2-Carb­oxy­pyridinium maleate

Pandi, P.; Peramaiyan, G.; Akilan, R.; Chakkaravarthi, G.; Mohankumar, R.

doi:10.1107/S1600536812041177

organic compounds

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Volume 68| Part 11| November 2012| Page o3081

doi:10.1107/S1600536812041177

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2-Carboxypyridinium maleate

P. Pandi,^a G. Peramaiyan,^b R. Akilan,^c G. Chakkaravarthi ^d ^* and R. Mohankumar ^b ^*

^aDepartment of Physics, Panimalar Engineering College, Chennai 600 123, India, ^bDepartment of Physics, Presidency College, Chennai 600 005, India, ^cDepartment of Physics, Aksheyaa College of Engineering, Kancheepuram 603 314, India, and ^dDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India
^*Correspondence e-mail: chakkaravarthi_2005@yahoo.com, mohan66@hotmail.com

(Received 1 September 2012; accepted 1 October 2012; online 6 October 2012)

In the title molecular salt, C₆H₆NO₂⁺^.C₄H₃O₄⁻, the 2-carboxypyridinium cation is essentially planar with a maximum deviation of 0.003 (3) Å. In the crystal, adjacent cations and anions are linked by an extensive system of weak N—H⋯O, O—H⋯O and C—H⋯O interactions, forming a layer parallel to the ab plane.

Related literature

For details of pyridine and its derivatives, see: Banerjee & Murugavel (2004 ); Bis et al. (2006 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₆H₆NO₂·C₄H₃O₄
M_r = 239.18
Monoclinic, P 2₁ /c
a = 14.6498 (9) Å
b = 10.3976 (8) Å
c = 6.9067 (5) Å
β = 100.089 (3)°
V = 1035.78 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 295 K
0.24 × 0.20 × 0.16 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.970, T_max = 0.980
9722 measured reflections
2557 independent reflections
2092 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.071
wR(F²) = 0.199
S = 1.10
2557 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.43 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	2.28	2.639 (3)	105
O5—H5A⋯O4	0.82	1.73	2.540 (3)	168
N1—H1⋯O1ⁱ	0.86	2.02	2.725 (3)	139
O2—H2A⋯O3ⁱⁱ	0.82	1.71	2.463 (3)	152
C2—H2⋯O2ⁱⁱⁱ	0.93	2.54	3.462 (4)	170
C3—H3⋯O6^iv	0.93	2.59	3.221 (4)	125
C5—H5⋯O4^v	0.93	2.40	3.251 (4)	152
C8—H8⋯O6^vi	0.93	2.40	3.285 (4)	158
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) -x+2, -y, -z+1; (v) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (vi) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812041177/rk2380sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812041177/rk2380Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812041177/rk2380Isup3.cml

checkCIF report

Comment top

Pyridine and its derivatives are some of the most frequently used synthons in supramolecular chemistry based on hydrogen bonds (Banerjee & Murugavel, 2004; Bis et al., 2006). We herewith report the molecular and crystal structures of the title compound, I, which belongs to this class of compounds.

The asymmetric unit of I, (Fig. 1), contains a 2–carboxypyridinium cation and a malonate anion. The bond lengths (Allen et al., 1987) and angles are within the normal range. The crystal structure exhibit weak intermolecular N—H···O, O—H···O and C—H···O (Table 1 & Fig. 2) interactions.

Related literature top

For details of pyridine and its derivatives, see: Banerjee & Murugavel (2004); Bis et al. (2006). For bond-length data, see: Allen et al. (1987).

Experimental top

A solution of picolinic acid (0.123 g, 1 mmol) in 10 ml ethanol was added with stirring to a solution of maleic acid (0.116 g, 1 mmol) in 10 ml of distilled water at 303 K. After some time, white precipitate was obtained, which was dissolved in ethanol and colourless block–shaped single crystals were obtained by slow evaporation of the ethanol solution.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of title compound with atom labels. Displacement ellipsoids are drawn at 30% probability level. H atoms are presented as asmall spheres of arbitrary radius.
	Fig. 2. The packing of I, viewed down c axis. Intermolecular hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.

2-Carboxypyridinium maleate top

Crystal data top

C₆H₆NO₂·C₄H₃O₄	F(000) = 496
M_r = 239.18	D_x = 1.534 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4245 reflections
a = 14.6498 (9) Å	θ = 2.4–28.3°
b = 10.3976 (8) Å	µ = 0.13 mm⁻¹
c = 6.9067 (5) Å	T = 295 K
β = 100.089 (3)°	Block, colourless
V = 1035.78 (13) Å³	0.24 × 0.20 × 0.16 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	2557 independent reflections
Radiation source: fine-focus sealed tube	2092 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ω– and ϕ–scans	θ_max = 28.3°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −19→18
T_min = 0.970, T_max = 0.980	k = −13→13
9722 measured reflections	l = −9→9

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.071	H-atom parameters constrained
wR(F²) = 0.199	w = 1/[σ²(F_o²) + (0.0625P)² + 1.8972P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
2557 reflections	Δρ_max = 0.43 e Å⁻³
155 parameters	Δρ_min = −0.33 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.015 (3)

Crystal data top

C₆H₆NO₂·C₄H₃O₄	V = 1035.78 (13) Å³
M_r = 239.18	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.6498 (9) Å	µ = 0.13 mm⁻¹
b = 10.3976 (8) Å	T = 295 K
c = 6.9067 (5) Å	0.24 × 0.20 × 0.16 mm
β = 100.089 (3)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2557 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2092 reflections with I > 2σ(I)
T_min = 0.970, T_max = 0.980	R_int = 0.027
9722 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.071	0 restraints
wR(F²) = 0.199	H-atom parameters constrained
S = 1.10	Δρ_max = 0.43 e Å⁻³
2557 reflections	Δρ_min = −0.33 e Å⁻³
155 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.57261 (18)	−0.0804 (3)	0.3125 (4)	0.0320 (6)
C2	0.6336 (2)	−0.1778 (3)	0.3751 (5)	0.0389 (7)
H2	0.6170	−0.2628	0.3454	0.047*
C3	0.7201 (2)	−0.1492 (3)	0.4825 (5)	0.0438 (7)
H3	0.7618	−0.2149	0.5261	0.053*
C4	0.7440 (2)	−0.0230 (3)	0.5246 (5)	0.0412 (7)
H4	0.8020	−0.0027	0.5963	0.049*
C5	0.6817 (2)	0.0725 (3)	0.4599 (5)	0.0401 (7)
H5	0.6971	0.1582	0.4869	0.048*
N1	0.59856 (15)	0.0413 (2)	0.3575 (4)	0.0342 (5)
H1	0.5599	0.1021	0.3187	0.041*
C6	0.47635 (19)	−0.1001 (3)	0.1946 (4)	0.0346 (6)
C7	0.79780 (19)	0.0490 (3)	0.0421 (4)	0.0354 (6)
C8	0.8827 (2)	−0.0055 (3)	0.1646 (5)	0.0373 (6)
H8	0.8762	−0.0878	0.2130	0.045*
C9	0.9664 (2)	0.0462 (3)	0.2149 (5)	0.0388 (7)
H9	1.0084	−0.0061	0.2955	0.047*
C10	1.0058 (2)	0.1714 (3)	0.1674 (5)	0.0401 (7)
O1	0.45516 (17)	−0.2082 (2)	0.1321 (4)	0.0566 (7)
O2	0.42766 (14)	0.0007 (2)	0.1721 (4)	0.0453 (6)
H2A	0.3766	−0.0161	0.1075	0.068*
O3	0.72935 (14)	−0.0300 (2)	0.0195 (4)	0.0446 (6)
O4	0.79341 (16)	0.1568 (2)	−0.0311 (4)	0.0601 (8)
O5	0.95136 (17)	0.2604 (2)	0.0741 (4)	0.0559 (7)
H5A	0.8978	0.2340	0.0523	0.084*
O6	1.08852 (16)	0.1899 (3)	0.2139 (4)	0.0580 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0282 (13)	0.0299 (13)	0.0366 (14)	−0.0020 (10)	0.0024 (10)	0.0014 (11)
C2	0.0389 (15)	0.0262 (13)	0.0493 (17)	0.0000 (11)	0.0014 (13)	0.0055 (12)
C3	0.0374 (15)	0.0392 (16)	0.0514 (18)	0.0078 (13)	−0.0014 (13)	0.0081 (14)
C4	0.0284 (13)	0.0471 (17)	0.0440 (17)	−0.0014 (12)	−0.0051 (12)	−0.0031 (13)
C5	0.0310 (14)	0.0349 (15)	0.0518 (18)	−0.0029 (11)	0.0001 (12)	−0.0068 (13)
N1	0.0270 (11)	0.0274 (11)	0.0458 (14)	0.0014 (9)	−0.0005 (10)	0.0004 (10)
C6	0.0270 (13)	0.0327 (14)	0.0417 (15)	−0.0060 (10)	−0.0003 (11)	0.0041 (11)
C7	0.0295 (13)	0.0331 (14)	0.0426 (15)	0.0006 (11)	0.0031 (11)	−0.0015 (12)
C8	0.0358 (14)	0.0296 (13)	0.0451 (16)	0.0011 (11)	0.0029 (12)	0.0029 (12)
C9	0.0352 (14)	0.0320 (14)	0.0452 (17)	0.0020 (11)	−0.0041 (12)	0.0017 (12)
C10	0.0378 (15)	0.0350 (15)	0.0459 (17)	−0.0054 (12)	0.0024 (13)	−0.0057 (13)
O1	0.0479 (13)	0.0352 (12)	0.0781 (18)	−0.0090 (10)	−0.0125 (12)	−0.0019 (12)
O2	0.0261 (10)	0.0393 (12)	0.0648 (15)	−0.0008 (9)	−0.0079 (9)	−0.0009 (10)
O3	0.0323 (10)	0.0425 (12)	0.0555 (14)	−0.0055 (9)	−0.0018 (9)	0.0043 (10)
O4	0.0395 (12)	0.0409 (13)	0.092 (2)	−0.0009 (10)	−0.0120 (12)	0.0193 (13)
O5	0.0458 (13)	0.0373 (12)	0.0786 (18)	−0.0083 (10)	−0.0054 (12)	0.0109 (12)
O6	0.0378 (12)	0.0526 (15)	0.0787 (19)	−0.0125 (11)	−0.0037 (12)	−0.0083 (13)

Geometric parameters (Å, º) top

C1—N1	1.342 (4)	C6—O2	1.261 (3)
C1—C2	1.370 (4)	C7—O4	1.227 (4)
C1—C6	1.514 (4)	C7—O3	1.284 (3)
C2—C3	1.384 (4)	C7—C8	1.488 (4)
C2—H2	0.9300	C8—C9	1.328 (4)
C3—C4	1.376 (5)	C8—H8	0.9300
C3—H3	0.9300	C9—C10	1.484 (4)
C4—C5	1.369 (4)	C9—H9	0.9300
C4—H4	0.9300	C10—O6	1.213 (4)
C5—N1	1.336 (4)	C10—O5	1.315 (4)
C5—H5	0.9300	O2—H2A	0.8200
N1—H1	0.8600	O5—H5A	0.8200
C6—O1	1.224 (4)

N1—C1—C2	118.8 (2)	O1—C6—O2	128.0 (3)
N1—C1—C6	116.8 (2)	O1—C6—C1	117.9 (3)
C2—C1—C6	124.4 (3)	O2—C6—C1	114.0 (2)
C1—C2—C3	119.7 (3)	O4—C7—O3	123.4 (3)
C1—C2—H2	120.1	O4—C7—C8	124.1 (3)
C3—C2—H2	120.1	O3—C7—C8	112.5 (3)
C4—C3—C2	119.5 (3)	C9—C8—C7	129.5 (3)
C4—C3—H3	120.2	C9—C8—H8	115.2
C2—C3—H3	120.2	C7—C8—H8	115.2
C5—C4—C3	119.5 (3)	C8—C9—C10	132.4 (3)
C5—C4—H4	120.3	C8—C9—H9	113.8
C3—C4—H4	120.3	C10—C9—H9	113.8
N1—C5—C4	119.4 (3)	O6—C10—O5	120.7 (3)
N1—C5—H5	120.3	O6—C10—C9	119.4 (3)
C4—C5—H5	120.3	O5—C10—C9	120.0 (3)
C5—N1—C1	123.1 (2)	C6—O2—H2A	109.5
C5—N1—H1	118.5	C10—O5—H5A	109.5
C1—N1—H1	118.5

N1—C1—C2—C3	0.0 (5)	C2—C1—C6—O1	−8.5 (5)
C6—C1—C2—C3	−179.9 (3)	N1—C1—C6—O2	−7.8 (4)
C1—C2—C3—C4	−0.3 (5)	C2—C1—C6—O2	172.1 (3)
C2—C3—C4—C5	0.2 (5)	O4—C7—C8—C9	−1.2 (6)
C3—C4—C5—N1	0.2 (5)	O3—C7—C8—C9	178.2 (3)
C4—C5—N1—C1	−0.6 (5)	C7—C8—C9—C10	−1.2 (6)
C2—C1—N1—C5	0.5 (5)	C8—C9—C10—O6	−171.4 (4)
C6—C1—N1—C5	−179.7 (3)	C8—C9—C10—O5	8.0 (6)
N1—C1—C6—O1	171.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	2.28	2.639 (3)	105
O5—H5A···O4	0.82	1.73	2.540 (3)	168
N1—H1···O1ⁱ	0.86	2.02	2.725 (3)	139
O2—H2A···O3ⁱⁱ	0.82	1.71	2.463 (3)	152
C2—H2···O2ⁱⁱⁱ	0.93	2.54	3.462 (4)	170
C3—H3···O6^iv	0.93	2.59	3.221 (4)	125
C5—H5···O4^v	0.93	2.40	3.251 (4)	152
C8—H8···O6^vi	0.93	2.40	3.285 (4)	158

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

Experimental details

Crystal data
Chemical formula	C₆H₆NO₂·C₄H₃O₄
M_r	239.18
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	14.6498 (9), 10.3976 (8), 6.9067 (5)
β (°)	100.089 (3)
V (Å³)	1035.78 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.24 × 0.20 × 0.16

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.970, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	9722, 2557, 2092
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.071, 0.199, 1.10
No. of reflections	2557
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.33

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), 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	2.28	2.639 (3)	105
O5—H5A···O4	0.82	1.73	2.540 (3)	168
N1—H1···O1ⁱ	0.86	2.02	2.725 (3)	139
O2—H2A···O3ⁱⁱ	0.82	1.71	2.463 (3)	152
C2—H2···O2ⁱⁱⁱ	0.93	2.54	3.462 (4)	170
C3—H3···O6^iv	0.93	2.59	3.221 (4)	125
C5—H5···O4^v	0.93	2.40	3.251 (4)	152
C8—H8···O6^vi	0.93	2.40	3.285 (4)	158

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

Acknowledgements

The authors wish to acknowledge the SAIF, IIT Madras, for the data collection.

References

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