2-Amino-3-methyl­pyridinium hydrogen phthalate

Sivakumar, P.; Anzline, C.; Sudhahar, S.; Israel, S.; Chakkaravarthi, G.

doi:10.1107/S2414314617004229

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 3| March 2017| x170422

https://doi.org/10.1107/S2414314617004229

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2-Amino-3-methylpyridinium hydrogen phthalate

P. Sivakumar,^a,^b C. Anzline,^c S. Sudhahar,^d S. Israel ^e ^* and G. Chakkaravarthi ^b ^*

^aResearch and Development Centre, Bharathiar University, Coimbatore 641 046, India, ^bDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India, ^cResearch Scholar in Physics, Mother Teresa University, Kodaikanal 624 102, India, ^dDepartment of Physics, Alagappa University, Karaikkudi 630 003, India, and ^ePost Graduate and Research Department of Physics, The American College, Madurai 625 002, India
^*Correspondence e-mail: israel.samuel@gmail.com, chakkaravarthi_2005@yahoo.com

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 8 March 2017; accepted 16 March 2017; online 21 March 2017)

In the title molecular salt, C₆H₉N₂⁺·C₈H₅O₄⁻, the cation is protonated at the pyridine N atom and the anion is deprotonated at the hydroxy O atom. The anion features an intramolecular O—H⋯O hydrogen bond with the H atom located almost in the middle of the two O atoms. The dihedral angle between the pyridine and benzene rings is 19.17 (12)°. The N—H⋯O hydrogen bonds generate R₂²(8) and R₂⁴(18) ring motifs. The crystal structure is stabilized by N—H⋯O hydrogen bonds. The structure is also influenced by weak π–π [centroid-to-centroid distance = 3.7347 (14) Å] interaction between the anions.

Keywords: crystal structure; molecular salt; hydrogen bonding.

CCDC reference: 1538296

Structure description

Pyridine derivatives exhibit antifungal, anticancer and anti-inflammatory activities (Liu & Hu, 2002 ; Spanka et al., 2010 ). We report herein the synthesis and the crystal structure of the title molecular salt (Fig. 1). The bond lengths are comparable with those in related structures (Sivakumar, Devi et al., 2016 ; Sivakumar, Sudhahar et al., 2016 ). The title molecular salt (Fig. 1) comprises a 2-amino-3-methylpyridinium cation and a hydrogen phthalate anion. The cation is protonated at the pyridine N atom and the anion is deprotonated at one of the hydroxy O atoms. The anion features an intramolecular O—H—O hydrogen bond with the H atom located almost in the middle of the two O atoms. The dihedral angle between the pyridine and benzene rings is 19.17 (12)°.

Figure 1
The molecular structure of the title molecular salt, with the atom labelling and 30% probability displacement ellipsoids.

In the asymmetric unit, the inter-ionic N1—H1⋯O4 and N2—H2A⋯O3 hydrogen bonds (Table 1) link the cation and anion, generating an R₂²(8) ring motif (Fig. 2). In the crystal, the N2—H2A⋯O3 and N2—H2B⋯O1ⁱ (Table 1) hydrogen bonds generate an R₂⁴(18) ring motif (Fig. 3). The structure is also influenced by a weak offset π–π [Cg1⋯Cg1(1 − x, 2 − y, 2 − z) = 3.7347 (14) Å; Cg1 is the centroid of the (C7–C12) ring] interaction between the anions.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H2⋯O2	1.18 (3)	1.25 (3)	2.417 (2)	169 (2)
N1—H1⋯O4	0.99 (3)	1.70 (3)	2.685 (3)	171 (3)
N2—H2A⋯O3	0.91 (3)	2.01 (3)	2.916 (3)	173 (2)
N2—H2B⋯O1ⁱ	0.93 (4)	1.99 (4)	2.885 (3)	162 (3)
Symmetry code: (i) -x+1, -y+2, -z+1.

Figure 2
A partial view of the crystal packing showing the various ring motifs.

Figure 3
The crystal packing of the title molecular salt viewed along a axis. The hydrogen bonds are shown as dashed lines. H atoms not involving in hydrogen bonds have been omitted for clarity.

Synthesis and crystallization

The title compound was synthesized using 2-amino-3-methylpyridine (0.54 g) and phthalic acid (0.83 g) in an equimolar ratio. These reactants were dissolved in 15 ml acetone. The white precipitate that formed was dissolved in water and kept at room temperature. Crystals suitable for X-ray diffraction were harvested after 90 d.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₆H₉N₂⁺·C₈H₅O₄⁻
M_r	274.27
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	295
a, b, c (Å)	7.1675 (4), 8.8143 (6), 10.6613 (7)
α, β, γ (°)	91.968 (4), 96.362 (3), 94.745 (3)
V (Å³)	666.46 (7)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.28 × 0.24 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.686, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	17030, 3982, 2056
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.714

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.189, 1.02
No. of reflections	3982
No. of parameters	198
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.21
Computer programs: APEX2 and SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008 ), SHELXL2016 (Sheldrick, 2015 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1538296

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314617004229/bt4045sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617004229/bt4045Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617004229/bt4045Isup3.cml

checkCIF report

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: SHELXL2016 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015) and PLATON (Spek, 2009).

2-Amino-3-methylpyridinium 2-carboxybenzoate top

Crystal data top

C₆H₉N₂⁺·C₈H₅O₄⁻	Z = 2
M_r = 274.27	F(000) = 288
Triclinic, P1	D_x = 1.367 Mg m⁻³
a = 7.1675 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.8143 (6) Å	Cell parameters from 5483 reflections
c = 10.6613 (7) Å	θ = 0.7–0.8°
α = 91.968 (4)°	µ = 0.10 mm⁻¹
β = 96.362 (3)°	T = 295 K
γ = 94.745 (3)°	Block, colourless
V = 666.46 (7) Å³	0.28 × 0.24 × 0.20 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2056 reflections with I > 2σ(I)
ω and φ scan	R_int = 0.032
Absorption correction: multi-scan (SADABS; Bruker, 2004)	θ_max = 30.5°, θ_min = 1.9°
T_min = 0.686, T_max = 0.746	h = −10→10
17030 measured reflections	k = −12→12
3982 independent reflections	l = −15→15

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.059	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.189	w = 1/[σ²(F_o²) + (0.0632P)² + 0.3832P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
3982 reflections	Δρ_max = 0.23 e Å⁻³
198 parameters	Δρ_min = −0.21 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
C1	0.1981 (3)	0.4914 (2)	0.4055 (2)	0.0475 (5)
C2	0.1063 (3)	0.4009 (3)	0.3006 (2)	0.0541 (6)
C3	0.0722 (4)	0.2491 (3)	0.3165 (3)	0.0643 (7)
H3	0.008907	0.188210	0.249572	0.077*
C4	0.1284 (4)	0.1811 (3)	0.4291 (3)	0.0713 (8)
H4	0.105614	0.076634	0.437016	0.086*
C5	0.2171 (4)	0.2715 (3)	0.5265 (3)	0.0652 (7)
H5	0.256743	0.229168	0.602565	0.078*
C6	0.0549 (4)	0.4731 (4)	0.1789 (3)	0.0785 (8)
H6A	−0.003326	0.396615	0.117308	0.118*
H6B	0.166452	0.520748	0.149629	0.118*
H6C	−0.031501	0.548357	0.191184	0.118*
C7	0.7494 (3)	0.9694 (3)	0.9900 (2)	0.0530 (5)
H7	0.825134	1.060789	1.001807	0.064*
C8	0.6526 (3)	0.9306 (2)	0.8717 (2)	0.0454 (5)
C9	0.5434 (3)	0.7897 (2)	0.85357 (19)	0.0449 (5)
C10	0.5318 (4)	0.6995 (3)	0.9578 (2)	0.0551 (6)
H10	0.458464	0.606925	0.947484	0.066*
C11	0.6243 (4)	0.7420 (3)	1.0749 (2)	0.0624 (6)
H11	0.610918	0.680227	1.142917	0.075*
C12	0.7365 (4)	0.8762 (3)	1.0907 (2)	0.0606 (6)
H12	0.803702	0.904462	1.168821	0.073*
C13	0.6793 (3)	1.0500 (3)	0.7754 (2)	0.0550 (6)
C14	0.4398 (3)	0.7183 (3)	0.7314 (2)	0.0513 (5)
N1	0.2482 (3)	0.4225 (2)	0.5137 (2)	0.0549 (5)
H1	0.305 (4)	0.489 (3)	0.587 (3)	0.081 (9)*
N2	0.2385 (3)	0.6404 (2)	0.4039 (2)	0.0616 (6)
H2A	0.295 (4)	0.692 (3)	0.475 (3)	0.069 (8)*
H2B	0.214 (5)	0.690 (4)	0.329 (4)	0.102 (11)*
O1	0.8082 (3)	1.1491 (2)	0.7962 (2)	0.0837 (6)
O2	0.5619 (3)	1.0490 (2)	0.67375 (17)	0.0682 (5)
H2	0.458 (4)	0.927 (3)	0.658 (3)	0.073 (8)*
O3	0.3884 (3)	0.8012 (2)	0.64200 (17)	0.0697 (5)
O4	0.4074 (3)	0.57795 (19)	0.72482 (17)	0.0698 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0440 (11)	0.0456 (11)	0.0546 (12)	0.0028 (9)	0.0125 (9)	0.0049 (9)
C2	0.0457 (12)	0.0579 (13)	0.0590 (13)	0.0013 (10)	0.0116 (10)	−0.0018 (11)
C3	0.0598 (15)	0.0574 (14)	0.0748 (17)	−0.0079 (11)	0.0181 (13)	−0.0106 (13)
C4	0.0817 (19)	0.0452 (13)	0.090 (2)	−0.0019 (12)	0.0298 (16)	0.0021 (13)
C5	0.0791 (17)	0.0515 (14)	0.0687 (16)	0.0057 (12)	0.0204 (14)	0.0156 (12)
C6	0.0835 (19)	0.089 (2)	0.0596 (16)	0.0048 (16)	−0.0041 (14)	0.0064 (14)
C7	0.0506 (12)	0.0498 (12)	0.0576 (13)	0.0043 (10)	−0.0002 (10)	0.0059 (10)
C8	0.0430 (11)	0.0459 (11)	0.0488 (11)	0.0094 (9)	0.0050 (9)	0.0110 (9)
C9	0.0481 (11)	0.0427 (11)	0.0454 (11)	0.0107 (9)	0.0053 (9)	0.0077 (9)
C10	0.0710 (15)	0.0419 (11)	0.0532 (13)	0.0086 (10)	0.0055 (11)	0.0122 (10)
C11	0.0827 (17)	0.0547 (14)	0.0508 (13)	0.0121 (12)	0.0031 (12)	0.0151 (11)
C12	0.0698 (15)	0.0622 (15)	0.0488 (13)	0.0101 (12)	−0.0029 (11)	0.0067 (11)
C13	0.0545 (13)	0.0506 (13)	0.0612 (14)	0.0055 (10)	0.0072 (11)	0.0150 (10)
C14	0.0511 (12)	0.0530 (13)	0.0502 (12)	0.0038 (10)	0.0063 (10)	0.0095 (10)
N1	0.0619 (12)	0.0476 (11)	0.0554 (11)	0.0023 (9)	0.0079 (9)	0.0065 (9)
N2	0.0789 (15)	0.0460 (11)	0.0576 (13)	−0.0022 (10)	0.0026 (11)	0.0049 (10)
O1	0.0794 (13)	0.0740 (13)	0.0917 (14)	−0.0203 (10)	−0.0063 (11)	0.0352 (11)
O2	0.0857 (12)	0.0547 (10)	0.0608 (10)	0.0000 (9)	−0.0071 (9)	0.0206 (8)
O3	0.0829 (12)	0.0593 (11)	0.0597 (10)	−0.0096 (9)	−0.0156 (9)	0.0151 (8)
O4	0.0957 (14)	0.0493 (10)	0.0600 (10)	−0.0054 (9)	−0.0018 (9)	0.0042 (8)

Geometric parameters (Å, º) top

C1—N2	1.322 (3)	C8—C13	1.511 (3)
C1—N1	1.350 (3)	C9—C10	1.394 (3)
C1—C2	1.417 (3)	C9—C14	1.516 (3)
C2—C3	1.360 (3)	C10—C11	1.372 (3)
C2—C6	1.488 (4)	C10—H10	0.9300
C3—C4	1.395 (4)	C11—C12	1.369 (4)
C3—H3	0.9300	C11—H11	0.9300
C4—C5	1.353 (4)	C12—H12	0.9300
C4—H4	0.9300	C13—O1	1.214 (3)
C5—N1	1.345 (3)	C13—O2	1.295 (3)
C5—H5	0.9300	C14—O4	1.238 (3)
C6—H6A	0.9600	C14—O3	1.262 (3)
C6—H6B	0.9600	N1—H1	0.99 (3)
C6—H6C	0.9600	N2—H2A	0.91 (3)
C7—C12	1.380 (3)	N2—H2B	0.93 (4)
C7—C8	1.388 (3)	O2—H2	1.25 (3)
C7—H7	0.9300	O3—H2	1.18 (3)
C8—C9	1.407 (3)

N2—C1—N1	117.6 (2)	C10—C9—C8	117.8 (2)
N2—C1—C2	123.9 (2)	C10—C9—C14	114.34 (19)
N1—C1—C2	118.6 (2)	C8—C9—C14	127.84 (19)
C3—C2—C1	117.4 (2)	C11—C10—C9	122.6 (2)
C3—C2—C6	122.9 (2)	C11—C10—H10	118.7
C1—C2—C6	119.7 (2)	C9—C10—H10	118.7
C2—C3—C4	122.6 (3)	C12—C11—C10	119.3 (2)
C2—C3—H3	118.7	C12—C11—H11	120.3
C4—C3—H3	118.7	C10—C11—H11	120.3
C5—C4—C3	118.0 (2)	C11—C12—C7	119.7 (2)
C5—C4—H4	121.0	C11—C12—H12	120.2
C3—C4—H4	121.0	C7—C12—H12	120.2
N1—C5—C4	120.2 (3)	O1—C13—O2	120.6 (2)
N1—C5—H5	119.9	O1—C13—C8	119.3 (2)
C4—C5—H5	119.9	O2—C13—C8	120.1 (2)
C2—C6—H6A	109.5	O4—C14—O3	122.6 (2)
C2—C6—H6B	109.5	O4—C14—C9	117.2 (2)
H6A—C6—H6B	109.5	O3—C14—C9	120.2 (2)
C2—C6—H6C	109.5	C5—N1—C1	123.1 (2)
H6A—C6—H6C	109.5	C5—N1—H1	119.8 (18)
H6B—C6—H6C	109.5	C1—N1—H1	117.0 (18)
C12—C7—C8	121.9 (2)	C1—N2—H2A	119.4 (17)
C12—C7—H7	119.1	C1—N2—H2B	120 (2)
C8—C7—H7	119.1	H2A—N2—H2B	121 (3)
C7—C8—C9	118.69 (19)	C13—O2—H2	111.5 (12)
C7—C8—C13	113.89 (19)	C14—O3—H2	112.0 (13)
C9—C8—C13	127.4 (2)

N2—C1—C2—C3	−179.4 (2)	C14—C9—C10—C11	176.7 (2)
N1—C1—C2—C3	0.8 (3)	C9—C10—C11—C12	−1.6 (4)
N2—C1—C2—C6	1.7 (4)	C10—C11—C12—C7	2.4 (4)
N1—C1—C2—C6	−178.1 (2)	C8—C7—C12—C11	−0.6 (4)
C1—C2—C3—C4	−1.8 (4)	C7—C8—C13—O1	16.2 (3)
C6—C2—C3—C4	177.0 (3)	C9—C8—C13—O1	−163.9 (2)
C2—C3—C4—C5	1.3 (4)	C7—C8—C13—O2	−161.7 (2)
C3—C4—C5—N1	0.3 (4)	C9—C8—C13—O2	18.3 (4)
C12—C7—C8—C9	−2.1 (3)	C10—C9—C14—O4	−21.6 (3)
C12—C7—C8—C13	177.8 (2)	C8—C9—C14—O4	155.8 (2)
C7—C8—C9—C10	2.8 (3)	C10—C9—C14—O3	157.6 (2)
C13—C8—C9—C10	−177.1 (2)	C8—C9—C14—O3	−24.9 (3)
C7—C8—C9—C14	−174.5 (2)	C4—C5—N1—C1	−1.4 (4)
C13—C8—C9—C14	5.5 (4)	N2—C1—N1—C5	−179.0 (2)
C8—C9—C10—C11	−1.0 (3)	C2—C1—N1—C5	0.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H2···O2	1.18 (3)	1.25 (3)	2.417 (2)	169 (2)
N1—H1···O4	0.99 (3)	1.70 (3)	2.685 (3)	171 (3)
N2—H2A···O3	0.91 (3)	2.01 (3)	2.916 (3)	173 (2)
N2—H2B···O1ⁱ	0.93 (4)	1.99 (4)	2.885 (3)	162 (3)

Symmetry code: (i) −x+1, −y+2, −z+1.

Acknowledgements

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

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