1-(2-Carb­oxy­eth­yl)-5-ethyl-2-methyl­pyridinium chloride

Sabari, V.; Kalaiselvi, G.; Balasubramanian, S.; Aravindhan, S.

doi:10.1107/S1600536812038809

organic compounds

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ISSN: 2056-9890

Volume 68| Part 10| October 2012| Page o2937

https://doi.org/10.1107/S1600536812038809

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1-(2-Carboxyethyl)-5-ethyl-2-methylpyridinium chloride

V. Sabari,^a G. Kalaiselvi,^b S. Balasubramanian ^b and S. Aravindhan ^a ^*

^aDepartment of Physics, Presidency College, Chennai 600 005, India, and ^bDepartment of Inorganic Chemistry, University of Madras, Chennai 600 025, India
^*Correspondence e-mail: aravindhanpresidency@gmail.com

(Received 24 August 2012; accepted 10 September 2012; online 15 September 2012)

In the crystal structure of the title salt, C₁₁H₁₆NO₂⁺·Cl⁻, the cations and anions are linked by O—H⋯Cl hydrogen bonds. The structure is further stabilized by weak C—H⋯Cl hydrogen bonds.

Related literature

For the biological activity of 4-aminopyridine, see: Judge & Bever (2006 ); Schwid et al. (1997 ); Strupp et al. (2004 ). For related structures, see: Anderson et al. (2005 ); Fun et al. (2009 ).

Experimental

Crystal data

C₁₁H₁₆NO₂⁺·Cl⁻
M_r = 229.70
Triclinic, $[P \overline 1]$
a = 7.5013 (4) Å
b = 9.0509 (5) Å
c = 9.3452 (5) Å
α = 75.253 (2)°
β = 80.985 (2)°
γ = 72.047 (2)°
V = 581.59 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 293 K
0.32 × 0.20 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.972, T_max = 0.992
11668 measured reflections
2772 independent reflections
2363 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.102
S = 0.83
2772 reflections
142 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯Cl1	0.92 (3)	2.06 (3)	2.9749 (12)	170 (2)
C2—H2⋯Cl1ⁱ	0.93	2.72	3.6249 (14)	166
C6—H6A⋯Cl1ⁱⁱ	0.97	2.68	3.6261 (14)	166
C11—H11A⋯Cl1ⁱⁱⁱ	0.96	2.79	3.7410 (16)	170
Symmetry codes: (i) x-1, y, z+1; (ii) x, y, z+1; (iii) -x+2, -y, -z+1.

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812038809/bt6827sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812038809/bt6827Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812038809/bt6827Isup3.cml

checkCIF report

Comment top

4-Aminopyridine (Fampridine) is used clinically in Lambert-Eaton myasthenic syndrome and multiple sclerosis because by blocking potassium channels it prolongs action potentials thereby increasing transmitter release at the neuromuscular junction (Judge & Bever et al., 2006; Schwid et al., 1997; Strupp et al., 2004).

In the title compound (Fig. 1), the bond lengths and angles have normal values. The asymmetric unit is composed of one 1-(2-carboxy ethyl) 5-ethyl 2-methyl pyridinium cation and one Cl^- anion. The C1—N1—C5 angle in the pyridinium ring is widened to 121.20 (15) °, compared to 115.25 (13)° in 4-aminopyridine (Anderson et al., 2005) and 120.7 (2)°, in Aminopyridinium (Fun et al., 2009). In the crystal structure, anions and cations are connected by O—H···Cl and C—H···Cl hydrogen bonds.

Related literature top

For the biological activity of 4-aminopyridine, see: Judge & Bever (2006); Schwid et al. (1997); Strupp et al. (2004). For related structures, see: Anderson et al. (2005); Fun et al. (2009).

Experimental top

1g (8.3mmol) of freshly distilled 5-ethyl 2-methyl pyridine was dissolved in 10 ml of THF at -10°C under nitrogen atmosphere. To the above solution, 0.8 ml (8.0 mmol) of acrylic acid in 10 ml of THF was added drop wise with continuous stirring. After stirring for 20 min in an ice bath, 0.5 mL of HCl was added and stirred for 24 h. White solid formed after the completion of the reaction and the solid was filtered, washed with THF and dried in vacuum. The product was recrystallized from methanol Yield: 1.52g (80%)

Structure description top

For the biological activity of 4-aminopyridine, see: Judge & Bever (2006); Schwid et al. (1997); Strupp et al. (2004). For related structures, see: Anderson et al. (2005); Fun et al. (2009).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

Fig. 1. View of one molecule of the title compound showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level (arbitrary spheres for the H atoms).

1-(2-Carboxyethyl)-5-ethyl-2-methylpyridinium chloride top

Crystal data top

C₁₁H₁₆NO₂⁺·Cl⁻	Z = 2
M_r = 229.70	F(000) = 244
Triclinic, P1	D_x = 1.312 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5013 (4) Å	Cell parameters from 5710 reflections
b = 9.0509 (5) Å	θ = 1.8–28.5°
c = 9.3452 (5) Å	µ = 0.31 mm⁻¹
α = 75.253 (2)°	T = 293 K
β = 80.985 (2)°	Triclinic, colourless
γ = 72.047 (2)°	0.32 × 0.20 × 0.10 mm
V = 581.59 (5) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	2772 independent reflections
Radiation source: fine-focus sealed tube	2363 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ω and φ scans	θ_max = 27.9°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −9→9
T_min = 0.972, T_max = 0.992	k = −11→11
11668 measured reflections	l = −10→12

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.102	w = 1/[σ²(F_o²) + (0.0665P)² + 0.2215P] where P = (F_o² + 2F_c²)/3
S = 0.83	(Δ/σ)_max < 0.001
2772 reflections	Δρ_max = 0.23 e Å⁻³
142 parameters	Δρ_min = −0.19 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.034 (6)

Crystal data top

C₁₁H₁₆NO₂⁺·Cl⁻	γ = 72.047 (2)°
M_r = 229.70	V = 581.59 (5) Å³
Triclinic, P1	Z = 2
a = 7.5013 (4) Å	Mo Kα radiation
b = 9.0509 (5) Å	µ = 0.31 mm⁻¹
c = 9.3452 (5) Å	T = 293 K
α = 75.253 (2)°	0.32 × 0.20 × 0.10 mm
β = 80.985 (2)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2772 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	2363 reflections with I > 2σ(I)
T_min = 0.972, T_max = 0.992	R_int = 0.026
11668 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 0.83	Δρ_max = 0.23 e Å⁻³
2772 reflections	Δρ_min = −0.19 e Å⁻³
142 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
O2	1.11724 (18)	0.12433 (14)	0.49990 (13)	0.0607 (3)
Cl1	1.13273 (5)	0.19233 (4)	0.17024 (4)	0.04786 (14)
N1	0.73265 (15)	0.39471 (13)	0.81065 (11)	0.0344 (2)
C1	0.60912 (19)	0.31985 (15)	0.89780 (13)	0.0373 (3)
C8	1.01152 (18)	0.23770 (16)	0.56489 (14)	0.0388 (3)
C5	0.67204 (19)	0.53934 (15)	0.72045 (13)	0.0374 (3)
H5	0.7607	0.5877	0.6639	0.045*
O1	0.92281 (18)	0.36464 (13)	0.49974 (11)	0.0570 (3)
C4	0.4848 (2)	0.61779 (16)	0.70897 (14)	0.0390 (3)
C11	0.6787 (2)	0.16261 (18)	1.00116 (16)	0.0503 (4)
H11A	0.7271	0.0810	0.9453	0.075*
H11B	0.5770	0.1396	1.0707	0.075*
H11C	0.7768	0.1662	1.0539	0.075*
C3	0.3566 (2)	0.54196 (18)	0.79512 (16)	0.0441 (3)
H3	0.2282	0.5900	0.7897	0.053*
C2	0.4195 (2)	0.39556 (17)	0.88856 (15)	0.0430 (3)
H2	0.3323	0.3465	0.9468	0.052*
C6	0.93976 (19)	0.32296 (19)	0.81201 (15)	0.0436 (3)
H6A	0.9709	0.2834	0.9143	0.052*
H6B	1.0014	0.4055	0.7671	0.052*
C7	1.0172 (2)	0.18822 (18)	0.73100 (15)	0.0448 (3)
H7B	1.1466	0.1356	0.7534	0.054*
H7A	0.9463	0.1110	0.7692	0.054*
C9	0.4262 (2)	0.77820 (17)	0.60617 (17)	0.0510 (4)
H9B	0.4899	0.8477	0.6273	0.061*
H9A	0.2920	0.8242	0.6246	0.061*
C10	0.4713 (3)	0.7697 (2)	0.44375 (17)	0.0566 (4)
H10A	0.4327	0.8749	0.3825	0.085*
H10C	0.4054	0.7038	0.4214	0.085*
H10B	0.6042	0.7252	0.4247	0.085*
H2A	1.108 (3)	0.153 (3)	0.399 (3)	0.099 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0687 (7)	0.0570 (7)	0.0404 (6)	0.0055 (6)	−0.0043 (5)	−0.0115 (5)
Cl1	0.0537 (2)	0.0563 (2)	0.03510 (19)	−0.01908 (17)	0.00042 (14)	−0.01085 (14)
N1	0.0393 (5)	0.0394 (6)	0.0274 (5)	−0.0143 (4)	−0.0016 (4)	−0.0091 (4)
C1	0.0487 (7)	0.0390 (7)	0.0276 (5)	−0.0171 (6)	0.0032 (5)	−0.0114 (5)
C8	0.0357 (6)	0.0436 (7)	0.0364 (6)	−0.0143 (5)	−0.0016 (5)	−0.0048 (5)
C5	0.0470 (7)	0.0387 (7)	0.0306 (6)	−0.0185 (5)	−0.0004 (5)	−0.0088 (5)
O1	0.0768 (8)	0.0457 (6)	0.0376 (5)	−0.0042 (5)	−0.0076 (5)	−0.0044 (4)
C4	0.0499 (7)	0.0368 (6)	0.0329 (6)	−0.0116 (5)	−0.0040 (5)	−0.0124 (5)
C11	0.0660 (9)	0.0424 (8)	0.0364 (7)	−0.0154 (7)	0.0070 (6)	−0.0044 (6)
C3	0.0407 (7)	0.0496 (8)	0.0443 (7)	−0.0111 (6)	−0.0002 (6)	−0.0185 (6)
C2	0.0454 (7)	0.0486 (8)	0.0395 (7)	−0.0211 (6)	0.0081 (6)	−0.0148 (6)
C6	0.0391 (7)	0.0578 (8)	0.0350 (6)	−0.0148 (6)	−0.0088 (5)	−0.0070 (6)
C7	0.0382 (7)	0.0514 (8)	0.0350 (6)	−0.0061 (6)	−0.0022 (5)	−0.0010 (6)
C9	0.0661 (10)	0.0376 (7)	0.0460 (8)	−0.0078 (7)	−0.0099 (7)	−0.0087 (6)
C10	0.0693 (10)	0.0565 (9)	0.0428 (8)	−0.0199 (8)	−0.0084 (7)	−0.0039 (7)

Geometric parameters (Å, º) top

O2—C8	1.3097 (18)	C11—H11C	0.9600
O2—H2A	0.92 (3)	C3—C2	1.377 (2)
N1—C5	1.3499 (17)	C3—H3	0.9300
N1—C1	1.3604 (16)	C2—H2	0.9300
N1—C6	1.4885 (17)	C6—C7	1.514 (2)
C1—C2	1.381 (2)	C6—H6A	0.9700
C1—C11	1.4938 (19)	C6—H6B	0.9700
C8—O1	1.1971 (17)	C7—H7B	0.9700
C8—C7	1.5058 (19)	C7—H7A	0.9700
C5—C4	1.372 (2)	C9—C10	1.519 (2)
C5—H5	0.9300	C9—H9B	0.9700
C4—C3	1.388 (2)	C9—H9A	0.9700
C4—C9	1.5009 (19)	C10—H10A	0.9600
C11—H11A	0.9600	C10—H10C	0.9600
C11—H11B	0.9600	C10—H10B	0.9600

C8—O2—H2A	110.8 (16)	C3—C2—H2	119.3
C5—N1—C1	121.15 (11)	C1—C2—H2	119.3
C5—N1—C6	116.99 (11)	N1—C6—C7	114.17 (11)
C1—N1—C6	121.85 (11)	N1—C6—H6A	108.7
N1—C1—C2	117.68 (12)	C7—C6—H6A	108.7
N1—C1—C11	120.43 (13)	N1—C6—H6B	108.7
C2—C1—C11	121.88 (12)	C7—C6—H6B	108.7
O1—C8—O2	123.99 (13)	H6A—C6—H6B	107.6
O1—C8—C7	124.60 (13)	C8—C7—C6	114.89 (12)
O2—C8—C7	111.41 (12)	C8—C7—H7B	108.5
N1—C5—C4	122.58 (12)	C6—C7—H7B	108.5
N1—C5—H5	118.7	C8—C7—H7A	108.5
C4—C5—H5	118.7	C6—C7—H7A	108.5
C5—C4—C3	117.08 (13)	H7B—C7—H7A	107.5
C5—C4—C9	120.07 (13)	C4—C9—C10	112.48 (12)
C3—C4—C9	122.85 (14)	C4—C9—H9B	109.1
C1—C11—H11A	109.5	C10—C9—H9B	109.1
C1—C11—H11B	109.5	C4—C9—H9A	109.1
H11A—C11—H11B	109.5	C10—C9—H9A	109.1
C1—C11—H11C	109.5	H9B—C9—H9A	107.8
H11A—C11—H11C	109.5	C9—C10—H10A	109.5
H11B—C11—H11C	109.5	C9—C10—H10C	109.5
C2—C3—C4	119.99 (13)	H10A—C10—H10C	109.5
C2—C3—H3	120.0	C9—C10—H10B	109.5
C4—C3—H3	120.0	H10A—C10—H10B	109.5
C3—C2—C1	121.50 (12)	H10C—C10—H10B	109.5

C5—N1—C1—C2	1.26 (17)	C4—C3—C2—C1	−0.9 (2)
C6—N1—C1—C2	−179.81 (11)	N1—C1—C2—C3	−0.25 (19)
C5—N1—C1—C11	−177.69 (11)	C11—C1—C2—C3	178.69 (13)
C6—N1—C1—C11	1.24 (18)	C5—N1—C6—C7	−105.73 (14)
C1—N1—C5—C4	−1.18 (18)	C1—N1—C6—C7	75.30 (15)
C6—N1—C5—C4	179.84 (11)	O1—C8—C7—C6	−14.0 (2)
N1—C5—C4—C3	0.01 (19)	O2—C8—C7—C6	165.58 (13)
N1—C5—C4—C9	−179.76 (11)	N1—C6—C7—C8	69.15 (16)
C5—C4—C3—C2	0.99 (19)	C5—C4—C9—C10	68.80 (18)
C9—C4—C3—C2	−179.24 (13)	C3—C4—C9—C10	−110.95 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Cl1ⁱ	0.93	2.72	3.6249 (14)	166
C6—H6A···Cl1ⁱⁱ	0.97	2.68	3.6261 (14)	166
O2—H2A···Cl1	0.92 (3)	2.06 (3)	2.9749 (12)	170 (2)
C11—H11A···Cl1ⁱⁱⁱ	0.96	2.79	3.7410 (16)	170

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₆NO₂⁺·Cl⁻
M_r	229.70
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.5013 (4), 9.0509 (5), 9.3452 (5)
α, β, γ (°)	75.253 (2), 80.985 (2), 72.047 (2)
V (Å³)	581.59 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.32 × 0.20 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.972, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	11668, 2772, 2363
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.659

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.102, 0.83
No. of reflections	2772
No. of parameters	142
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.19

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Cl1ⁱ	0.93	2.72	3.6249 (14)	165.9
C6—H6A···Cl1ⁱⁱ	0.97	2.68	3.6261 (14)	166.3
O2—H2A···Cl1	0.92 (3)	2.06 (3)	2.9749 (12)	170 (2)
C11—H11A···Cl1ⁱⁱⁱ	0.96	2.79	3.7410 (16)	170

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

Acknowledgements

The authors thank the UGC, India, for financial support and Dr Babu Varghese, Senior Scientific Officer, SAIF, IIT, Chennai, India, for the X-ray intensity data collection.

References

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