2-Amino-5-methyl­pyridinium 3-hy­droxy­pyridine-2-carboxyl­ate

Abbas Farhadikoutenaei; Kaliyaperumal Thanigaimani; Suhana Arshad; Ibrahim Abdul Razak

doi:10.1107/S1600536813016322

. 2013 Jun 19;69(Pt 7):o1118–o1119. doi: 10.1107/S1600536813016322

2-Amino-5-methylpyridinium 3-hydroxypyridine-2-carboxylate

Abbas Farhadikoutenaei ^a,^b, Kaliyaperumal Thanigaimani ^a, Suhana Arshad ^a, Ibrahim Abdul Razak ^a,^*,^‡

PMCID: PMC3770389 PMID: 24046674

Abstract

In the 3-hydroxypicolinate anion of the title salt, C₆H₉N₂ ⁺·C₆H₄NO₃ ⁻, an intramolecular O—H⋯O hydrogen bond with an S(6) graph-set motif is formed, so that the anion is essentially planar, with a dihedral angle of 9.55 (9)° between the pyridine ring and the carboxylate group. In the crystal, the cations and anions are linked via N—H⋯O hydrogen bonds, forming a centrosymmetric 2 + 2 aggregate with R ₂ ²(8) and R ₄ ²(8) ring motifs. The crystal structure also features N—H⋯N and weak C—H⋯π interactions.

Related literature

For details of non-covalent interactions, see: Desiraju (2007 ▶); Aakeroy & Seddon (1993 ▶). For related structures, see: Nahringbauer & Kvick (1977 ▶); Robert et al. (2001 ▶); Thanigaimani et al. (2010 ▶, 2013 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶). For stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶). graphic file with name e-69-o1118-scheme1.jpg

Experimental

Crystal data

C₆H₉N₂ ⁺·C₆H₄NO₃ ⁻
M _r = 247.25
Monoclinic,
a = 7.3443 (4) Å
b = 16.4321 (9) Å
c = 10.8235 (5) Å
β = 118.250 (3)°
V = 1150.62 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100 K
0.58 × 0.29 × 0.16 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.942, T _max = 0.984
15996 measured reflections
4132 independent reflections
3596 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.115
S = 1.04
4132 reflections
180 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.22 e Å⁻³

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

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813016322/is5281sup1.cif

e-69-o1118-sup1.cif^{(22.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813016322/is5281Isup2.hkl

e-69-o1118-Isup2.hkl^{(202.5KB, hkl)}

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

Supplementary material file. DOI: 10.1107/S1600536813016322/is5281Isup3.cml

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

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

Cg1 is the centroid of the N1/C1–C5 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯O2	0.93 (2)	1.66 (2)	2.5239 (10)	152 (2)
N3—H2N3⋯O3ⁱ	0.885 (15)	1.969 (15)	2.8504 (11)	174.0 (14)
N3—H1N3⋯O3ⁱⁱ	0.859 (14)	2.248 (15)	2.8093 (10)	123.0 (12)
N3—H1N3⋯N1ⁱⁱ	0.859 (14)	2.416 (14)	3.2481 (10)	163.2 (13)
N2—H1N2⋯O2ⁱ	0.943 (16)	1.796 (16)	2.7327 (10)	171.4 (13)
C9—H9A⋯Cg1	0.95	2.59	3.4702 (10)	154
C11—H11A⋯Cg1ⁱⁱⁱ	0.95	2.71	3.3956 (8)	130

Open in a new tab

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

Acknowledgments

The authors thank the Malaysian Government and Universiti Sains Malaysia (USM) for the research facilities and USM Short Term Grant, No. 304/PFIZIK/6312078 to conduct this work. KT thanks The Academy of Sciences for the Developing World and USM for the TWAS–USM fellowship.

supplementary crystallographic information

Comment

Supramolecular architectures assembled via various delicate noncovalent interactions such as hydrogen bonds, π–π stacking and electrostatic interactions, etc., have attracted intense interest in recent years because of their fascinating structural diversity and potential applications for functional materials (Desiraju, 2007). Especially, the application of intermolecular hydrogen bonds is a well known and efficient tool in the field of organic crystal design owing to its strength and directional properties (Aakeroy & Seddon, 1993). In order to study potential hydrogen bonding interactions, the crystal structure determination of the title compound (I) was carried out.

The asymmetric unit (Fig. 1) contains one 2-amino-5-methylpyridinium cation and one 3-hydroxypicolinate anion. An intramolecular O1—H1O1···O2 hydrogen bond in the 3-hydroxypicolinate anion generates an S(6) ring motif. (Bernstein et al., 1995). This motif is also observed in the crystal structure of acetoguanaminium 3-hydroxypicolinate monohydrate (Thanigaimani et al., 2010). The proton transfers from the one of the carboxyl group oxygen atom (O2) to atom N1 of 2-amino-5-methylpyrimidine resulted in the widening of C7—N2—C11 angle of the pyridinium ring to 122.89 (7)°, compared to the corresponding angle of 117.4 (3)° in neutral 2-amino-5-methylpyridine (Nahringbauer & Kvick, 1977). The 2-amino-5-methylpyridinium cation is essentially planar, with a maximum deviation of 0.011 (1) Å for atom C9. The bond lengths (Allen et al., 1987) and angles are normal.

In the crystal packing (Fig. 2), the protonated N2 atom and a nitrogen atom of the 2-amino group (N3) are hydrogen-bonded to the carboxylate oxygen atoms (O2 and O3) via a pair of intramolecular N2—H1N2···O2ⁱ and N3—H2N3···O3ⁱ hydrogen bonds (symmetry code in Table 1), forming a ring motif R₂²(8) (Bernstein et al., 1995). These motifs are linked by N3—H1N3···O3ⁱⁱ hydrogen bonds (symmetry code in Table 1), forming a ring spanning the centre of symmetry at (1, -3/2, 1/2) to produce a DDAA array (where D is a hydrogen-bond donor and A is a hydrogen-bond acceptor) of four hydrogen bonds. This set of fused rings can be represented by the graph-set notations R₂²(8), R₄²(8) and R₂²(8) arrangement. This type of motif has been reported in the crystal structures of trimethoprim hydrogen glutarate (Robert et al., 2001), acetoguanaminium 3-hydroxypicolinate monohydrate (Thanigaimani et al., 2010) and 2-amino-6-methylpyridinium 3-chlorobenzoate (Thanigaimani et al., 2013). The 2-aminogroup at N3 forms a bifurcated hydrogen bond (Table 1) with carboxyl atom O3ⁱⁱ and atom N1ⁱⁱ of a 3-hydroxypicolinate anion [graph-set R₁²(5)]. The crystal structure is further stabilized by weak C—H···π interactions (Table 1) involving the N1/C1–C5 (centroid Cg1) ring.

Experimental

Hot methanol solutions (20 ml) of 2-amino5-methylpyridine (54 mg, Aldrich) and 3-hydoxypicolinic acid (34 mg, Aldrich) were mixed and warmed over a heating magnetic stirrer hotplate for a few minutes. The resulting solution was allowed to cool slowly at room temperature and crystals of the title compound (I) appeared after a few days.