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

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[Judge, S. & Bever, C. (2006). Pharmacol. Ther. 111, 224-259.]); Schwid et al. (1997[Schwid, S. B., Petrie, M. D., McDermott, M. P., Tierney, D. S., Mason, D. H. & Goodman, A. D. (1997). Neurology, 48, 817-821.]); Strupp et al. (2004[Strupp, M., Kalla, R., Dichgans, M., Fraitinger, T., Glasauer, S. & Brandt, T. (2004). Neurology, 62, 1623-1625.]). For related structures, see: Anderson et al. (2005[Anderson, F. P., Gallagher, J. F., Kenny, P. T. M. & Lough, A. J. (2005). Acta Cryst. E61, o1350-o1353.]); Fun et al. (2009[Fun, H.-K., John, J., Jebas, S. R. & Balasubramanian, T. (2009). Acta Cryst. E65, o765-o766.]).

[Scheme 1]

Experimental

Crystal data
  • C11H16NO2+·Cl

  • Mr = 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[Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison Wisconsin, USA.]) Tmin = 0.972, Tmax = 0.992

  • 11668 measured reflections

  • 2772 independent reflections

  • 2363 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.23 e Å−3

  • Δρmin = −0.19 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2008[Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


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%)

Refinement top

All H atoms on carbons were positioned geometrically with C—H distances ranging from 0.95 to 1.00 Å and refined as riding on their parent atoms, with Uiso(H) = 1.2Ueq(C) or Uiso(H) = 1.5Ueq(Cmethyl) The hydroxyl H atom was freely refined.

Structure description 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.

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
[Figure 1] 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+·ClZ = 2
Mr = 229.70F(000) = 244
Triclinic, P1Dx = 1.312 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.5013 (4) ÅCell parameters from 5710 reflections
b = 9.0509 (5) Åθ = 1.8–28.5°
c = 9.3452 (5) ŵ = 0.31 mm1
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 tube2363 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
ω and φ scansθmax = 27.9°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
h = 99
Tmin = 0.972, Tmax = 0.992k = 1111
11668 measured reflectionsl = 1012
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.033H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.102 w = 1/[σ2(Fo2) + (0.0665P)2 + 0.2215P]
where P = (Fo2 + 2Fc2)/3
S = 0.83(Δ/σ)max < 0.001
2772 reflectionsΔρmax = 0.23 e Å3
142 parametersΔρmin = 0.19 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.034 (6)
Crystal data top
C11H16NO2+·Clγ = 72.047 (2)°
Mr = 229.70V = 581.59 (5) Å3
Triclinic, P1Z = 2
a = 7.5013 (4) ÅMo Kα radiation
b = 9.0509 (5) ŵ = 0.31 mm1
c = 9.3452 (5) ÅT = 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)
Tmin = 0.972, Tmax = 0.992Rint = 0.026
11668 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.102H atoms treated by a mixture of independent and constrained refinement
S = 0.83Δρmax = 0.23 e Å3
2772 reflectionsΔρmin = 0.19 e Å3
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
xyzUiso*/Ueq
O21.11724 (18)0.12433 (14)0.49990 (13)0.0607 (3)
Cl11.13273 (5)0.19233 (4)0.17024 (4)0.04786 (14)
N10.73265 (15)0.39471 (13)0.81065 (11)0.0344 (2)
C10.60912 (19)0.31985 (15)0.89780 (13)0.0373 (3)
C81.01152 (18)0.23770 (16)0.56489 (14)0.0388 (3)
C50.67204 (19)0.53934 (15)0.72045 (13)0.0374 (3)
H50.76070.58770.66390.045*
O10.92281 (18)0.36464 (13)0.49974 (11)0.0570 (3)
C40.4848 (2)0.61779 (16)0.70897 (14)0.0390 (3)
C110.6787 (2)0.16261 (18)1.00116 (16)0.0503 (4)
H11A0.72710.08100.94530.075*
H11B0.57700.13961.07070.075*
H11C0.77680.16621.05390.075*
C30.3566 (2)0.54196 (18)0.79512 (16)0.0441 (3)
H30.22820.59000.78970.053*
C20.4195 (2)0.39556 (17)0.88856 (15)0.0430 (3)
H20.33230.34650.94680.052*
C60.93976 (19)0.32296 (19)0.81201 (15)0.0436 (3)
H6A0.97090.28340.91430.052*
H6B1.00140.40550.76710.052*
C71.0172 (2)0.18822 (18)0.73100 (15)0.0448 (3)
H7B1.14660.13560.75340.054*
H7A0.94630.11100.76920.054*
C90.4262 (2)0.77820 (17)0.60617 (17)0.0510 (4)
H9B0.48990.84770.62730.061*
H9A0.29200.82420.62460.061*
C100.4713 (3)0.7697 (2)0.44375 (17)0.0566 (4)
H10A0.43270.87490.38250.085*
H10C0.40540.70380.42140.085*
H10B0.60420.72520.42470.085*
H2A1.108 (3)0.153 (3)0.399 (3)0.099 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O20.0687 (7)0.0570 (7)0.0404 (6)0.0055 (6)0.0043 (5)0.0115 (5)
Cl10.0537 (2)0.0563 (2)0.03510 (19)0.01908 (17)0.00042 (14)0.01085 (14)
N10.0393 (5)0.0394 (6)0.0274 (5)0.0143 (4)0.0016 (4)0.0091 (4)
C10.0487 (7)0.0390 (7)0.0276 (5)0.0171 (6)0.0032 (5)0.0114 (5)
C80.0357 (6)0.0436 (7)0.0364 (6)0.0143 (5)0.0016 (5)0.0048 (5)
C50.0470 (7)0.0387 (7)0.0306 (6)0.0185 (5)0.0004 (5)0.0088 (5)
O10.0768 (8)0.0457 (6)0.0376 (5)0.0042 (5)0.0076 (5)0.0044 (4)
C40.0499 (7)0.0368 (6)0.0329 (6)0.0116 (5)0.0040 (5)0.0124 (5)
C110.0660 (9)0.0424 (8)0.0364 (7)0.0154 (7)0.0070 (6)0.0044 (6)
C30.0407 (7)0.0496 (8)0.0443 (7)0.0111 (6)0.0002 (6)0.0185 (6)
C20.0454 (7)0.0486 (8)0.0395 (7)0.0211 (6)0.0081 (6)0.0148 (6)
C60.0391 (7)0.0578 (8)0.0350 (6)0.0148 (6)0.0088 (5)0.0070 (6)
C70.0382 (7)0.0514 (8)0.0350 (6)0.0061 (6)0.0022 (5)0.0010 (6)
C90.0661 (10)0.0376 (7)0.0460 (8)0.0078 (7)0.0099 (7)0.0087 (6)
C100.0693 (10)0.0565 (9)0.0428 (8)0.0199 (8)0.0084 (7)0.0039 (7)
Geometric parameters (Å, º) top
O2—C81.3097 (18)C11—H11C0.9600
O2—H2A0.92 (3)C3—C21.377 (2)
N1—C51.3499 (17)C3—H30.9300
N1—C11.3604 (16)C2—H20.9300
N1—C61.4885 (17)C6—C71.514 (2)
C1—C21.381 (2)C6—H6A0.9700
C1—C111.4938 (19)C6—H6B0.9700
C8—O11.1971 (17)C7—H7B0.9700
C8—C71.5058 (19)C7—H7A0.9700
C5—C41.372 (2)C9—C101.519 (2)
C5—H50.9300C9—H9B0.9700
C4—C31.388 (2)C9—H9A0.9700
C4—C91.5009 (19)C10—H10A0.9600
C11—H11A0.9600C10—H10C0.9600
C11—H11B0.9600C10—H10B0.9600
C8—O2—H2A110.8 (16)C3—C2—H2119.3
C5—N1—C1121.15 (11)C1—C2—H2119.3
C5—N1—C6116.99 (11)N1—C6—C7114.17 (11)
C1—N1—C6121.85 (11)N1—C6—H6A108.7
N1—C1—C2117.68 (12)C7—C6—H6A108.7
N1—C1—C11120.43 (13)N1—C6—H6B108.7
C2—C1—C11121.88 (12)C7—C6—H6B108.7
O1—C8—O2123.99 (13)H6A—C6—H6B107.6
O1—C8—C7124.60 (13)C8—C7—C6114.89 (12)
O2—C8—C7111.41 (12)C8—C7—H7B108.5
N1—C5—C4122.58 (12)C6—C7—H7B108.5
N1—C5—H5118.7C8—C7—H7A108.5
C4—C5—H5118.7C6—C7—H7A108.5
C5—C4—C3117.08 (13)H7B—C7—H7A107.5
C5—C4—C9120.07 (13)C4—C9—C10112.48 (12)
C3—C4—C9122.85 (14)C4—C9—H9B109.1
C1—C11—H11A109.5C10—C9—H9B109.1
C1—C11—H11B109.5C4—C9—H9A109.1
H11A—C11—H11B109.5C10—C9—H9A109.1
C1—C11—H11C109.5H9B—C9—H9A107.8
H11A—C11—H11C109.5C9—C10—H10A109.5
H11B—C11—H11C109.5C9—C10—H10C109.5
C2—C3—C4119.99 (13)H10A—C10—H10C109.5
C2—C3—H3120.0C9—C10—H10B109.5
C4—C3—H3120.0H10A—C10—H10B109.5
C3—C2—C1121.50 (12)H10C—C10—H10B109.5
C5—N1—C1—C21.26 (17)C4—C3—C2—C10.9 (2)
C6—N1—C1—C2179.81 (11)N1—C1—C2—C30.25 (19)
C5—N1—C1—C11177.69 (11)C11—C1—C2—C3178.69 (13)
C6—N1—C1—C111.24 (18)C5—N1—C6—C7105.73 (14)
C1—N1—C5—C41.18 (18)C1—N1—C6—C775.30 (15)
C6—N1—C5—C4179.84 (11)O1—C8—C7—C614.0 (2)
N1—C5—C4—C30.01 (19)O2—C8—C7—C6165.58 (13)
N1—C5—C4—C9179.76 (11)N1—C6—C7—C869.15 (16)
C5—C4—C3—C20.99 (19)C5—C4—C9—C1068.80 (18)
C9—C4—C3—C2179.24 (13)C3—C4—C9—C10110.95 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···Cl1i0.932.723.6249 (14)166
C6—H6A···Cl1ii0.972.683.6261 (14)166
O2—H2A···Cl10.92 (3)2.06 (3)2.9749 (12)170 (2)
C11—H11A···Cl1iii0.962.793.7410 (16)170
Symmetry codes: (i) x1, y, z+1; (ii) x, y, z+1; (iii) x+2, y, z+1.

Experimental details

Crystal data
Chemical formulaC11H16NO2+·Cl
Mr229.70
Crystal system, space groupTriclinic, 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)
V3)581.59 (5)
Z2
Radiation typeMo Kα
µ (mm1)0.31
Crystal size (mm)0.32 × 0.20 × 0.10
Data collection
DiffractometerBruker APEXII CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2008)
Tmin, Tmax0.972, 0.992
No. of measured, independent and
observed [I > 2σ(I)] reflections
11668, 2772, 2363
Rint0.026
(sin θ/λ)max1)0.659
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.102, 0.83
No. of reflections2772
No. of parameters142
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
C2—H2···Cl1i0.932.723.6249 (14)165.9
C6—H6A···Cl1ii0.972.683.6261 (14)166.3
O2—H2A···Cl10.92 (3)2.06 (3)2.9749 (12)170 (2)
C11—H11A···Cl1iii0.962.793.7410 (16)170
Symmetry codes: (i) x1, 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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