C4—C5	48.5 (3)	C2—C1—C12—C13	−95.1 (3)
C1—N1—C5—C6	−170.0 (2)	N1—C1—C12—C17	−156.6 (3)
C1—N1—C5—C4	66.3 (3)	C2—C1—C12—C17	82.1 (3)
C20—C4—C5—N1	177.2 (3)	C17—C12—C13—C14	1.2 (4)
C3—C4—C5—N1	−56.3 (3)	C1—C12—C13—C14	178.5 (3)
C20—C4—C5—C6	55.1 (3)	C18—O2—C14—C15	−6.7 (5)
C3—C4—C5—C6	−178.3 (2)	C18—O2—C14—C13	173.8 (3)
N1—C5—C6—C7	124.1 (3)	C12—C13—C14—C15	0.1 (5)
C4—C5—C6—C7	−114.6 (3)	C12—C13—C14—O2	179.5 (3)
N1—C5—C6—C11	−56.0 (3)	O2—C14—C15—C16	179.3 (3)
C4—C5—C6—C11	65.4 (3)	C13—C14—C15—C16	−1.3 (5)
C11—C6—C7—C8	−0.7 (4)	C14—C15—C16—C17	1.2 (5)
C5—C6—C7—C8	179.2 (2)	C15—C16—C17—C12	0.0 (5)
C19—O3—C8—C9	−3.2 (4)	C13—C12—C17—C16	−1.2 (4)
C19—O3—C8—C7	177.0 (3)	C1—C12—C17—C16	−178.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···O3ⁱ	0.97	2.45	3.170 (4)	131
C19—H19C···O1ⁱⁱ	0.96	2.48	3.392 (4)	159

Symmetry codes: (i) x, −y+1, z−1/2; (ii) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₂₀H₂₃NO₃
M_r	325.39
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	290
a, b, c (Å)	28.695 (3), 10.9717 (12), 11.3946 (13)
β (°)	95.078 (2)
V (Å³)	3573.3 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.35 × 0.12 × 0.08

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	12581, 3148, 1751
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.154, 1.04
No. of reflections	3148
No. of parameters	224
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.14

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Acknowledgements

The authors thank the Department of Science and Technology, India, for use of the diffraction facility set up under the IRHPA–DST programme at IISc. FNK thanks the DST for Fast Track Proposal funding. The authors also thank VIT University and the University of Malaya for supporting this study.

References

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