2-Amino-5-methyl-pyridinium 6-oxo-1,6-dihydro-pyridine-2-carboxyl-ate.

The anion of the title salt, C(6)H(9)N(2) (+)·C(6)H(4)NO(3) (-), undergoes an enol-to-keto tautomerism during the crystallization. In the crystal structure, the cation and anion are held together by a relatively short N-H⋯O hydrogen bond, and the two anions are further connected to each other by a pair of N-H⋯O hydrogen bonds with an R(2) (2)(8) ring motif, thus forming a centrosymmetric 2 + 2 aggregate. The aggregates are further linked through weak N-H⋯O and C-H⋯O hydrogen bonds, resulting a three-dimensional network.

Related literature

For details of 2-amino­pyridine and its derivatives, see: Banerjee & Murugavel (2004 ▶); Bis & Zaworotko (2005 ▶); Bis et al. (2006 ▶). For details of 6-hy­droxy­picolinic acid, see: Sun et al. (2004 ▶); Soares-Santos et al. (2003 ▶). For a related structure, see: Sawada & Ohashi (1998 ▶). 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 in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C6H9N2 +·C6H4NO3 −

M = 247.25

Monoclinic,

a = 11.7093 (6) Å

b = 10.4594 (6) Å

c = 11.4590 (6) Å

β = 119.203 (1)°

V = 1225.03 (11) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 100 K

0.45 × 0.35 × 0.23 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.957, T max = 0.978

15984 measured reflections

4430 independent reflections

3745 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.116

S = 1.02

4430 reflections

180 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.43 e Å−3

Δρmin = −0.21 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 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812041359/is5197sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812041359/is5197Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812041359/is5197Isup3.cml

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

C6H9N2+·C6H4NO3−	F(000) = 520
Mr = 247.25	Dx = 1.341 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6176 reflections
a = 11.7093 (6) Å	θ = 3.6–32.6°
b = 10.4594 (6) Å	µ = 0.10 mm−1
c = 11.4590 (6) Å	T = 100 K
β = 119.203 (1)°	Block, colourless
V = 1225.03 (11) Å3	0.45 × 0.35 × 0.23 mm
Z = 4

Bruker SMART APEXII DUO CCD area-detector diffractometer	4430 independent reflections
Radiation source: fine-focus sealed tube	3745 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
φ and ω scans	θmax = 32.6°, θmin = 3.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −17→17
Tmin = 0.957, Tmax = 0.978	k = −15→15
15984 measured reflections	l = −16→17

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0661P)2 + 0.2292P] where P = (Fo2 + 2Fc2)/3
4430 reflections	(Δ/σ)max < 0.001
180 parameters	Δρmax = 0.43 e Å−3
0 restraints	Δρmin = −0.21 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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.

	x	y	z	Uiso*/Ueq
O1	0.37734 (6)	0.60282 (6)	0.39711 (6)	0.01806 (13)
O2	0.80810 (7)	0.48126 (7)	0.29773 (7)	0.02633 (15)
O3	0.79587 (6)	0.45930 (6)	0.48584 (7)	0.02282 (14)
N1	0.55569 (6)	0.55843 (7)	0.37336 (7)	0.01512 (13)
N2	0.02845 (7)	0.72276 (7)	0.43791 (7)	0.01818 (14)
N3	0.14291 (7)	0.77377 (8)	0.32695 (8)	0.02345 (16)
C1	0.43630 (7)	0.61584 (7)	0.33157 (8)	0.01518 (14)
C2	0.38707 (8)	0.68852 (8)	0.21019 (8)	0.02096 (16)
H2A	0.3064	0.7328	0.1776	0.025*
C3	0.45395 (9)	0.69519 (10)	0.14089 (9)	0.02493 (18)
H3A	0.4195	0.7439	0.0608	0.030*
C4	0.57443 (9)	0.63000 (9)	0.18740 (9)	0.02318 (17)
H4A	0.6203	0.6326	0.1382	0.028*
C5	0.62317 (8)	0.56351 (8)	0.30428 (8)	0.01706 (15)
C6	0.75338 (8)	0.49530 (8)	0.36664 (9)	0.01855 (15)
C7	−0.25015 (10)	0.86990 (10)	0.46610 (12)	0.0311 (2)
H7A	−0.2490	0.7998	0.5234	0.047*
H7B	−0.3361	0.8737	0.3856	0.047*
H7C	−0.2328	0.9509	0.5149	0.047*
C8	−0.14653 (8)	0.84727 (8)	0.42693 (9)	0.02107 (16)
C9	−0.12821 (9)	0.93128 (9)	0.34046 (10)	0.02358 (17)
H9A	−0.1834	1.0039	0.3055	0.028*
C10	−0.03306 (9)	0.91053 (9)	0.30608 (9)	0.02217 (17)
H10A	−0.0219	0.9685	0.2486	0.027*
C11	0.04861 (7)	0.80162 (8)	0.35711 (8)	0.01760 (15)
C12	−0.06528 (8)	0.74369 (8)	0.47303 (8)	0.01970 (16)
H12A	−0.0746	0.6849	0.5310	0.024*
H1N1	0.5904 (14)	0.5129 (15)	0.4496 (14)	0.033 (3)*
H2N3	0.1961 (15)	0.7063 (15)	0.3644 (15)	0.037 (4)*
H1N3	0.1663 (14)	0.8348 (15)	0.2824 (14)	0.034 (3)*
H1N2	0.0830 (15)	0.6489 (15)	0.4686 (16)	0.040 (4)*

	U11	U22	U33	U12	U13	U23
O1	0.0171 (3)	0.0218 (3)	0.0192 (3)	0.0032 (2)	0.0119 (2)	0.0018 (2)
O2	0.0276 (3)	0.0276 (3)	0.0359 (4)	0.0033 (2)	0.0250 (3)	0.0001 (3)
O3	0.0197 (3)	0.0248 (3)	0.0278 (3)	0.0060 (2)	0.0146 (2)	0.0074 (2)
N1	0.0151 (3)	0.0164 (3)	0.0162 (3)	0.0019 (2)	0.0095 (2)	0.0018 (2)
N2	0.0169 (3)	0.0183 (3)	0.0205 (3)	0.0015 (2)	0.0101 (2)	0.0027 (2)
N3	0.0218 (3)	0.0263 (4)	0.0279 (4)	0.0065 (3)	0.0166 (3)	0.0067 (3)
C1	0.0146 (3)	0.0155 (3)	0.0166 (3)	0.0011 (2)	0.0084 (3)	−0.0002 (2)
C2	0.0188 (3)	0.0228 (4)	0.0218 (4)	0.0046 (3)	0.0104 (3)	0.0068 (3)
C3	0.0245 (4)	0.0297 (4)	0.0229 (4)	0.0045 (3)	0.0134 (3)	0.0097 (3)
C4	0.0245 (4)	0.0278 (4)	0.0234 (4)	0.0029 (3)	0.0165 (3)	0.0062 (3)
C5	0.0178 (3)	0.0177 (3)	0.0201 (3)	0.0008 (2)	0.0128 (3)	0.0003 (3)
C6	0.0184 (3)	0.0156 (3)	0.0269 (4)	0.0005 (2)	0.0152 (3)	0.0003 (3)
C7	0.0284 (4)	0.0308 (5)	0.0453 (6)	−0.0001 (4)	0.0269 (4)	−0.0044 (4)
C8	0.0190 (3)	0.0219 (4)	0.0259 (4)	−0.0008 (3)	0.0138 (3)	−0.0025 (3)
C9	0.0213 (4)	0.0218 (4)	0.0293 (4)	0.0058 (3)	0.0137 (3)	0.0036 (3)
C10	0.0223 (4)	0.0217 (4)	0.0246 (4)	0.0053 (3)	0.0131 (3)	0.0063 (3)
C11	0.0160 (3)	0.0194 (3)	0.0182 (3)	0.0009 (2)	0.0090 (3)	0.0009 (3)
C12	0.0195 (3)	0.0210 (4)	0.0215 (4)	−0.0020 (3)	0.0122 (3)	−0.0002 (3)

O1—C1	1.2511 (9)	C3—H3A	0.9500
O2—C6	1.2447 (9)	C4—C5	1.3628 (12)
O3—C6	1.2617 (11)	C4—H4A	0.9500
N1—C5	1.3654 (9)	C5—C6	1.5104 (11)
N1—C1	1.3751 (10)	C7—C8	1.5036 (12)
N1—H1N1	0.899 (15)	C7—H7A	0.9800
N2—C11	1.3440 (11)	C7—H7B	0.9800
N2—C12	1.3585 (10)	C7—H7C	0.9800
N2—H1N2	0.954 (16)	C8—C12	1.3665 (12)
N3—C11	1.3402 (10)	C8—C9	1.4169 (13)
N3—H2N3	0.900 (16)	C9—C10	1.3681 (12)
N3—H1N3	0.938 (15)	C9—H9A	0.9500
C1—C2	1.4361 (11)	C10—C11	1.4172 (11)
C2—C3	1.3622 (12)	C10—H10A	0.9500
C2—H2A	0.9500	C12—H12A	0.9500
C3—C4	1.4161 (12)
C5—N1—C1	123.96 (7)	O2—C6—O3	126.76 (8)
C5—N1—H1N1	118.0 (9)	O2—C6—C5	117.96 (8)
C1—N1—H1N1	118.0 (9)	O3—C6—C5	115.27 (7)
C11—N2—C12	122.96 (7)	C8—C7—H7A	109.5
C11—N2—H1N2	116.1 (9)	C8—C7—H7B	109.5
C12—N2—H1N2	121.0 (9)	H7A—C7—H7B	109.5
C11—N3—H2N3	120.9 (9)	C8—C7—H7C	109.5
C11—N3—H1N3	119.2 (9)	H7A—C7—H7C	109.5
H2N3—N3—H1N3	118.4 (13)	H7B—C7—H7C	109.5
O1—C1—N1	120.55 (7)	C12—C8—C9	116.59 (8)
O1—C1—C2	124.11 (7)	C12—C8—C7	121.36 (8)
N1—C1—C2	115.33 (7)	C9—C8—C7	122.05 (8)
C3—C2—C1	121.23 (7)	C10—C9—C8	121.70 (8)
C3—C2—H2A	119.4	C10—C9—H9A	119.2
C1—C2—H2A	119.4	C8—C9—H9A	119.2
C2—C3—C4	120.43 (8)	C9—C10—C11	119.28 (8)
C2—C3—H3A	119.8	C9—C10—H10A	120.4
C4—C3—H3A	119.8	C11—C10—H10A	120.4
C5—C4—C3	118.57 (7)	N3—C11—N2	119.21 (8)
C5—C4—H4A	120.7	N3—C11—C10	122.91 (8)
C3—C4—H4A	120.7	N2—C11—C10	117.88 (7)
C4—C5—N1	120.42 (7)	N2—C12—C8	121.60 (8)
C4—C5—C6	123.23 (7)	N2—C12—H12A	119.2
N1—C5—C6	116.33 (7)	C8—C12—H12A	119.2
C5—N1—C1—O1	176.99 (7)	C4—C5—C6—O3	167.03 (9)
C5—N1—C1—C2	−2.64 (11)	N1—C5—C6—O3	−11.36 (11)
O1—C1—C2—C3	−177.60 (9)	C12—C8—C9—C10	−0.71 (14)
N1—C1—C2—C3	2.02 (12)	C7—C8—C9—C10	179.51 (9)
C1—C2—C3—C4	0.03 (15)	C8—C9—C10—C11	0.60 (14)
C2—C3—C4—C5	−1.64 (15)	C12—N2—C11—N3	−179.75 (8)
C3—C4—C5—N1	1.11 (14)	C12—N2—C11—C10	−0.56 (12)
C3—C4—C5—C6	−177.22 (8)	C9—C10—C11—N3	179.19 (9)
C1—N1—C5—C4	1.13 (13)	C9—C10—C11—N2	0.03 (13)
C1—N1—C5—C6	179.56 (7)	C11—N2—C12—C8	0.45 (13)
C4—C5—C6—O2	−12.31 (13)	C9—C8—C12—N2	0.19 (13)
N1—C5—C6—O2	169.31 (8)	C7—C8—C12—N2	179.97 (8)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1i	0.899 (15)	2.011 (15)	2.8922 (10)	166.0 (16)
N3—H2N3···O1	0.900 (16)	2.245 (19)	3.0373 (12)	146.7 (15)
N3—H2N3···O3i	0.900 (16)	2.408 (16)	3.0916 (11)	133.0 (15)
N3—H1N3···O2ii	0.938 (15)	1.884 (16)	2.8071 (12)	167.7 (15)
N2—H1N2···O3i	0.954 (16)	1.686 (18)	2.6206 (11)	165.7 (17)
C3—H3A···O1iii	0.95	2.33	3.2598 (11)	166
C9—H9A···O1iv	0.95	2.54	3.3750 (12)	146

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O1i	0.899 (15)	2.011 (15)	2.8922 (10)	166.0 (16)
N3—H2N3⋯O1	0.900 (16)	2.245 (19)	3.0373 (12)	146.7 (15)
N3—H2N3⋯O3i	0.900 (16)	2.408 (16)	3.0916 (11)	133.0 (15)
N3—H1N3⋯O2ii	0.938 (15)	1.884 (16)	2.8071 (12)	167.7 (15)
N2—H1N2⋯O3i	0.954 (16)	1.686 (18)	2.6206 (11)	165.7 (17)
C3—H3A⋯O1iii	0.95	2.33	3.2598 (11)	166
C9—H9A⋯O1iv	0.95	2.54	3.3750 (12)	146

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