4-(2-Carb­oxy­vin­yl)pyridinium iodide

Hu, D.-Y.

doi:10.1107/S1600536810021501

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1639

doi:10.1107/S1600536810021501

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4-(2-Carboxyvinyl)pyridinium iodide

Dong-Yue Hu ^a ^*

^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 ); Qu et al. (2004 ).

Experimental

Crystal data

C₈H₈NO₂⁺·I⁻
M_r = 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 ) 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[F² > 2σ(F²)] = 0.028
wR(F²) = 0.064
S = 1.11
2099 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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); cell refinement: CrystalClear; data reduction: CrystalClear; 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 ).

Supporting information

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

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

checkCIF report

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

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.

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

	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.

4-(2-Carboxyvinyl)pyridinium iodide top

Crystal data top

C₈H₈NO₂⁺·I⁻	F(000) = 528.0
M_r = 277.05	D_x = 2.012 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1866 reflections
a = 4.9685 (10) Å	θ = 3.2–27.0°
b = 15.494 (3) Å	µ = 3.46 mm⁻¹
c = 12.123 (2) Å	T = 293 K
β = 101.48 (3)°	Prism, orange
V = 914.6 (3) Å³	0.20 × 0.20 × 0.20 mm
Z = 4

Data collection top

Rigaku SCXmini diffractometer	2101 independent reflections
Radiation source: fine-focus sealed tube	1786 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scan	h = −6→6
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −20→20
T_min = 0.492, T_max = 0.518	l = −15→15
9130 measured reflections

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.064	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0215P)² + 0.0886P] where P = (F_o² + 2F_c²)/3
2099 reflections	(Δ/σ)_max = 0.001
110 parameters	Δρ_max = 0.54 e Å⁻³
0 restraints	Δρ_min = −0.49 e Å⁻³

Crystal data top

C₈H₈NO₂⁺·I⁻	V = 914.6 (3) Å³
M_r = 277.05	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 4.9685 (10) Å	µ = 3.46 mm⁻¹
b = 15.494 (3) Å	T = 293 K
c = 12.123 (2) Å	0.20 × 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)
T_min = 0.492, T_max = 0.518	R_int = 0.046
9130 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.064	H-atom parameters constrained
S = 1.11	Δρ_max = 0.54 e Å⁻³
2099 reflections	Δρ_min = −0.49 e Å⁻³
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

	x	y	z	U_iso*/U_eq
N1	0.8838 (5)	0.62959 (16)	0.6895 (2)	0.0397 (6)
H1	1.0091	0.5971	0.7275	0.048*
C8	0.0739 (7)	0.91308 (18)	0.4041 (3)	0.0371 (7)
C3	0.7164 (6)	0.76753 (19)	0.6401 (3)	0.0387 (7)
H3	0.7325	0.8271	0.6486	0.046*
C6	0.2864 (6)	0.78463 (18)	0.4944 (3)	0.0362 (7)
H6	0.1361	0.7556	0.4527	0.043*
C4	0.4734 (6)	0.64341 (19)	0.5602 (3)	0.0396 (8)
H4	0.3229	0.6179	0.5138	0.048*
C5	0.4953 (6)	0.73228 (18)	0.5661 (2)	0.0321 (6)
C2	0.9097 (6)	0.7147 (2)	0.7004 (3)	0.0423 (8)
H2	1.0602	0.7382	0.7492	0.051*
C1	0.6722 (7)	0.59325 (19)	0.6224 (3)	0.0447 (8)
H1A	0.6590	0.5334	0.6176	0.054*
O1	0.1334 (5)	0.99482 (13)	0.3899 (2)	0.0527 (7)
H1B	0.0129	1.0164	0.3417	0.079*
O2	−0.1307 (4)	0.87875 (15)	0.3553 (2)	0.0545 (7)
C9	0.2913 (6)	0.8691 (2)	0.4834 (3)	0.0377 (7)
H9	0.4334	0.9009	0.5262	0.045*
I1	1.17185 (4)	0.413232 (12)	0.682811 (18)	0.04391 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0317 (13)	0.0381 (14)	0.0457 (16)	0.0063 (12)	−0.0011 (12)	0.0076 (12)
C8	0.0352 (17)	0.0361 (17)	0.0362 (18)	0.0011 (13)	−0.0017 (14)	0.0004 (13)
C3	0.0338 (16)	0.0316 (15)	0.0467 (18)	−0.0007 (13)	−0.0019 (13)	−0.0005 (14)
C6	0.0326 (16)	0.0378 (16)	0.0348 (17)	−0.0021 (13)	−0.0019 (13)	−0.0013 (13)
C4	0.0345 (17)	0.0370 (16)	0.0425 (19)	−0.0007 (13)	−0.0042 (14)	−0.0072 (14)
C5	0.0296 (14)	0.0357 (15)	0.0290 (16)	0.0020 (12)	0.0011 (12)	0.0011 (12)
C2	0.0324 (16)	0.0444 (18)	0.044 (2)	−0.0041 (14)	−0.0058 (14)	0.0001 (15)
C1	0.047 (2)	0.0318 (17)	0.052 (2)	−0.0002 (14)	0.0021 (17)	0.0012 (14)
O1	0.0523 (15)	0.0370 (12)	0.0579 (16)	−0.0062 (11)	−0.0152 (12)	0.0125 (11)
O2	0.0441 (14)	0.0390 (12)	0.0663 (17)	−0.0051 (11)	−0.0227 (12)	0.0069 (12)
C9	0.0330 (16)	0.0394 (17)	0.0350 (17)	−0.0017 (13)	−0.0067 (13)	0.0005 (13)
I1	0.04248 (15)	0.03397 (14)	0.04898 (17)	−0.00119 (9)	−0.00609 (11)	−0.00440 (9)

Geometric parameters (Å, º) top

N1—C1	1.321 (4)	C6—C5	1.460 (4)
N1—C2	1.330 (4)	C6—H6	0.9300
N1—H1	0.8600	C4—C1	1.360 (4)
C8—O2	1.195 (4)	C4—C5	1.382 (4)
C8—O1	1.319 (3)	C4—H4	0.9300
C8—C9	1.464 (4)	C2—H2	0.9300
C3—C2	1.359 (4)	C1—H1A	0.9300
C3—C5	1.385 (4)	O1—H1B	0.8200
C3—H3	0.9300	C9—H9	0.9300
C6—C9	1.316 (4)

C1—N1—C2	122.3 (3)	C5—C4—H4	120.0
C1—N1—H1	118.9	C4—C5—C3	118.0 (3)
C2—N1—H1	118.9	C4—C5—C6	118.9 (3)
O2—C8—O1	123.6 (3)	C3—C5—C6	123.0 (3)
O2—C8—C9	124.2 (3)	N1—C2—C3	120.0 (3)
O1—C8—C9	112.2 (3)	N1—C2—H2	120.0
C2—C3—C5	119.7 (3)	C3—C2—H2	120.0
C2—C3—H3	120.1	N1—C1—C4	119.9 (3)
C5—C3—H3	120.1	N1—C1—H1A	120.0
C9—C6—C5	126.0 (3)	C4—C1—H1A	120.0
C9—C6—H6	117.0	C8—O1—H1B	109.5
C5—C6—H6	117.0	C6—C9—C8	120.2 (3)
C1—C4—C5	120.0 (3)	C6—C9—H9	119.9
C1—C4—H4	120.0	C8—C9—H9	119.9

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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+3/2, −y+3/2, z+1/2; (ii) x−3/2, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₈H₈NO₂⁺·I⁻
M_r	277.05
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	4.9685 (10), 15.494 (3), 12.123 (2)
β (°)	101.48 (3)
V (Å³)	914.6 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.46
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.492, 0.518
No. of measured, independent and observed [I > 2σ(I)] reflections	9130, 2101, 1786
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.064, 1.11
No. of reflections	2099
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	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+3/2, −y+3/2, z+1/2; (ii) x−3/2, −y+3/2, z−1/2.

Acknowledgements

This work was supported by Southeast University.

References

Cohen, 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
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada. Google Scholar
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. Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar