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ISSN: 2056-9890

4-(2-Carb­­oxy­vin­yl)pyridinium iodide

aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
*Correspondence e-mail: hdyhudongyue@163.com

(Received 21 May 2010; accepted 5 June 2010; online 16 June 2010)

In the crystal structure of the title salt, C8H8NO2+·I, the cations and anions are linked by bifurcated N—H⋯(O,I) hydrogen bonds. A near-linear O—H⋯I hydrogen bond also exists between the cation and anion, resulting in a two-dimensional network. In the cation, the carboxyl group is twisted with respect to the pyridine ring at a dihedral angle of 15.34 (17)°.

Related literature

3-(Pyridin-4-yl)acrylic acid is an inter­mediate in the synthesis of 3-amino-3-(pyridin-4-yl)propanoic acid, which is of inter­est as a precursor for the synthesis of novel biologically active compounds, see: Cohen et al. (2002[Cohen, J. H., Abdel-Magid, A. F., Almond, H. R. Jr & Maryanoff, C. A. (2002). Tetrahedron Lett. 43, 1977-1981.]); Qu et al. (2004[Qu, Z.-R., Zhao, H., Wang, Y.-P., Wang, X.-S., Ye, Q., Li, Y.-H., Xiong, R.-G., Abrahams, B. F., Liu, Z.-G. & Xue, Z.-L. (2004). Chem. Eur. J. 10, 54-60.]).

[Scheme 1]

Experimental

Crystal data
  • C8H8NO2+·I

  • Mr = 277.05

  • Monoclinic, P 21 /n

  • a = 4.9685 (10) Å

  • b = 15.494 (3) Å

  • c = 12.123 (2) Å

  • β = 101.48 (3)°

  • V = 914.6 (3) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 3.46 mm−1

  • T = 293 K

  • 0.20 × 0.20 × 0.20 mm

Data collection
  • Rigaku SCXmini diffractometer

  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.492, Tmax = 0.518

  • 9130 measured reflections

  • 2099 independent reflections

  • 1786 reflections with I > 2σ(I)

  • Rint = 0.046

Refinement
  • R[F2 > 2σ(F2)] = 0.028

  • wR(F2) = 0.064

  • S = 1.11

  • 2099 reflections

  • 110 parameters

  • H-atom parameters constrained

  • Δρmax = 0.54 e Å−3

  • Δρmin = −0.49 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1⋯I1 0.86 3.04 3.652 (3) 130
N1—H1⋯O2i 0.86 2.15 2.819 (3) 134
O1—H1B⋯I1ii 0.82 2.54 3.362 (2) 175
Symmetry codes: (i) [x+{\script{3\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]; (ii) [x-{\script{3\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}].

Data collection: CrystalClear (Rigaku, 2005[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999[Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.]).

Supporting information


Comment top

β-Amino acids are important molecules due to their pharmacological properties. Recently, there has been an increased interest in the enantiomeric preparation of β-amino acids as precursors for the synthesis of novel biologically active compounds (Cohen et al., 2002; Qu et al., 2004). 3-(Pyridin-4-yl)acrylic acid is the intermediate to synthesize 3-amino-3-(pyridin-4-yl)propanoic acid.

The asymmetric unit of the title compound (Fig. 1) contains one 4-(2-carboxyvinyl) pyridinium and one iodate anion. The conformation of the cation is stabilized by an intramolecular N—H···I and C—H···O hydrogen bond (Table 1). In the crystal structure (Fig. 2), molecules are connected by intermolecular N—H···O, O—H···I and C—H···O hydrogen bonds into chains running parallel to the b axis (Table 1).

The dielectric constant of the title compound as a function of temperature indicates that the permittivity is basically temperature-independent, suggesting that this compound should be not a real ferroelectrics or there may be no distinct phase transition occurred within the measured temperature range.

Related literature top

3-(Pyridin-4-yl)acrylic acid is an intermediate in the synthesis of 3-amino-3-(pyridin-4-yl)propanoic acid, which is of interest as a precursor for the synthesis of novel biologically active compounds, see: Cohen et al. (2002); Qu et al. (2004).

Experimental top

In a dry, N2-filled three-necked flask fitted with stirrer, 4-pyridinecarboxaldehyde (1.07 g, 10 mmol) and malonic acid (2.50 g, 24 mmol) were dissolved in pyridine (4 ml) and piperidine (0.1 ml) and this solution was refluxed for 4.5 h and the mixture was then worked up. To the suspension was then added ethylether (5 ml), and the white precipitate was filtered and washed with ethylether (3.5 ml) to give (E)-3-(4-pyridyl)acrylic acid. (E)-3-(4-pyridyl)acrylic acid (0.5 g, 3 mmol) and hydriodic acid (0.43 g, 3 mmol) were dissolved in ethanol (10 ml). After slow evaporation of the solution over a period of 3 days, orange prismatic crystals of the title compound suitable for X-ray diffraction analysis were isolated.

Refinement top

All H atoms were placed at calculated positions with C—H = 0.93, N—H = 0.86 and O—H = 0.82 Å, and refined in riding mode with Uiso(H) = 1.5Ueq(O) and 1.2Ueq(C,N).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999).

Figures top
[Figure 1] Fig. 1. A partial packing diagram of the title compound, with the displacement ellipsoids were drawn at the 30% probability level.
[Figure 2] Fig. 2. Packing diagram of the title compound, showing the structure along the b axis. Hydrogen bonds are shown as dashed lines.
4-(2-Carboxyvinyl)pyridinium iodide top
Crystal data top
C8H8NO2+·IF(000) = 528.0
Mr = 277.05Dx = 2.012 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1866 reflections
a = 4.9685 (10) Åθ = 3.2–27.0°
b = 15.494 (3) ŵ = 3.46 mm1
c = 12.123 (2) ÅT = 293 K
β = 101.48 (3)°Prism, orange
V = 914.6 (3) Å30.20 × 0.20 × 0.20 mm
Z = 4
Data collection top
Rigaku SCXmini
diffractometer
2101 independent reflections
Radiation source: fine-focus sealed tube1786 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.046
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.1°
ω scanh = 66
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
k = 2020
Tmin = 0.492, Tmax = 0.518l = 1515
9130 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.064H-atom parameters constrained
S = 1.11 w = 1/[σ2(Fo2) + (0.0215P)2 + 0.0886P]
where P = (Fo2 + 2Fc2)/3
2099 reflections(Δ/σ)max = 0.001
110 parametersΔρmax = 0.54 e Å3
0 restraintsΔρmin = 0.49 e Å3
Crystal data top
C8H8NO2+·IV = 914.6 (3) Å3
Mr = 277.05Z = 4
Monoclinic, P21/nMo Kα radiation
a = 4.9685 (10) ŵ = 3.46 mm1
b = 15.494 (3) ÅT = 293 K
c = 12.123 (2) Å0.20 × 0.20 × 0.20 mm
β = 101.48 (3)°
Data collection top
Rigaku SCXmini
diffractometer
2101 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
1786 reflections with I > 2σ(I)
Tmin = 0.492, Tmax = 0.518Rint = 0.046
9130 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0280 restraints
wR(F2) = 0.064H-atom parameters constrained
S = 1.11Δρmax = 0.54 e Å3
2099 reflectionsΔρmin = 0.49 e Å3
110 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
N10.8838 (5)0.62959 (16)0.6895 (2)0.0397 (6)
H11.00910.59710.72750.048*
C80.0739 (7)0.91308 (18)0.4041 (3)0.0371 (7)
C30.7164 (6)0.76753 (19)0.6401 (3)0.0387 (7)
H30.73250.82710.64860.046*
C60.2864 (6)0.78463 (18)0.4944 (3)0.0362 (7)
H60.13610.75560.45270.043*
C40.4734 (6)0.64341 (19)0.5602 (3)0.0396 (8)
H40.32290.61790.51380.048*
C50.4953 (6)0.73228 (18)0.5661 (2)0.0321 (6)
C20.9097 (6)0.7147 (2)0.7004 (3)0.0423 (8)
H21.06020.73820.74920.051*
C10.6722 (7)0.59325 (19)0.6224 (3)0.0447 (8)
H1A0.65900.53340.61760.054*
O10.1334 (5)0.99482 (13)0.3899 (2)0.0527 (7)
H1B0.01291.01640.34170.079*
O20.1307 (4)0.87875 (15)0.3553 (2)0.0545 (7)
C90.2913 (6)0.8691 (2)0.4834 (3)0.0377 (7)
H90.43340.90090.52620.045*
I11.17185 (4)0.413232 (12)0.682811 (18)0.04391 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0317 (13)0.0381 (14)0.0457 (16)0.0063 (12)0.0011 (12)0.0076 (12)
C80.0352 (17)0.0361 (17)0.0362 (18)0.0011 (13)0.0017 (14)0.0004 (13)
C30.0338 (16)0.0316 (15)0.0467 (18)0.0007 (13)0.0019 (13)0.0005 (14)
C60.0326 (16)0.0378 (16)0.0348 (17)0.0021 (13)0.0019 (13)0.0013 (13)
C40.0345 (17)0.0370 (16)0.0425 (19)0.0007 (13)0.0042 (14)0.0072 (14)
C50.0296 (14)0.0357 (15)0.0290 (16)0.0020 (12)0.0011 (12)0.0011 (12)
C20.0324 (16)0.0444 (18)0.044 (2)0.0041 (14)0.0058 (14)0.0001 (15)
C10.047 (2)0.0318 (17)0.052 (2)0.0002 (14)0.0021 (17)0.0012 (14)
O10.0523 (15)0.0370 (12)0.0579 (16)0.0062 (11)0.0152 (12)0.0125 (11)
O20.0441 (14)0.0390 (12)0.0663 (17)0.0051 (11)0.0227 (12)0.0069 (12)
C90.0330 (16)0.0394 (17)0.0350 (17)0.0017 (13)0.0067 (13)0.0005 (13)
I10.04248 (15)0.03397 (14)0.04898 (17)0.00119 (9)0.00609 (11)0.00440 (9)
Geometric parameters (Å, º) top
N1—C11.321 (4)C6—C51.460 (4)
N1—C21.330 (4)C6—H60.9300
N1—H10.8600C4—C11.360 (4)
C8—O21.195 (4)C4—C51.382 (4)
C8—O11.319 (3)C4—H40.9300
C8—C91.464 (4)C2—H20.9300
C3—C21.359 (4)C1—H1A0.9300
C3—C51.385 (4)O1—H1B0.8200
C3—H30.9300C9—H90.9300
C6—C91.316 (4)
C1—N1—C2122.3 (3)C5—C4—H4120.0
C1—N1—H1118.9C4—C5—C3118.0 (3)
C2—N1—H1118.9C4—C5—C6118.9 (3)
O2—C8—O1123.6 (3)C3—C5—C6123.0 (3)
O2—C8—C9124.2 (3)N1—C2—C3120.0 (3)
O1—C8—C9112.2 (3)N1—C2—H2120.0
C2—C3—C5119.7 (3)C3—C2—H2120.0
C2—C3—H3120.1N1—C1—C4119.9 (3)
C5—C3—H3120.1N1—C1—H1A120.0
C9—C6—C5126.0 (3)C4—C1—H1A120.0
C9—C6—H6117.0C8—O1—H1B109.5
C5—C6—H6117.0C6—C9—C8120.2 (3)
C1—C4—C5120.0 (3)C6—C9—H9119.9
C1—C4—H4120.0C8—C9—H9119.9
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···I10.863.043.652 (3)130
N1—H1···O2i0.862.152.819 (3)134
O1—H1B···I1ii0.822.543.362 (2)175
Symmetry codes: (i) x+3/2, y+3/2, z+1/2; (ii) x3/2, y+3/2, z1/2.

Experimental details

Crystal data
Chemical formulaC8H8NO2+·I
Mr277.05
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)4.9685 (10), 15.494 (3), 12.123 (2)
β (°) 101.48 (3)
V3)914.6 (3)
Z4
Radiation typeMo Kα
µ (mm1)3.46
Crystal size (mm)0.20 × 0.20 × 0.20
Data collection
DiffractometerRigaku SCXmini
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.492, 0.518
No. of measured, independent and
observed [I > 2σ(I)] reflections
9130, 2101, 1786
Rint0.046
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.064, 1.11
No. of reflections2099
No. of parameters110
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.54, 0.49

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···I10.863.043.652 (3)130
N1—H1···O2i0.862.152.819 (3)134
O1—H1B···I1ii0.822.543.362 (2)175
Symmetry codes: (i) x+3/2, y+3/2, z+1/2; (ii) x3/2, y+3/2, z1/2.
 

Acknowledgements

This work was supported by Southeast University.

References

First citationCohen, J. H., Abdel-Magid, A. F., Almond, H. R. Jr & Maryanoff, C. A. (2002). Tetrahedron Lett. 43, 1977–1981.  Web of Science CrossRef CAS Google Scholar
First citationFerguson, G. (1999). PRPKAPPA. University of Guelph, Canada.  Google Scholar
First citationQu, Z.-R., Zhao, H., Wang, Y.-P., Wang, X.-S., Ye, Q., Li, Y.-H., Xiong, R.-G., Abrahams, B. F., Liu, Z.-G. & Xue, Z.-L. (2004). Chem. Eur. J. 10, 54–60.  Google Scholar
First citationRigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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