3-[(E)-2,4-Dichloro­benzyl­idene]-1-methyl­piperidin-4-one

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

doi:10.1107/S1600536808002286

organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o520

doi:10.1107/S1600536808002286

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3-[(E)-2,4-Dichlorobenzylidene]-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 18 January 2008; accepted 22 January 2008; online 25 January 2008)

The piperidine ring of the title compound, C₁₃H₁₃Cl₂NO, adopts an envelope conformation. Intermolecular C—H⋯O interactions link the molecules into a C(7) chain running along the b axis.

Related literature

For biological activities of 4-piperidones, see: Badorrey et al. (1999 ); Grishina et al. (1994 ); Nalanishi et al. (1974a ,b ). For ring conformations, see: Cremer & Pople (1975 ); Nardelli (1983 ).

Experimental

Crystal data

C₁₃H₁₃Cl₂NO
M_r = 270.14
Monoclinic, P 2₁ /n
a = 12.2013 (9) Å
b = 8.5901 (6) Å
c = 12.6391 (9) Å
β = 92.997 (1)°
V = 1322.90 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.47 mm⁻¹
T = 293 (2) K
0.24 × 0.23 × 0.20 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: none
14377 measured reflections
3071 independent reflections
2654 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.120
S = 0.97
3071 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13⋯O1ⁱ	0.93	2.46	3.366 (2)	163
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{5\over 2}}]$ .

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/S1600536808002286/ci2557sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808002286/ci2557Isup2.hkl

checkCIF report

Comment top

Synthesis of 4-piperidones is of current interest due to their potential medical applications (Grishina et al., 1994). 4-Piperidones have been found to exhibit blood cholesterol-lowering activities (Nalanishi et al., 1974a,b). Various piperidones and piperidine derivatives are present in numerous alkaloids (Badorrey et al., 1999). As the title compound is of biological significance, the crystal structure of the title compound has been determined by X-ray diffraction.

The sum of the bond angles around atom N1 (330 °) indicates sp³– hybridization. Atoms Cl1 and Cl2 deviate from the plane of the attached benzene ring by 0.075 (1) and -0.094 (1) Å, respectively. The piperidine ring adopts an envelope conformation, with puckering parameters (Cremer & Pople, 1975) and smallest displacement asymmetry parameters (Nardelli, 1983) of Q = 0.504 (2) Å, θ = 141.1 (2)°, ϕ = 193.7 (4)° and ΔC_s[N1] = 8.7 (2)°.

In the crystal structure, the C—H···O intermolecular interactions generate a C(7) chain running along the b axis.

Related literature top

For biological activities of 4-piperidones, see: Badorrey et al. (1999); Grishina et al. (1994); Nalanishi et al. (1974a,b). For ring conformations, see: Cremer & Pople (1975); Nardelli (1983).

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, 2,4-dichlorobenzaldehyde (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 7 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. fter 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 338 K. 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 the title compound, showing 30% probability displacement ellipsoids.
	Fig. 2. The molecular packing in the title compound, viewed approximately down the a axis.

3-[(E)-2,4-Dichlorobenzylidene]-1-methylpiperidin-4-one top

Crystal data top

C₁₃H₁₃Cl₂NO	F(000) = 560
M_r = 270.14	D_x = 1.356 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1509 reflections
a = 12.2013 (9) Å	θ = 2.3–25.0°
b = 8.5901 (6) Å	µ = 0.47 mm⁻¹
c = 12.6391 (9) Å	T = 293 K
β = 92.997 (1)°	Block, pale yellow
V = 1322.90 (16) Å³	0.24 × 0.23 × 0.20 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2654 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.019
Graphite monochromator	θ_max = 28.1°, θ_min = 2.3°
ω scans	h = −15→15
14377 measured reflections	k = −10→11
3071 independent reflections	l = −16→16

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H-atom parameters constrained
S = 0.97	w = 1/[σ²(F_o²) + (0.0724P)² + 0.3356P] where P = (F_o² + 2F_c²)/3
3071 reflections	(Δ/σ)_max = 0.001
155 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₃H₁₃Cl₂NO	V = 1322.90 (16) Å³
M_r = 270.14	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.2013 (9) Å	µ = 0.47 mm⁻¹
b = 8.5901 (6) Å	T = 293 K
c = 12.6391 (9) Å	0.24 × 0.23 × 0.20 mm
β = 92.997 (1)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2654 reflections with I > 2σ(I)
14377 measured reflections	R_int = 0.019
3071 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 0.97	Δρ_max = 0.34 e Å⁻³
3071 reflections	Δρ_min = −0.28 e Å⁻³
155 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	0.53390 (18)	0.5088 (2)	1.24853 (18)	0.0781 (5)
H1A	0.5518	0.5079	1.1755	0.117*
H1B	0.5966	0.5421	1.2917	0.117*
H1C	0.4740	0.5792	1.2576	0.117*
C2	0.47091 (17)	0.3512 (2)	1.38999 (14)	0.0700 (5)
H2A	0.4038	0.4104	1.3959	0.084*
H2B	0.5280	0.4004	1.4346	0.084*
C3	0.4536 (2)	0.1860 (3)	1.42729 (13)	0.0791 (6)
H3A	0.5248	0.1374	1.4403	0.095*
H3B	0.4182	0.1896	1.4942	0.095*
C4	0.38604 (15)	0.0855 (2)	1.35183 (13)	0.0660 (5)
C5	0.37681 (12)	0.1336 (2)	1.23733 (11)	0.0524 (3)
C6	0.41053 (13)	0.29745 (19)	1.21048 (12)	0.0532 (3)
H6A	0.4317	0.3008	1.1376	0.064*
H6B	0.3484	0.3667	1.2168	0.064*
C7	0.34326 (12)	0.0240 (2)	1.16663 (12)	0.0545 (4)
H7	0.3257	−0.0728	1.1939	0.065*
C8	0.33134 (11)	0.04126 (18)	1.05058 (11)	0.0486 (3)
C9	0.35991 (12)	−0.08015 (17)	0.98306 (12)	0.0489 (3)
C10	0.35760 (12)	−0.06504 (17)	0.87383 (12)	0.0496 (3)
H10	0.3791	−0.1465	0.8311	0.059*
C11	0.32225 (13)	0.07535 (18)	0.83036 (11)	0.0500 (3)
C12	0.28628 (14)	0.19534 (19)	0.89226 (13)	0.0565 (4)
H12	0.2592	0.2867	0.8613	0.068*
C13	0.29116 (13)	0.17732 (19)	1.00152 (13)	0.0557 (4)
H13	0.2670	0.2581	1.0434	0.067*
N1	0.50222 (11)	0.35202 (16)	1.28025 (10)	0.0539 (3)
O1	0.34393 (15)	−0.0325 (2)	1.38258 (12)	0.1014 (6)
Cl1	0.40318 (5)	−0.25836 (5)	1.03652 (4)	0.07721 (18)
Cl2	0.32208 (5)	0.09909 (5)	0.69335 (3)	0.07158 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0843 (13)	0.0546 (10)	0.0934 (14)	−0.0057 (9)	−0.0158 (11)	0.0027 (10)
C2	0.0752 (11)	0.0799 (12)	0.0544 (9)	0.0079 (9)	−0.0035 (8)	−0.0182 (9)
C3	0.0949 (14)	0.1009 (15)	0.0412 (8)	−0.0155 (12)	0.0012 (8)	0.0010 (9)
C4	0.0617 (9)	0.0896 (13)	0.0472 (8)	−0.0133 (9)	0.0065 (7)	0.0089 (8)
C5	0.0465 (7)	0.0672 (9)	0.0437 (7)	−0.0049 (6)	0.0037 (6)	0.0033 (6)
C6	0.0523 (8)	0.0595 (9)	0.0475 (7)	0.0023 (7)	−0.0001 (6)	−0.0007 (7)
C7	0.0509 (8)	0.0625 (9)	0.0501 (8)	−0.0084 (7)	0.0038 (6)	0.0046 (7)
C8	0.0424 (7)	0.0541 (8)	0.0493 (7)	−0.0043 (6)	0.0011 (5)	−0.0007 (6)
C9	0.0473 (7)	0.0448 (7)	0.0543 (8)	−0.0020 (6)	−0.0011 (6)	0.0045 (6)
C10	0.0512 (7)	0.0460 (7)	0.0513 (8)	−0.0012 (6)	0.0016 (6)	−0.0035 (6)
C11	0.0535 (8)	0.0504 (7)	0.0455 (7)	−0.0036 (6)	−0.0018 (6)	0.0003 (6)
C12	0.0639 (9)	0.0483 (8)	0.0563 (8)	0.0069 (7)	−0.0084 (7)	−0.0006 (7)
C13	0.0561 (8)	0.0555 (8)	0.0549 (8)	0.0071 (7)	−0.0032 (6)	−0.0090 (7)
N1	0.0546 (7)	0.0524 (7)	0.0540 (7)	0.0017 (5)	−0.0029 (5)	−0.0036 (5)
O1	0.1116 (12)	0.1262 (13)	0.0654 (8)	−0.0543 (11)	−0.0048 (8)	0.0325 (9)
Cl1	0.1059 (4)	0.0545 (3)	0.0708 (3)	0.0144 (2)	0.0005 (3)	0.01340 (19)
Cl2	0.1041 (4)	0.0622 (3)	0.0482 (2)	−0.0037 (2)	0.0024 (2)	0.00406 (17)

Geometric parameters (Å, º) top

C1—N1	1.463 (2)	C6—H6A	0.97
C1—H1A	0.96	C6—H6B	0.97
C1—H1B	0.96	C7—C8	1.474 (2)
C1—H1C	0.96	C7—H7	0.93
C2—N1	1.458 (2)	C8—C13	1.400 (2)
C2—C3	1.514 (3)	C8—C9	1.403 (2)
C2—H2A	0.97	C9—C10	1.385 (2)
C2—H2B	0.97	C9—Cl1	1.7440 (15)
C3—C4	1.501 (3)	C10—C11	1.385 (2)
C3—H3A	0.97	C10—H10	0.93
C3—H3B	0.97	C11—C12	1.380 (2)
C4—O1	1.209 (2)	C11—Cl2	1.7435 (15)
C4—C5	1.504 (2)	C12—C13	1.388 (2)
C5—C7	1.346 (2)	C12—H12	0.93
C5—C6	1.510 (2)	C13—H13	0.93
C6—N1	1.465 (2)

N1—C1—H1A	109.5	N1—C6—H6B	109.3
N1—C1—H1B	109.5	C5—C6—H6B	109.3
H1A—C1—H1B	109.5	H6A—C6—H6B	107.9
N1—C1—H1C	109.5	C5—C7—C8	126.95 (15)
H1A—C1—H1C	109.5	C5—C7—H7	116.5
H1B—C1—H1C	109.5	C8—C7—H7	116.5
N1—C2—C3	110.39 (15)	C13—C8—C9	116.34 (13)
N1—C2—H2A	109.6	C13—C8—C7	122.59 (14)
C3—C2—H2A	109.6	C9—C8—C7	121.07 (14)
N1—C2—H2B	109.6	C10—C9—C8	122.94 (13)
C3—C2—H2B	109.6	C10—C9—Cl1	117.27 (11)
H2A—C2—H2B	108.1	C8—C9—Cl1	119.78 (12)
C4—C3—C2	114.99 (16)	C11—C10—C9	117.82 (13)
C4—C3—H3A	108.5	C11—C10—H10	121.1
C2—C3—H3A	108.5	C9—C10—H10	121.1
C4—C3—H3B	108.5	C12—C11—C10	121.83 (14)
C2—C3—H3B	108.5	C12—C11—Cl2	119.47 (12)
H3A—C3—H3B	107.5	C10—C11—Cl2	118.69 (12)
O1—C4—C5	121.85 (17)	C11—C12—C13	118.85 (15)
O1—C4—C3	120.41 (16)	C11—C12—H12	120.6
C5—C4—C3	117.69 (16)	C13—C12—H12	120.6
C7—C5—C4	116.86 (16)	C12—C13—C8	121.99 (14)
C7—C5—C6	125.39 (14)	C12—C13—H13	119.0
C4—C5—C6	117.70 (14)	C8—C13—H13	119.0
N1—C6—C5	111.81 (13)	C1—N1—C2	110.56 (15)
N1—C6—H6A	109.3	C1—N1—C6	109.51 (14)
C5—C6—H6A	109.3	C2—N1—C6	109.96 (13)

N1—C2—C3—C4	−46.3 (2)	C13—C8—C9—Cl1	−176.27 (11)
C2—C3—C4—O1	−161.3 (2)	C7—C8—C9—Cl1	3.54 (19)
C2—C3—C4—C5	21.1 (3)	C8—C9—C10—C11	−2.0 (2)
O1—C4—C5—C7	−15.5 (3)	Cl1—C9—C10—C11	179.32 (11)
C3—C4—C5—C7	162.09 (18)	C9—C10—C11—C12	−2.4 (2)
O1—C4—C5—C6	167.14 (19)	C9—C10—C11—Cl2	178.30 (11)
C3—C4—C5—C6	−15.2 (2)	C10—C11—C12—C13	3.4 (2)
C7—C5—C6—N1	−142.95 (16)	Cl2—C11—C12—C13	−177.33 (13)
C4—C5—C6—N1	34.12 (19)	C11—C12—C13—C8	0.0 (2)
C4—C5—C7—C8	−177.87 (14)	C9—C8—C13—C12	−4.0 (2)
C6—C5—C7—C8	−0.8 (3)	C7—C8—C13—C12	176.22 (14)
C5—C7—C8—C13	−38.6 (2)	C3—C2—N1—C1	−172.10 (17)
C5—C7—C8—C9	141.58 (17)	C3—C2—N1—C6	66.9 (2)
C13—C8—C9—C10	5.0 (2)	C5—C6—N1—C1	178.07 (14)
C7—C8—C9—C10	−175.16 (13)	C5—C6—N1—C2	−60.26 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O1ⁱ	0.93	2.46	3.366 (2)	163

Symmetry code: (i) −x+1/2, y+1/2, −z+5/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₃Cl₂NO
M_r	270.14
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	12.2013 (9), 8.5901 (6), 12.6391 (9)
β (°)	92.997 (1)
V (Å³)	1322.90 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.47
Crystal size (mm)	0.24 × 0.23 × 0.20

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	14377, 3071, 2654
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.663

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.120, 0.97
No. of reflections	3071
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.28

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
C13—H13···O1ⁱ	0.93	2.46	3.366 (2)	163

Symmetry code: (i) −x+1/2, y+1/2, −z+5/2.

Acknowledgements

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

References

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