3-[(E)-4-Methoxy­benzyl­idene]-1-methyl­piperidin-4-one

Gayathri, D.; Velmurugan, D.; Kumar, R.R.; Perumal, S.; Ravikumar, K.

doi:10.1107/S1600536808003280

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 3| March 2008| Page o552

doi:10.1107/S1600536808003280

Open

access

3-[(E)-4-Methoxybenzylidene]-1-methylpiperidin-4-one

D. Gayathri,^a D. Velmurugan,^a ^* R. Ranjith Kumar,^b S. Perumal ^b and K. Ravikumar ^c

^aCentre of Advanced Study in Crystallography and Biophysics, University of Madras, Guindy Campus, Chennai 600 025, India, ^bDepartment of Organic Chemistry, School of Chemistry, Madurai Kamaraj University, Madurai 625 021, India, and ^cLaboratory of X-ray Crystallography, Indian Institute of Chemical Technology, Hyderabad 500 007, India
^*Correspondence e-mail: d_velu@yahoo.com

(Received 21 January 2008; accepted 30 January 2008; online 6 February 2008)

The piperidone ring of the title compound, C₁₄H₁₇NO₂, adopts a half-chair conformation. The crystal packing is stabilized by intermolecular C—H⋯O interactions, which generate a C(8) chain running along the b axis.

Related literature

For related literature, see: Abignente & Biniecka-Picazio (1977 ); Angle & Breitenbucher (1995 ); Cremer & Pople (1975 ); Nardelli (1983 ); Wang & Wuorola (1992 ).

Experimental

Crystal data

C₁₄H₁₇NO₂
M_r = 231.29
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.5212 (7) Å
b = 12.4097 (11) Å
c = 13.5062 (12) Å
V = 1260.6 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 (2) K
0.24 × 0.22 × 0.21 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
10874 measured reflections
1729 independent reflections
1577 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.128
S = 1.11
1729 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯O1ⁱ	0.93	2.54	3.419 (3)	157
Symmetry code: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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, 2003 ); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808003280/bt2673sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808003280/bt2673Isup2.hkl

checkCIF report

Comment top

Substituted 4-piperidones are important synthetic intermediates for the preparation of various pharmaceuticals (Wang & Wuorola, 1992). 4-Piperidones are also widely prevalent in natural products such as alkaloids (Angle & Breitenbucher, 1995). Derivatives of 4-piperidones have been found to exhibit spasmolytic activities (Abignente & Biniecka-Picazio, 1977). Since, the title compound is pharmacologically important, the crystal structure of the title compound has been determined by X-ray diffraction.

The sum of the bond angles around N1 [331.4 (6)°] indicate the sp³ hybridization. The torsion angles around C10—C11—O2—C14 [179.4 (2)°] and C12—C11—O2—C14 [-0.8 (3)°] indicate that the methoxy group is planar with the phenyl ring.

The piperidone ring adopts a half-chair conformation with the puckering parameters (Cremer & Pople, 1975) and the smallest displacement asymmetry parameters (Nardelli, 1983) being q₂ = 0.366 (3) Å, q₃ = 0.361 (3) Å, Q_T = 0.515 (3)Å and θ = 45.4 (3)°. The molecular conformation is stabilized by weak C—H···O intramolecular interactions. The crystal packing is stabilized by C—H···O intermolecular interactions generating a chain C(8) running along b axis.

Related literature top

Forrelated literature, see: Abignente & Biniecka-Picazio (1977); Angle & Breitenbucher (1995); Cremer & Pople (1975); Nardelli (1983); Wang & Wuorola (1992).

Experimental top

A mixture of 1-methyl-4-piperidone (1 mmol) and pyrrolidine (1.2 mmol) was taken in a glass tube, mixed well and kept aside for 5 min at ambient temperature. To this mixture, 4-methoxybenzaldehyde (1 mmol) was added, mixed thoroughly and the tube containing the mixture was partially immersed in a silica bath placed in a microwave oven and irradiated at 4 power level for 8 minutes. The progress of the reaction was monitored after every 1 min of irradiation by TLC with petroleum ether:ethyl acetate (1:2 v/v mixture) as eluent. After each irradiation, the reaction mixture was cooled to room temperature and mixed well. The maximum temperature of the silica bath, measured immediately after each irradiation was over by stirring the silica bath with the thermometer, was found to be 65 °C. After completion of the reaction as evident from the TLC, the product was purified by column chromatography using petroleum ether:ethyl acetate (7:2 v/v) mixture and crystallized from ethyl acetate.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PARST (Nardelli, 1995).

Figures top

	Fig. 1. The molecular structure of title compound, showing 30% probability displacement ellipsoids.
	Fig. 2. The molecular packing of the title compound, viewed down the a axis.

3-[(E)-4-Methoxybenzylidene]-1-methylpiperidin-4-one top

Crystal data top

C₁₄H₁₇NO₂	F(000) = 496
M_r = 231.29	D_x = 1.219 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 861 reflections
a = 7.5212 (7) Å	θ = 2.2–25.0°
b = 12.4097 (11) Å	µ = 0.08 mm⁻¹
c = 13.5062 (12) Å	T = 293 K
V = 1260.6 (2) Å³	Block, pale yellow
Z = 4	0.24 × 0.22 × 0.21 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1577 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.019
Graphite monochromator	θ_max = 28.1°, θ_min = 2.2°
ω scans	h = −9→9
10874 measured reflections	k = −16→16
1729 independent reflections	l = −17→17

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.083P)² + 0.0611P] where P = (F_o² + 2F_c²)/3
1729 reflections	(Δ/σ)_max < 0.001
156 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.13 e Å⁻³

Crystal data top

C₁₄H₁₇NO₂	V = 1260.6 (2) Å³
M_r = 231.29	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.5212 (7) Å	µ = 0.08 mm⁻¹
b = 12.4097 (11) Å	T = 293 K
c = 13.5062 (12) Å	0.24 × 0.22 × 0.21 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1577 reflections with I > 2σ(I)
10874 measured reflections	R_int = 0.019
1729 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 1.11	Δρ_max = 0.28 e Å⁻³
1729 reflections	Δρ_min = −0.13 e Å⁻³
156 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
C1	−0.1137 (5)	0.0252 (2)	1.28219 (18)	0.0864 (8)
H1A	−0.0039	0.0433	1.3144	0.130*
H1B	−0.1816	−0.0218	1.3241	0.130*
H1C	−0.1803	0.0898	1.2697	0.130*
C2	0.0338 (4)	−0.1243 (2)	1.20225 (17)	0.0802 (7)
H2A	−0.0149	−0.1685	1.2549	0.096*
H2B	0.1533	−0.1031	1.2210	0.096*
C3	0.0400 (5)	−0.18853 (18)	1.1072 (2)	0.0845 (7)
H3A	0.1321	−0.2429	1.1131	0.101*
H3B	−0.0725	−0.2257	1.0992	0.101*
C4	0.0749 (4)	−0.12308 (16)	1.01586 (16)	0.0697 (6)
C5	0.0494 (3)	−0.00418 (14)	1.02172 (14)	0.0548 (5)
C6	0.0120 (3)	0.04524 (15)	1.12177 (14)	0.0558 (4)
H6A	0.1232	0.0685	1.1512	0.067*
H6B	−0.0622	0.1085	1.1130	0.067*
C7	0.0594 (3)	0.05043 (14)	0.93680 (15)	0.0560 (5)
H7	0.0790	0.0090	0.8805	0.067*
C8	0.0436 (3)	0.16662 (14)	0.91996 (13)	0.0510 (4)
C9	−0.0213 (3)	0.20203 (14)	0.82852 (13)	0.0562 (5)
H9	−0.0506	0.1515	0.7804	0.067*
C10	−0.0427 (3)	0.30978 (15)	0.80817 (12)	0.0576 (5)
H10	−0.0879	0.3314	0.7472	0.069*
C11	0.0031 (2)	0.38597 (14)	0.87840 (13)	0.0511 (4)
C12	0.0740 (3)	0.35353 (14)	0.96828 (14)	0.0585 (5)
H12	0.1079	0.4045	1.0151	0.070*
C13	0.0938 (3)	0.24434 (17)	0.98781 (15)	0.0581 (5)
H13	0.1422	0.2229	1.0481	0.070*
C14	0.0194 (4)	0.57070 (15)	0.92477 (17)	0.0667 (6)
H14A	−0.0449	0.5570	0.9849	0.100*
H14B	−0.0116	0.6407	0.8999	0.100*
H14C	0.1448	0.5681	0.9379	0.100*
N1	−0.0762 (3)	−0.02883 (15)	1.18885 (13)	0.0656 (5)
O1	0.1230 (4)	−0.16737 (12)	0.94008 (14)	0.0993 (7)
O2	−0.0251 (2)	0.49113 (10)	0.85323 (10)	0.0627 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.105 (2)	0.0972 (18)	0.0569 (12)	−0.0171 (16)	0.0036 (13)	0.0011 (12)
C2	0.1040 (18)	0.0634 (11)	0.0731 (13)	−0.0072 (14)	−0.0128 (14)	0.0222 (11)
C3	0.1134 (19)	0.0459 (9)	0.0942 (16)	−0.0027 (13)	−0.0080 (17)	0.0165 (11)
C4	0.0965 (15)	0.0404 (8)	0.0723 (12)	0.0031 (10)	−0.0171 (13)	−0.0023 (9)
C5	0.0662 (11)	0.0391 (7)	0.0590 (10)	0.0011 (8)	−0.0092 (9)	−0.0002 (7)
C6	0.0660 (11)	0.0464 (8)	0.0551 (9)	−0.0030 (8)	−0.0093 (9)	0.0009 (7)
C7	0.0701 (11)	0.0430 (8)	0.0551 (9)	0.0031 (8)	−0.0019 (9)	−0.0053 (7)
C8	0.0603 (10)	0.0433 (8)	0.0493 (8)	0.0005 (8)	0.0021 (8)	0.0001 (6)
C9	0.0787 (12)	0.0476 (8)	0.0423 (7)	−0.0009 (9)	0.0058 (9)	−0.0040 (6)
C10	0.0793 (12)	0.0538 (9)	0.0397 (7)	0.0015 (10)	0.0022 (9)	0.0058 (7)
C11	0.0602 (9)	0.0421 (7)	0.0510 (8)	−0.0017 (8)	0.0055 (8)	0.0055 (7)
C12	0.0744 (11)	0.0443 (9)	0.0568 (10)	−0.0085 (9)	−0.0103 (9)	−0.0004 (7)
C13	0.0713 (11)	0.0488 (9)	0.0544 (9)	−0.0029 (9)	−0.0150 (9)	0.0057 (7)
C14	0.0878 (14)	0.0414 (8)	0.0708 (12)	−0.0001 (10)	0.0100 (12)	−0.0005 (8)
N1	0.0784 (11)	0.0618 (9)	0.0565 (8)	−0.0120 (9)	−0.0084 (9)	0.0061 (7)
O1	0.169 (2)	0.0465 (7)	0.0828 (11)	0.0139 (12)	−0.0067 (13)	−0.0083 (8)
O2	0.0866 (10)	0.0415 (6)	0.0600 (7)	−0.0016 (7)	−0.0008 (8)	0.0077 (5)

Geometric parameters (Å, º) top

C1—N1	1.456 (3)	C7—C8	1.465 (2)
C1—H1A	0.9600	C7—H7	0.9300
C1—H1B	0.9600	C8—C13	1.383 (3)
C1—H1C	0.9600	C8—C9	1.399 (3)
C2—N1	1.457 (3)	C9—C10	1.374 (3)
C2—C3	1.511 (4)	C9—H9	0.9300
C2—H2A	0.9700	C10—C11	1.383 (3)
C2—H2B	0.9700	C10—H10	0.9300
C3—C4	1.500 (3)	C11—O2	1.365 (2)
C3—H3A	0.9700	C11—C12	1.385 (3)
C3—H3B	0.9700	C12—C13	1.389 (3)
C4—O1	1.217 (3)	C12—H12	0.9300
C4—C5	1.490 (3)	C13—H13	0.9300
C5—C7	1.334 (3)	C14—O2	1.421 (3)
C5—C6	1.510 (3)	C14—H14A	0.9600
C6—N1	1.451 (3)	C14—H14B	0.9600
C6—H6A	0.9700	C14—H14C	0.9600
C6—H6B	0.9700

N1—C1—H1A	109.5	C5—C7—H7	115.5
N1—C1—H1B	109.5	C8—C7—H7	115.5
H1A—C1—H1B	109.5	C13—C8—C9	117.47 (16)
N1—C1—H1C	109.5	C13—C8—C7	124.17 (18)
H1A—C1—H1C	109.5	C9—C8—C7	118.33 (16)
H1B—C1—H1C	109.5	C10—C9—C8	121.53 (17)
N1—C2—C3	109.93 (19)	C10—C9—H9	119.2
N1—C2—H2A	109.7	C8—C9—H9	119.2
C3—C2—H2A	109.7	C9—C10—C11	119.92 (17)
N1—C2—H2B	109.7	C9—C10—H10	120.0
C3—C2—H2B	109.7	C11—C10—H10	120.0
H2A—C2—H2B	108.2	O2—C11—C12	123.75 (16)
C4—C3—C2	114.74 (18)	O2—C11—C10	116.37 (16)
C4—C3—H3A	108.6	C12—C11—C10	119.88 (16)
C2—C3—H3A	108.6	C11—C12—C13	119.43 (17)
C4—C3—H3B	108.6	C11—C12—H12	120.3
C2—C3—H3B	108.6	C13—C12—H12	120.3
H3A—C3—H3B	107.6	C8—C13—C12	121.69 (18)
O1—C4—C5	122.0 (2)	C8—C13—H13	119.2
O1—C4—C3	119.95 (19)	C12—C13—H13	119.2
C5—C4—C3	118.0 (2)	O2—C14—H14A	109.5
C7—C5—C4	116.75 (17)	O2—C14—H14B	109.5
C7—C5—C6	124.98 (16)	H14A—C14—H14B	109.5
C4—C5—C6	118.27 (16)	O2—C14—H14C	109.5
N1—C6—C5	112.74 (16)	H14A—C14—H14C	109.5
N1—C6—H6A	109.0	H14B—C14—H14C	109.5
C5—C6—H6A	109.0	C6—N1—C1	109.72 (18)
N1—C6—H6B	109.0	C6—N1—C2	109.5 (2)
C5—C6—H6B	109.0	C1—N1—C2	112.18 (19)
H6A—C6—H6B	107.8	C11—O2—C14	117.27 (15)
C5—C7—C8	128.98 (17)

N1—C2—C3—C4	46.7 (3)	C8—C9—C10—C11	1.1 (3)
C2—C3—C4—O1	163.0 (3)	C9—C10—C11—O2	−178.8 (2)
C2—C3—C4—C5	−16.8 (4)	C9—C10—C11—C12	1.3 (3)
O1—C4—C5—C7	8.4 (4)	O2—C11—C12—C13	178.5 (2)
C3—C4—C5—C7	−171.8 (2)	C10—C11—C12—C13	−1.7 (3)
O1—C4—C5—C6	−172.5 (3)	C9—C8—C13—C12	2.7 (3)
C3—C4—C5—C6	7.3 (3)	C7—C8—C13—C12	−179.2 (2)
C7—C5—C6—N1	151.3 (2)	C11—C12—C13—C8	−0.4 (3)
C4—C5—C6—N1	−27.8 (3)	C5—C6—N1—C1	−178.0 (2)
C4—C5—C7—C8	−178.6 (2)	C5—C6—N1—C2	58.5 (2)
C6—C5—C7—C8	2.3 (4)	C3—C2—N1—C6	−68.5 (3)
C5—C7—C8—C13	30.6 (4)	C3—C2—N1—C1	169.4 (2)
C5—C7—C8—C9	−151.3 (2)	C12—C11—O2—C14	−0.8 (3)
C13—C8—C9—C10	−3.1 (3)	C10—C11—O2—C14	179.37 (19)
C7—C8—C9—C10	178.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···O1ⁱ	0.93	2.54	3.419 (3)	157

Symmetry code: (i) −x, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₇NO₂
M_r	231.29
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	7.5212 (7), 12.4097 (11), 13.5062 (12)
V (Å³)	1260.6 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.24 × 0.22 × 0.21

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	10874, 1729, 1577
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.662

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.128, 1.11
No. of reflections	1729
No. of parameters	156
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.13

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), PLATON (Spek, 2003), SHELXL97 (Sheldrick, 2008) and PARST (Nardelli, 1995).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···O1ⁱ	0.93	2.54	3.419 (3)	156.9

Symmetry code: (i) −x, y+1/2, −z+3/2.

Acknowledgements

DG thanks the Council of Scientific and Industrial Research (CSIR), India, for a Senior Research Fellowship. Financial support from the University Grants Commission (UGC–SAP) and the Department of Science & Technology (DST–FIST), Government of India, is acknowledged by DV for providing facilities to the department.

References

Abignente, E. & Biniecka-Picazio, M. (1977). Acta Pol. Pharm. 34, 241–242. CAS PubMed Web of Science Google Scholar
Angle, S. R. & Breitenbucher, J. G. (1995). In Studies in Natural Products Chemistry; Stereoselective Synthesis, edited by Atta-ur-Rahman, Vol. 16, Part J, pp 453–502. New York: Elsevier. Google Scholar
Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Nardelli, M. (1983). Acta Cryst. C39, 1141–1142. CrossRef CAS Web of Science IUCr Journals Google Scholar
Nardelli, M. (1995). J. Appl. Cryst. 28, 659. CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, C.-L. & Wuorola, M. A. (1992). Org. Prep. Proced. Int. 24, 585–621. Google Scholar