2-Amino-6-methyl­pyridinium 4-hy­droxy­benzoate

V Kannan; P Sugumar; S Brahadeeswaran; M N Ponnuswamy

doi:10.1107/S1600536813007939

. 2013 Mar 28;69(Pt 4):o610. doi: 10.1107/S1600536813007939

2-Amino-6-methylpyridinium 4-hydroxybenzoate

V Kannan ^a, P Sugumar ^b, S Brahadeeswaran ^c, M N Ponnuswamy ^b,^*

PMCID: PMC3629648 PMID: 23634135

Abstract

In the title molecular salt, C₆H₉N₂ ⁺·C₇H₅O₃ ⁻, the dihedral angle between the benzene ring and the CO₂ group in the anion is 6.1 (2)°. In the crystal, the cation and anion are linked by N—H⋯O and C—H⋯O hydrogen bonds, and the anions are connected by O—H⋯O hydrogen bonds, forming a three-dimensional network.

Related literature

For general background to methylpyridinium derivatives, see: Blessing (1986 ▶); Brahadeeswaran et al. (2006 ▶); Brown (1976 ▶); Kvenvolden et al. (1971 ▶); Tomaru et al. (1991 ▶).

Experimental

Crystal data

C₆H₉N₂ ⁺·C₇H₅O₃ ⁻
M _r = 246.26
Monoclinic,
a = 11.9488 (3) Å
b = 9.2952 (3) Å
c = 12.4067 (3) Å
β = 117.116 (2)°
V = 1226.51 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.20 × 0.18 × 0.17 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.981, T _max = 0.984
11403 measured reflections
3084 independent reflections
2471 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.122
S = 1.04
3084 reflections
168 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.20 e Å⁻³

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 ▶) and DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Click here for additional data file.^{(21KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813007939/lx2273sup1.cif

e-69-0o610-sup1.cif^{(21KB, cif)}

Click here for additional data file.^{(151.3KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813007939/lx2273Isup2.hkl

e-69-0o610-Isup2.hkl^{(151.3KB, hkl)}

Click here for additional data file.^{(4.9KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813007939/lx2273Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	2.00	2.8499 (13)	169
N2—H2A⋯O2ⁱ	0.86	1.94	2.7879 (14)	168
N2—H2B⋯O1ⁱⁱ	0.86	2.18	2.9902 (14)	157
O3—H3A⋯O2ⁱⁱⁱ	0.97 (2)	1.67 (2)	2.6281 (14)	168.5 (19)
C4—H4⋯O3^iv	0.93	2.51	3.4134 (17)	163

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

VK and SB are grateful to the Department of Science and Technology (DST), New Delhi, India, for financial support through grant SR/FTP/PS-53/2007 Dt. 22–08-08.

supplementary crystallographic information

Comment

Pyridine heterocycles and their derivatives are present in many large molecules having photo chemical, electro chemical and catalytic applications. Pyridine derivatives possess nonlinear optical (NLO) properties(Tomaru et al., 1991). 4–N,N–dimethylamino–4'–N'–methyl stilbazolium tosylate (DAST) is used in generating and detecting terahertz (THz) frequencies (Brahadeeswaran et al.,2006). Carboxylic acids are believed to have existed in the prebiotic earth (Kvenvolden et al., 1971) and form aggregation patterns. An attempt is made to solve the pyridine based crystal structures to explore the NLO behaviour.

The crystal structure of the title compound (Fig.1) consists of aminomethylpyridinium cation and hydroxybenzoate anion connected via N—H···O & C—H···O hydrogen bonds (Blessing,1986; Brown, 1976). The pyridinium ring is essentially planar, with a maximum deviation of -0.005 (1) Å for atom N1. The dihedral angle between the pyridinium ring in the cation and the benzene ring in the anion is 78.32 (7)°.

In the crystal structure (Fig. 2), the cation and anion are linked by N—H···O and C—H···O hydrogen bonds (Table 1), and the anions are connected by O—H···O hydrogen bonds (Table 1), forming a three–dimensional network.

Experimental

Methanol solutions of 2–amino–6–methylpyridine (54 mg) and 4–hydroxybenzoic acid (69 mg) were mixed together and stirred for about 1 h to get a homogeneous mixture. The resulting solution was allowed to evaporate at 303 K slowly in a water bath which has a temperature accuracy of ± 0.01° C at ambient atmosphere. Brownish crystals with developed morphology of title compound were obtained after 15 days.