2-Ethyl­piperidinium chloride

Al-Dajani, M.T.M.; Talaat, J.; Salhin, A.; Hemamalini, M.; Fun, H.-K.

doi:10.1107/S1600536811036804

organic compounds

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ISSN: 2056-9890

Volume 67| Part 10| October 2011| Page o2653

https://doi.org/10.1107/S1600536811036804

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2-Ethylpiperidinium chloride

Mohammad T. M. Al-Dajani,^a Jamal Talaat,^b Abdusalam Salhin,^c Madhukar Hemamalini ^d and Hoong-Kun Fun ^d ^*‡

^aSchool of Pharmaceutical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bVirginia Commonwealth University, Chemistry School, USA, ^cSchool of Chemical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^dX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 6 September 2011; accepted 10 September 2011; online 17 September 2011)

In the title molecular salt, C₇H₁₆N⁺·Cl⁻, the piperidinium ring adopts a chair conformation. In the crystal, the two components are connected by N—H⋯Cl and C—H⋯Cl hydrogen bonds, forming a supramolecular double-chain structure along the c axis.

Related literature

For biological applications of piperidine, see: Waelbroeck et al. (1992 ); El Hadri et al. (1995 ). For puckering parameters, see: Cremer & Pople (1975 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₇H₁₆N⁺·Cl⁻
M_r = 149.66
Orthorhombic, P b c n
a = 24.2052 (6) Å
b = 9.7594 (3) Å
c = 7.2764 (2) Å
V = 1718.89 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.37 mm⁻¹
T = 100 K
0.72 × 0.27 × 0.15 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.778, T_max = 0.948
50389 measured reflections
4453 independent reflections
3438 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.088
S = 1.07
4453 reflections
91 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1NA⋯Cl1ⁱ	0.886 (14)	2.220 (14)	3.1054 (7)	176.9 (11)
N1—H2NA⋯Cl1	0.899 (15)	2.217 (15)	3.1149 (7)	177.8 (12)
C1—H1A⋯Cl1ⁱⁱ	0.99	2.80	3.6121 (8)	139
Symmetry codes: (i) $[x, -y, z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811036804/is2773sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811036804/is2773Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811036804/is2773Isup3.cml

checkCIF report

Comment top

Piperidine derivatives are the valued heterocyclic compounds in the field of medicinal chemistry. The piperidine nucleus is present in a wide range of biologically active compounds. For example, the binding properties of 4-diphenylacetoxy-N-methylpiperidine methiodide (4-DAMP) and its analogs have been evaluated at muscarinic receptors in human neuroblastoma NB-OK1 cells (M1 receptor subtype), rat heart (M2 subtype), rat pancreas (M3 subtype) and the putative M4 receptor subtype in striatum (Waelbroeck et al., 1992). NMDA receptor antagonist properties of piperidine-2-carboxylic acid derivatives have also been reported (El Hadri et al., 1995). Herein, we have present the crystal structure of the title compound (I).

The asymmetric unit of (I), (Fig. 1), consists of a 2-ethylpiperidinium cation and a chloride anion. The piperidine (N1/C1–C5) ring adopts a chair conformation with puckering parameters Q = 0.5708 (9) Å, θ = 180.00 (9)° and φ = 282 (7)° (Cremer & Pople, 1975). In the crystal structure (Fig. 2), the cations and anions are connected by intermolecular N1—H1NA···Cl1, N1—H2NA···Cl1 and C1—H1A···Cl1 hydrogen bonds (Table 1), forming one-dimensional supramolecular chains along the c-axis.

Related literature top

For biological applications of piperidine, see: Waelbroeck et al. (1992); El Hadri et al. (1995). For puckering parameters, see: Cremer & Pople (1975). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Experimental top

In a round bottom flask, 25ml of tetrahydronfuran (THF) was mixed with 2-ethylpiperidine (0.01 mol, 0.8 g) with stirring. Drops of benzylchloride (0.01 mol, 1.0 g) dissolved in THF was then added. The reaction mixture was refluxed for 30 min. The precipitate formed was washed with THF. The precipitate was then dissolved in methanol at room temperature. After few days, colourless needle-shaped crystals were formed by slow evaporation.

Structure description top

For biological applications of piperidine, see: Waelbroeck et al. (1992); El Hadri et al. (1995). For puckering parameters, see: Cremer & Pople (1975). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The asymmetric unit of the title compound, showing 50% probability displacement ellipsoids. An intermolecular N—H···Cl hydrogen bond is shown by a dashed line.
	Fig. 2. The crystal packing of the title compound, viewed along the a axis.

2-Ethylpiperidinium chloride top

Crystal data top

C₇H₁₆N⁺·Cl⁻	F(000) = 656
M_r = 149.66	D_x = 1.157 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 9898 reflections
a = 24.2052 (6) Å	θ = 2.3–36.9°
b = 9.7594 (3) Å	µ = 0.37 mm⁻¹
c = 7.2764 (2) Å	T = 100 K
V = 1718.89 (8) Å³	Block, colourless
Z = 8	0.72 × 0.27 × 0.15 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	4453 independent reflections
Radiation source: fine-focus sealed tube	3438 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
φ and ω scans	θ_max = 37.3°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −40→40
T_min = 0.778, T_max = 0.948	k = −16→16
50389 measured reflections	l = −12→12

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) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0343P)² + 0.4206P] where P = (F_o² + 2F_c²)/3
4453 reflections	(Δ/σ)_max = 0.001
91 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₇H₁₆N⁺·Cl⁻	V = 1718.89 (8) Å³
M_r = 149.66	Z = 8
Orthorhombic, Pbcn	Mo Kα radiation
a = 24.2052 (6) Å	µ = 0.37 mm⁻¹
b = 9.7594 (3) Å	T = 100 K
c = 7.2764 (2) Å	0.72 × 0.27 × 0.15 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	4453 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3438 reflections with I > 2σ(I)
T_min = 0.778, T_max = 0.948	R_int = 0.045
50389 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.34 e Å⁻³
4453 reflections	Δρ_min = −0.27 e Å⁻³
91 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
N1	0.39971 (3)	0.13082 (7)	0.95142 (9)	0.01471 (11)
C1	0.45090 (3)	0.18923 (8)	1.03505 (12)	0.01927 (15)
H1A	0.4838	0.1482	0.9761	0.023*
H1B	0.4520	0.1670	1.1678	0.023*
C2	0.45182 (4)	0.34373 (9)	1.00941 (12)	0.02298 (17)
H2A	0.4543	0.3655	0.8768	0.028*
H2B	0.4848	0.3823	1.0710	0.028*
C3	0.39979 (4)	0.40873 (9)	1.08969 (12)	0.02384 (17)
H3A	0.3999	0.5084	1.0647	0.029*
H3B	0.3993	0.3955	1.2246	0.029*
C4	0.34807 (4)	0.34393 (8)	1.00500 (12)	0.01959 (15)
H4A	0.3148	0.3837	1.0638	0.024*
H4B	0.3467	0.3664	0.8724	0.024*
C5	0.34710 (3)	0.18860 (8)	1.02842 (10)	0.01526 (13)
H5A	0.3452	0.1667	1.1625	0.018*
C6	0.29921 (4)	0.11725 (8)	0.93081 (12)	0.01881 (14)
H6A	0.3011	0.1382	0.7978	0.023*
H6B	0.3033	0.0169	0.9455	0.023*
C7	0.24270 (4)	0.16025 (11)	1.00354 (15)	0.02814 (19)
H7A	0.2138	0.1106	0.9369	0.042*
H7B	0.2378	0.2590	0.9855	0.042*
H7C	0.2403	0.1388	1.1349	0.042*
H1NA	0.4002 (5)	0.0410 (14)	0.9689 (17)	0.021 (3)*
H2NA	0.4007 (4)	0.1476 (13)	0.830 (2)	0.024 (3)*
Cl1	0.401145 (8)	0.182057 (18)	0.52892 (2)	0.01611 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0164 (3)	0.0142 (3)	0.0135 (3)	0.0003 (2)	0.0004 (2)	0.0007 (2)
C1	0.0173 (3)	0.0207 (3)	0.0198 (3)	−0.0028 (3)	−0.0031 (3)	0.0026 (3)
C2	0.0263 (4)	0.0213 (4)	0.0213 (4)	−0.0086 (3)	−0.0037 (3)	0.0031 (3)
C3	0.0368 (5)	0.0158 (3)	0.0189 (3)	−0.0042 (3)	−0.0016 (3)	−0.0012 (3)
C4	0.0254 (4)	0.0137 (3)	0.0197 (3)	0.0020 (3)	0.0015 (3)	0.0000 (3)
C5	0.0176 (3)	0.0142 (3)	0.0140 (3)	0.0010 (2)	0.0026 (3)	0.0008 (2)
C6	0.0166 (3)	0.0188 (3)	0.0210 (3)	−0.0001 (3)	0.0004 (3)	0.0002 (3)
C7	0.0186 (4)	0.0286 (4)	0.0372 (5)	0.0007 (3)	0.0062 (4)	0.0015 (4)
Cl1	0.02022 (9)	0.01473 (8)	0.01339 (7)	−0.00044 (6)	0.00104 (6)	0.00007 (5)

Geometric parameters (Å, º) top

N1—C1	1.4935 (11)	C3—H3B	0.9900
N1—C5	1.5012 (10)	C4—C5	1.5256 (11)
N1—H1NA	0.886 (13)	C4—H4A	0.9900
N1—H2NA	0.896 (14)	C4—H4B	0.9900
C1—C2	1.5195 (12)	C5—C6	1.5275 (11)
C1—H1A	0.9900	C5—H5A	1.0000
C1—H1B	0.9900	C6—C7	1.5256 (13)
C2—C3	1.5264 (14)	C6—H6A	0.9900
C2—H2A	0.9900	C6—H6B	0.9900
C2—H2B	0.9900	C7—H7A	0.9800
C3—C4	1.5318 (13)	C7—H7B	0.9800
C3—H3A	0.9900	C7—H7C	0.9800

C1—N1—C5	114.10 (6)	C5—C4—C3	112.20 (7)
C1—N1—H1NA	108.0 (7)	C5—C4—H4A	109.2
C5—N1—H1NA	109.2 (7)	C3—C4—H4A	109.2
C1—N1—H2NA	108.0 (7)	C5—C4—H4B	109.2
C5—N1—H2NA	108.7 (7)	C3—C4—H4B	109.2
H1NA—N1—H2NA	108.7 (11)	H4A—C4—H4B	107.9
N1—C1—C2	109.93 (7)	N1—C5—C4	108.57 (7)
N1—C1—H1A	109.7	N1—C5—C6	107.40 (6)
C2—C1—H1A	109.7	C4—C5—C6	114.38 (7)
N1—C1—H1B	109.7	N1—C5—H5A	108.8
C2—C1—H1B	109.7	C4—C5—H5A	108.8
H1A—C1—H1B	108.2	C6—C5—H5A	108.8
C1—C2—C3	110.69 (7)	C7—C6—C5	113.19 (7)
C1—C2—H2A	109.5	C7—C6—H6A	108.9
C3—C2—H2A	109.5	C5—C6—H6A	108.9
C1—C2—H2B	109.5	C7—C6—H6B	108.9
C3—C2—H2B	109.5	C5—C6—H6B	108.9
H2A—C2—H2B	108.1	H6A—C6—H6B	107.8
C2—C3—C4	110.41 (7)	C6—C7—H7A	109.5
C2—C3—H3A	109.6	C6—C7—H7B	109.5
C4—C3—H3A	109.6	H7A—C7—H7B	109.5
C2—C3—H3B	109.6	C6—C7—H7C	109.5
C4—C3—H3B	109.6	H7A—C7—H7C	109.5
H3A—C3—H3B	108.1	H7B—C7—H7C	109.5

C5—N1—C1—C2	−58.09 (9)	C1—N1—C5—C6	−179.25 (6)
N1—C1—C2—C3	56.11 (9)	C3—C4—C5—N1	−54.61 (9)
C1—C2—C3—C4	−55.59 (9)	C3—C4—C5—C6	−174.51 (7)
C2—C3—C4—C5	55.68 (9)	N1—C5—C6—C7	176.69 (7)
C1—N1—C5—C4	56.59 (8)	C4—C5—C6—C7	−62.75 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1NA···Cl1ⁱ	0.886 (14)	2.220 (14)	3.1054 (7)	176.9 (11)
N1—H2NA···Cl1	0.899 (15)	2.217 (15)	3.1149 (7)	177.8 (12)
C1—H1A···Cl1ⁱⁱ	0.99	2.80	3.6121 (8)	139

Symmetry codes: (i) x, −y, z+1/2; (ii) −x+1, y, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₇H₁₆N⁺·Cl⁻
M_r	149.66
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	100
a, b, c (Å)	24.2052 (6), 9.7594 (3), 7.2764 (2)
V (Å³)	1718.89 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.37
Crystal size (mm)	0.72 × 0.27 × 0.15

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.778, 0.948
No. of measured, independent and observed [I > 2σ(I)] reflections	50389, 4453, 3438
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.852

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.088, 1.07
No. of reflections	4453
No. of parameters	91
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.27

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1NA···Cl1ⁱ	0.886 (14)	2.220 (14)	3.1054 (7)	176.9 (11)
N1—H2NA···Cl1	0.899 (15)	2.217 (15)	3.1149 (7)	177.8 (12)
C1—H1A···Cl1ⁱⁱ	0.99	2.80	3.6121 (8)	139

Symmetry codes: (i) x, −y, z+1/2; (ii) −x+1, y, −z+3/2.

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

AS gratefully acknowledges funding from Universiti Sains Malaysia (USM) under the University Research Grant (No. 1001/PKIMIA/811055). HKF and MH thank the Malaysian Government and Universiti Sains Malaysia for the Research University Grant No. 1001/PFIZIK/811160. MH also thanks Universiti Sains Malaysia for a post-doctoral research fellowship.

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