2-Amino-5-methyl-pyridinium 3-hy-droxy-pyridine-2-carboxyl-ate.

In the 3-hy-droxy-picolinate anion of the title salt, C6H9N2 (+)·C6H4NO3 (-), an intra-molecular 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 carboxyl-ate 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 inter-actions.

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 ▶).

Experimental

Crystal data

C6H9N2 +·C6H4NO3 −

M = 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

Δρmax = 0.47 e Å−3

Δρmin = −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 ▶).

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

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

Click here for additional data file.

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

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

C6H9N2+·C6H4NO3−	F(000) = 520
Mr = 247.25	Dx = 1.427 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8234 reflections
a = 7.3443 (4) Å	θ = 2.5–32.6°
b = 16.4321 (9) Å	µ = 0.11 mm−1
c = 10.8235 (5) Å	T = 100 K
β = 118.250 (3)°	Block, colourless
V = 1150.62 (10) Å3	0.58 × 0.29 × 0.16 mm
Z = 4

Bruker SMART APEXII DUO CCD area-detector diffractometer	4132 independent reflections
Radiation source: fine-focus sealed tube	3596 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
φ and ω scans	θmax = 32.6°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→9
Tmin = 0.942, Tmax = 0.984	k = −24→24
15996 measured reflections	l = −16→16

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0686P)2 + 0.2463P] where P = (Fo2 + 2Fc2)/3
4132 reflections	(Δ/σ)max = 0.001
180 parameters	Δρmax = 0.47 e Å−3
0 restraints	Δρmin = −0.22 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	0.38403 (10)	0.83927 (4)	0.52572 (6)	0.02228 (14)
O2	0.41088 (9)	0.89008 (4)	0.31488 (7)	0.01954 (13)
O3	0.12614 (10)	0.90599 (4)	0.10825 (6)	0.01974 (13)
N1	−0.10602 (10)	0.82189 (4)	0.20289 (7)	0.01502 (13)
C1	−0.22027 (12)	0.78730 (5)	0.25475 (8)	0.01684 (14)
H1A	−0.3598	0.7738	0.1920	0.020*
C2	−0.14303 (13)	0.77021 (4)	0.39745 (8)	0.01669 (14)
H2A	−0.2297	0.7465	0.4307	0.020*
C3	0.06046 (13)	0.78818 (4)	0.48931 (8)	0.01635 (14)
H3A	0.1159	0.7773	0.5867	0.020*
C4	0.18388 (12)	0.82274 (4)	0.43669 (8)	0.01437 (14)
C5	0.09352 (11)	0.83951 (4)	0.29191 (7)	0.01291 (13)
C6	0.21674 (12)	0.88142 (4)	0.23125 (8)	0.01460 (14)
N2	0.39598 (10)	0.50115 (4)	0.27137 (7)	0.01444 (13)
N3	0.70889 (12)	0.55236 (5)	0.44004 (8)	0.02005 (14)
C7	0.50370 (12)	0.55708 (4)	0.37131 (8)	0.01518 (14)
C8	0.38865 (14)	0.61797 (5)	0.39723 (8)	0.01833 (15)
H8A	0.4581	0.6590	0.4655	0.022*
C9	0.17762 (14)	0.61731 (5)	0.32352 (9)	0.01811 (15)
H9A	0.1020	0.6576	0.3431	0.022*
C10	0.06826 (12)	0.55828 (4)	0.21858 (8)	0.01489 (14)
C11	0.18508 (12)	0.50126 (4)	0.19649 (8)	0.01427 (14)
H11A	0.1179	0.4606	0.1272	0.017*
C12	−0.16380 (13)	0.56034 (5)	0.13631 (9)	0.01984 (16)
H12A	−0.2134	0.5109	0.0793	0.030*
H12B	−0.2072	0.6082	0.0750	0.030*
H12C	−0.2220	0.5633	0.2011	0.030*
H2N3	0.766 (2)	0.5071 (9)	0.4311 (15)	0.030 (3)*
H1N3	0.779 (2)	0.5866 (8)	0.5053 (15)	0.029 (3)*
H1O1	0.437 (3)	0.8585 (12)	0.469 (2)	0.058 (5)*
H1N2	0.465 (2)	0.4611 (9)	0.2494 (15)	0.036 (4)*

	U11	U22	U33	U12	U13	U23
O1	0.0138 (3)	0.0296 (3)	0.0167 (3)	−0.0022 (2)	0.0017 (2)	0.0055 (2)
O2	0.0115 (3)	0.0238 (3)	0.0219 (3)	−0.0005 (2)	0.0067 (2)	0.0054 (2)
O3	0.0173 (3)	0.0264 (3)	0.0151 (3)	−0.0030 (2)	0.0073 (2)	0.0024 (2)
N1	0.0137 (3)	0.0162 (3)	0.0150 (3)	−0.0018 (2)	0.0067 (2)	−0.0012 (2)
C1	0.0144 (3)	0.0181 (3)	0.0183 (3)	−0.0032 (2)	0.0080 (3)	−0.0014 (2)
C2	0.0187 (3)	0.0156 (3)	0.0190 (3)	−0.0011 (3)	0.0116 (3)	0.0000 (2)
C3	0.0202 (4)	0.0150 (3)	0.0148 (3)	0.0006 (2)	0.0090 (3)	0.0010 (2)
C4	0.0136 (3)	0.0139 (3)	0.0139 (3)	0.0007 (2)	0.0050 (3)	0.0007 (2)
C5	0.0123 (3)	0.0130 (3)	0.0136 (3)	0.0005 (2)	0.0063 (3)	0.0003 (2)
C6	0.0135 (3)	0.0148 (3)	0.0165 (3)	−0.0001 (2)	0.0079 (3)	−0.0001 (2)
N2	0.0137 (3)	0.0146 (3)	0.0148 (3)	0.0010 (2)	0.0066 (2)	−0.0013 (2)
N3	0.0148 (3)	0.0217 (3)	0.0187 (3)	−0.0003 (2)	0.0039 (3)	−0.0020 (2)
C7	0.0162 (3)	0.0151 (3)	0.0130 (3)	−0.0005 (2)	0.0058 (3)	0.0006 (2)
C8	0.0217 (4)	0.0153 (3)	0.0162 (3)	0.0011 (3)	0.0076 (3)	−0.0024 (2)
C9	0.0216 (4)	0.0155 (3)	0.0185 (3)	0.0044 (3)	0.0105 (3)	0.0004 (2)
C10	0.0154 (3)	0.0150 (3)	0.0153 (3)	0.0023 (2)	0.0082 (3)	0.0028 (2)
C11	0.0141 (3)	0.0147 (3)	0.0141 (3)	−0.0003 (2)	0.0067 (3)	−0.0001 (2)
C12	0.0152 (3)	0.0223 (3)	0.0230 (4)	0.0034 (3)	0.0098 (3)	0.0051 (3)

O1—C4	1.3499 (9)	N2—H1N2	0.927 (15)
O1—H1O1	0.926 (19)	N3—C7	1.3301 (10)
O2—C6	1.2848 (9)	N3—H2N3	0.883 (15)
O3—C6	1.2408 (9)	N3—H1N3	0.859 (14)
N1—C1	1.3372 (10)	C7—C8	1.4207 (11)
N1—C5	1.3502 (10)	C8—C9	1.3668 (12)
C1—C2	1.3989 (11)	C8—H8A	0.9500
C1—H1A	0.9500	C9—C10	1.4187 (11)
C2—C3	1.3793 (11)	C9—H9A	0.9500
C2—H2A	0.9500	C10—C11	1.3657 (10)
C3—C4	1.3990 (11)	C10—C12	1.5040 (11)
C3—H3A	0.9500	C11—H11A	0.9500
C4—C5	1.4098 (10)	C12—H12A	0.9800
C5—C6	1.5122 (10)	C12—H12B	0.9800
N2—C7	1.3529 (10)	C12—H12C	0.9800
N2—C11	1.3666 (10)
C4—O1—H1O1	104.5 (12)	C7—N3—H1N3	120.3 (10)
C1—N1—C5	118.45 (6)	H2N3—N3—H1N3	120.5 (13)
N1—C1—C2	122.80 (7)	N3—C7—N2	119.11 (7)
N1—C1—H1A	118.6	N3—C7—C8	123.57 (7)
C2—C1—H1A	118.6	N2—C7—C8	117.32 (7)
C3—C2—C1	119.19 (7)	C9—C8—C7	119.69 (7)
C3—C2—H2A	120.4	C9—C8—H8A	120.2
C1—C2—H2A	120.4	C7—C8—H8A	120.2
C2—C3—C4	118.90 (7)	C8—C9—C10	121.91 (7)
C2—C3—H3A	120.6	C8—C9—H9A	119.0
C4—C3—H3A	120.6	C10—C9—H9A	119.0
O1—C4—C3	119.18 (7)	C11—C10—C9	116.40 (7)
O1—C4—C5	122.33 (7)	C11—C10—C12	122.79 (7)
C3—C4—C5	118.49 (7)	C9—C10—C12	120.80 (7)
N1—C5—C4	122.15 (7)	C10—C11—N2	121.78 (7)
N1—C5—C6	117.28 (6)	C10—C11—H11A	119.1
C4—C5—C6	120.53 (7)	N2—C11—H11A	119.1
O3—C6—O2	124.93 (7)	C10—C12—H12A	109.5
O3—C6—C5	119.13 (7)	C10—C12—H12B	109.5
O2—C6—C5	115.92 (6)	H12A—C12—H12B	109.5
C7—N2—C11	122.89 (6)	C10—C12—H12C	109.5
C7—N2—H1N2	120.2 (9)	H12A—C12—H12C	109.5
C11—N2—H1N2	116.9 (9)	H12B—C12—H12C	109.5
C7—N3—H2N3	117.5 (9)
C5—N1—C1—C2	1.36 (11)	N1—C5—C6—O2	−173.26 (6)
N1—C1—C2—C3	−1.19 (12)	C4—C5—C6—O2	9.01 (10)
C1—C2—C3—C4	−0.26 (11)	C11—N2—C7—N3	179.59 (7)
C2—C3—C4—O1	−178.95 (7)	C11—N2—C7—C8	−0.11 (11)
C2—C3—C4—C5	1.41 (11)	N3—C7—C8—C9	−178.71 (7)
C1—N1—C5—C4	−0.11 (11)	N2—C7—C8—C9	0.97 (11)
C1—N1—C5—C6	−177.80 (6)	C7—C8—C9—C10	−1.42 (12)
O1—C4—C5—N1	179.10 (7)	C8—C9—C10—C11	0.95 (11)
C3—C4—C5—N1	−1.28 (11)	C8—C9—C10—C12	−178.32 (7)
O1—C4—C5—C6	−3.29 (11)	C9—C10—C11—N2	−0.06 (11)
C3—C4—C5—C6	176.34 (6)	C12—C10—C11—N2	179.19 (6)
N1—C5—C6—O3	8.08 (10)	C7—N2—C11—C10	−0.35 (11)
C4—C5—C6—O3	−169.65 (7)

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

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

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