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Acta Crystallogr Sect E Struct Rep Online. 2010 July 1; 66(Pt 7): o1639.
Published online 2010 June 16. doi:  10.1107/S1600536810021501
PMCID: PMC3006743

4-(2-Carb­oxy­vin­yl)pyridinium iodide

Abstract

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 [triangle]); Qu et al. (2004 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1639-scheme1.jpg

Experimental

Crystal data

  • C8H8NO2 +·I
  • M r = 277.05
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1639-efi1.jpg
  • 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 [triangle]) T min = 0.492, T max = 0.518
  • 9130 measured reflections
  • 2099 independent reflections
  • 1786 reflections with I > 2σ(I)
  • R int = 0.046

Refinement

  • R[F 2 > 2σ(F 2)] = 0.028
  • wR(F 2) = 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

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810021501/xu2766sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810021501/xu2766Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by Southeast University.

supplementary crystallographic information

Comment

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.

Experimental

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

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).

Figures

Fig. 1.
A partial packing diagram of the title compound, with the displacement ellipsoids were drawn at the 30% probability level.
Fig. 2.
Packing diagram of the title compound, showing the structure along the b axis. Hydrogen bonds are shown as dashed lines.

Crystal data

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

Rigaku SCXmini diffractometer2101 independent reflections
Radiation source: fine-focus sealed tube1786 reflections with I > 2σ(I)
graphiteRint = 0.046
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.1°
ω scanh = −6→6
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −20→20
Tmin = 0.492, Tmax = 0.518l = −15→15
9130 measured reflections

Refinement

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 = 1.11w = 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

Special details

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)

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*
O2−0.1307 (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)

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, °)

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, °)

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) x−3/2, −y+3/2, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU2766).

References

  • Cohen, J. H., Abdel-Magid, A. F., Almond, H. R. Jr & Maryanoff, C. A. (2002). Tetrahedron Lett.43, 1977–1981.
  • Ferguson, G. (1999). PRPKAPPA University of Guelph, Canada.
  • 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. [PubMed]
  • Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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