3-Methyl-2-vinyl­pyridinium phosphate

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

doi:10.1107/S160053681300576X

organic compounds

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ISSN: 2056-9890

Volume 69| Part 4| April 2013| Page o487

doi:10.1107/S160053681300576X

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3-Methyl-2-vinylpyridinium phosphate

Ganesan Kalaiselvi,^a Vijayakumar Sabari,^b Sengottuvelan Balasubramanian ^a and Sanmargam Aravindhan ^b ^*

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

(Received 1 February 2013; accepted 27 February 2013; online 6 March 2013)

In the title salt, C₈H₁₀N⁺·H₂PO₄⁻, the cation is essentially planar (r.m.s. deviation = 0.063 Å). In the crystal, the phosphate anions form inversion R₂²(8) dimers via pairs of O—H⋯O hydrogen bonds. These dimers are further linked by pairs of O—H⋯O hydrogen bonds, also enclosing R₂²(8) loops, forming chains running along [001]. The cations are bonded to the anions via N—H⋯O hydrogen bonds and C—H⋯O contacts.

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 ); Sabari et al. (2012 ).

Experimental

Crystal data

C₈H₁₀N⁺·H₂PO₄⁻
M_r = 217.16
Monoclinic, P 2₁ /c
a = 7.7089 (6) Å
b = 16.3668 (13) Å
c = 8.0649 (6) Å
β = 109.689 (4)°
V = 958.06 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 293 K
0.30 × 0.30 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker 2008 ) T_min = 0.922, T_max = 0.947
8970 measured reflections
2362 independent reflections
2052 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.114
S = 1.08
2362 reflections
136 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.86	1.83	2.6558 (18)	160
O3—H3A⋯O1ⁱ	0.89 (1)	1.72 (1)	2.5995 (18)	173 (3)
O4—H4A⋯O2ⁱⁱ	0.89 (1)	1.72 (1)	2.6002 (17)	170 (3)
C1—H1A⋯O1ⁱⁱⁱ	0.93	2.48	3.172 (2)	131
Symmetry codes: (i) -x, -y+1, -z+2; (ii) -x, -y+1, -z+1; (iii) -x+1, -y+1, -z+2.

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 for Windows (Farrugia, 2012 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681300576X/bt6887sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681300576X/bt6887Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681300576X/bt6887Isup3.cml

checkCIF report

Comment top

4-Aminopyridine (Fampridine) is used clinically in Lambert-Eaton myastheni 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 3-methyl 2-vinyl pyridinium cation and one phosphate anion. The C1—N1—C5 angle in the pyridinium ring is widened to 123.35 (2) °, compared to 115.25 (13)° in 4-aminopyridine (Anderson et al., 2005), 121.20 (15) in 1-(2-carboxyethyl)-5-ethyl-2-methylpyridinium (Sabari et al., 2012) and 120.7 (2)° in Aminopyridinium (Fun et al., 2009). The 3-methyl 2-vinyl pyridinium ring is essentially planar with the maximum deviation from planarity being 0.008 (2) Å for atom C5. The sum of the bond angles around the N1 atom (359.89°) indicates sp² hybridization.

The phosphate anions form centrosymmetric R₂²(8) dimers via O—H···O hydrogen bonds. These dimers are further linked to chains running along the c axis. The cations are boned to the anions via N—H···O hydrogen bonds and C—H···O contacts.

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); Sabari et al. (2012).

Experimental top

1 g (0.0084 mol) of freshly distilled 3-methyl 2-vinyl pyridine was dissolved in 15 ml of diethyl ether at -10°C under nitrogen atmosphere. To the above solution, 0.5 ml of H₃PO₄ and 10 ml of diethyl ether mixture was added in drops with continuous stirring. The product obtained as a white solid was filtered, washed with diethyl ether and dried under vacuum, the product was recrystallized from methanol. Yield: 100% (1.82 g).

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 for Windows (Farrugia, 2012); 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).
	Fig. 2. A view of the crystal packing. Hydrogen bonds are drawn as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.

3-Methyl-2-vinylpyridinium phosphate top

Crystal data top

C₈H₁₀N⁺·H₂O₄P⁻	F(000) = 456
M_r = 217.16	D_x = 1.506 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8834 reflections
a = 7.7089 (6) Å	θ = 2.1–31.2°
b = 16.3668 (13) Å	µ = 0.28 mm⁻¹
c = 8.0649 (6) Å	T = 293 K
β = 109.689 (4)°	Block, colourless
V = 958.06 (13) Å³	0.30 × 0.30 × 0.20 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	2362 independent reflections
Radiation source: fine-focus sealed tube	2052 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ω and ϕ scan	θ_max = 28.3°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker 2008)	h = −10→10
T_min = 0.922, T_max = 0.947	k = −21→17
8970 measured reflections	l = −10→10

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0631P)² + 0.2803P] where P = (F_o² + 2F_c²)/3
2362 reflections	(Δ/σ)_max = 0.003
136 parameters	Δρ_max = 0.28 e Å⁻³
3 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₈H₁₀N⁺·H₂O₄P⁻	V = 958.06 (13) Å³
M_r = 217.16	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.7089 (6) Å	µ = 0.28 mm⁻¹
b = 16.3668 (13) Å	T = 293 K
c = 8.0649 (6) Å	0.30 × 0.30 × 0.20 mm
β = 109.689 (4)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2362 independent reflections
Absorption correction: multi-scan (SADABS; Bruker 2008)	2052 reflections with I > 2σ(I)
T_min = 0.922, T_max = 0.947	R_int = 0.026
8970 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	3 restraints
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.28 e Å⁻³
2362 reflections	Δρ_min = −0.33 e Å⁻³
136 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
C1	0.5293 (2)	0.35216 (10)	0.9141 (2)	0.0394 (4)
H1A	0.5318	0.4089	0.9225	0.047*
C2	0.6707 (3)	0.30687 (12)	1.0253 (3)	0.0446 (4)
H2	0.7706	0.3322	1.1082	0.054*
C3	0.6608 (2)	0.22259 (11)	1.0112 (3)	0.0420 (4)
H3	0.7546	0.1911	1.0870	0.050*
C4	0.5138 (2)	0.18417 (10)	0.8859 (2)	0.0349 (4)
C5	0.3751 (2)	0.23315 (9)	0.7738 (2)	0.0304 (3)
C6	0.2165 (2)	0.19908 (11)	0.6336 (2)	0.0404 (4)
H6	0.1973	0.1432	0.6382	0.048*
C7	0.1003 (3)	0.23843 (13)	0.5042 (3)	0.0514 (5)
H7A	0.1131	0.2945	0.4934	0.062*
H7B	0.0040	0.2106	0.4221	0.062*
C8	0.5063 (3)	0.09263 (11)	0.8732 (3)	0.0545 (5)
H8A	0.3981	0.0732	0.8944	0.082*
H8B	0.6139	0.0699	0.9594	0.082*
H8C	0.5020	0.0762	0.7576	0.082*
N1	0.38850 (18)	0.31502 (8)	0.79424 (17)	0.0319 (3)
H1	0.3015	0.3448	0.7263	0.038*
O1	0.20750 (17)	0.49478 (7)	0.95492 (15)	0.0374 (3)
O2	0.12761 (18)	0.42554 (7)	0.65535 (15)	0.0414 (3)
O3	−0.11397 (18)	0.44558 (8)	0.78857 (17)	0.0460 (3)
O4	0.0217 (2)	0.56754 (7)	0.68547 (16)	0.0446 (3)
P1	0.06935 (6)	0.48168 (2)	0.77599 (5)	0.03024 (15)
H3A	−0.143 (4)	0.4698 (16)	0.875 (3)	0.082 (9)*
H4A	−0.032 (4)	0.5639 (19)	0.5694 (14)	0.093 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0427 (9)	0.0273 (8)	0.0485 (10)	−0.0054 (6)	0.0156 (8)	−0.0067 (7)
C2	0.0361 (9)	0.0435 (10)	0.0475 (10)	−0.0078 (7)	0.0052 (8)	−0.0079 (8)
C3	0.0358 (9)	0.0410 (10)	0.0443 (10)	0.0033 (7)	0.0070 (8)	0.0046 (8)
C4	0.0373 (8)	0.0276 (8)	0.0396 (9)	0.0001 (6)	0.0127 (7)	0.0030 (6)
C5	0.0335 (8)	0.0259 (7)	0.0333 (8)	−0.0020 (6)	0.0132 (6)	0.0008 (6)
C6	0.0433 (9)	0.0311 (8)	0.0416 (9)	−0.0076 (7)	0.0075 (8)	−0.0013 (7)
C7	0.0503 (11)	0.0437 (10)	0.0529 (11)	0.0008 (8)	0.0077 (9)	−0.0073 (9)
C8	0.0614 (12)	0.0271 (9)	0.0652 (13)	0.0024 (8)	0.0085 (10)	0.0084 (9)
N1	0.0333 (7)	0.0259 (7)	0.0360 (7)	0.0012 (5)	0.0113 (6)	0.0007 (5)
O1	0.0367 (6)	0.0395 (6)	0.0296 (6)	−0.0004 (5)	0.0028 (5)	−0.0013 (5)
O2	0.0573 (8)	0.0318 (6)	0.0308 (6)	0.0166 (5)	0.0092 (5)	0.0004 (5)
O3	0.0444 (7)	0.0518 (8)	0.0377 (7)	−0.0129 (6)	0.0083 (6)	−0.0120 (6)
O4	0.0703 (9)	0.0243 (6)	0.0330 (6)	0.0110 (5)	0.0093 (6)	0.0008 (5)
P1	0.0375 (2)	0.0230 (2)	0.0260 (2)	0.00340 (14)	0.00509 (17)	−0.00119 (14)

Geometric parameters (Å, º) top

C1—N1	1.333 (2)	C7—H7A	0.9300
C1—C2	1.372 (3)	C7—H7B	0.9300
C1—H1A	0.9300	C8—H8A	0.9600
C2—C3	1.384 (3)	C8—H8B	0.9600
C2—H2	0.9300	C8—H8C	0.9600
C3—C4	1.389 (2)	N1—H1	0.8600
C3—H3	0.9300	O1—P1	1.4923 (12)
C4—C5	1.397 (2)	O2—P1	1.5122 (12)
C4—C8	1.502 (2)	O3—P1	1.5663 (13)
C5—N1	1.350 (2)	O3—H3A	0.889 (10)
C5—C6	1.467 (2)	O4—P1	1.5691 (12)
C6—C7	1.295 (3)	O4—H4A	0.889 (10)
C6—H6	0.9300

N1—C1—C2	120.08 (16)	C6—C7—H7B	120.0
N1—C1—H1A	120.0	H7A—C7—H7B	120.0
C2—C1—H1A	120.0	C4—C8—H8A	109.5
C1—C2—C3	118.37 (17)	C4—C8—H8B	109.5
C1—C2—H2	120.8	H8A—C8—H8B	109.5
C3—C2—H2	120.8	C4—C8—H8C	109.5
C2—C3—C4	121.31 (17)	H8A—C8—H8C	109.5
C2—C3—H3	119.3	H8B—C8—H8C	109.5
C4—C3—H3	119.3	C1—N1—C5	123.48 (14)
C3—C4—C5	118.04 (15)	C1—N1—H1	118.3
C3—C4—C8	120.31 (16)	C5—N1—H1	118.3
C5—C4—C8	121.65 (16)	P1—O3—H3A	110.5 (19)
N1—C5—C4	118.69 (14)	P1—O4—H4A	113 (2)
N1—C5—C6	118.75 (14)	O1—P1—O2	116.08 (7)
C4—C5—C6	122.55 (15)	O1—P1—O3	110.92 (7)
C7—C6—C5	127.06 (17)	O2—P1—O3	106.41 (8)
C7—C6—H6	116.5	O1—P1—O4	107.46 (7)
C5—C6—H6	116.5	O2—P1—O4	108.58 (7)
C6—C7—H7A	120.0	O3—P1—O4	107.04 (8)

N1—C1—C2—C3	−1.1 (3)	C8—C4—C5—C6	−1.8 (2)
C1—C2—C3—C4	1.1 (3)	N1—C5—C6—C7	13.1 (3)
C2—C3—C4—C5	0.1 (3)	C4—C5—C6—C7	−166.36 (19)
C2—C3—C4—C8	−179.99 (18)	C2—C1—N1—C5	−0.2 (2)
C3—C4—C5—N1	−1.3 (2)	C4—C5—N1—C1	1.3 (2)
C8—C4—C5—N1	178.81 (16)	C6—C5—N1—C1	−178.12 (15)
C3—C4—C5—C6	178.18 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	1.83	2.6558 (18)	160
O3—H3A···O1ⁱ	0.89 (1)	1.72 (1)	2.5995 (18)	173 (3)
O4—H4A···O2ⁱⁱ	0.89 (1)	1.72 (1)	2.6002 (17)	170 (3)
C1—H1A···O1ⁱⁱⁱ	0.93	2.48	3.172 (2)	131

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

Experimental details

Crystal data
Chemical formula	C₈H₁₀N⁺·H₂O₄P⁻
M_r	217.16
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.7089 (6), 16.3668 (13), 8.0649 (6)
β (°)	109.689 (4)
V (Å³)	958.06 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.30 × 0.30 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker 2008)
T_min, T_max	0.922, 0.947
No. of measured, independent and observed [I > 2σ(I)] reflections	8970, 2362, 2052
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.114, 1.08
No. of reflections	2362
No. of parameters	136
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.33

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), 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
N1—H1···O2	0.86	1.83	2.6558 (18)	159.9
O3—H3A···O1ⁱ	0.889 (10)	1.715 (11)	2.5995 (18)	173 (3)
O4—H4A···O2ⁱⁱ	0.889 (10)	1.720 (11)	2.6002 (17)	170 (3)
C1—H1A···O1ⁱⁱⁱ	0.93	2.48	3.172 (2)	131.1

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

Acknowledgements

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

References

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