2-Amino-4-methyl-pyridinium 2-carb-oxy-benzoate.

In the title mol-ecular salt, C(6)H(9)N(2) (+)·C(8)H(5)O(4) (-), the anion is stabilized by an intra-molecular O-H⋯O hydrogen bond, which generates an S(7) ring motif. In the crystal, the cations and anions are linked to form extended chains along [001] by O-H⋯O and N-H⋯O hydrogen bonds. Adjacent chains are crosslinked via C-H⋯O inter-actions into sheets lying parallel to (100).

Related literature

For substituted pyridines, see: Pozharski et al. (1997 ▶); Katritzky et al. (1996 ▶). For details of hydrogen bonding, see: Scheiner (1997 ▶); Jeffrey & Saenger (1991 ▶); Jeffrey (1997 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For related structures, see: Quah et al. (2008a ▶,b ▶,c ▶). For reference bond lengths, see: Allen et al. (1987 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C6H9N2 +·C8H5O4 −

M = 274.27

Monoclinic,

a = 13.0558 (15) Å

b = 6.9182 (8) Å

c = 14.2575 (17) Å

β = 90.218 (2)°

V = 1287.8 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 100 K

0.41 × 0.19 × 0.11 mm

Data collection

Bruker SMART APEXII DUO CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.958, T max = 0.989

26319 measured reflections

3856 independent reflections

3332 reflections with I > 2σ(I)

R int = 0.046

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.131

S = 1.13

3856 reflections

233 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.41 e Å−3

Δρmin = −0.33 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 datablocks global, I. DOI: 10.1107/S1600536810025900/hb5537sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810025900/hb5537Isup2.hkl

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

C6H9N2+·C8H5O4−	F(000) = 576
Mr = 274.27	Dx = 1.415 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6320 reflections
a = 13.0558 (15) Å	θ = 2.9–30.3°
b = 6.9182 (8) Å	µ = 0.11 mm−1
c = 14.2575 (17) Å	T = 100 K
β = 90.218 (2)°	Block, colourless
V = 1287.8 (3) Å3	0.41 × 0.19 × 0.11 mm
Z = 4

Bruker SMART APEXII DUO CCD diffractometer	3856 independent reflections
Radiation source: fine-focus sealed tube	3332 reflections with I > 2σ(I)
graphite	Rint = 0.046
φ and ω scans	θmax = 30.3°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −18→18
Tmin = 0.958, Tmax = 0.989	k = −9→9
26319 measured reflections	l = −20→20

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ2(Fo2) + (0.0537P)2 + 0.7248P] where P = (Fo2 + 2Fc2)/3
3856 reflections	(Δ/σ)max = 0.001
233 parameters	Δρmax = 0.41 e Å−3
0 restraints	Δρmin = −0.33 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems 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
N1	0.92537 (9)	0.10419 (17)	0.64609 (8)	0.0185 (2)
N2	0.85884 (10)	0.0110 (2)	0.78891 (8)	0.0230 (3)
C1	0.84333 (10)	0.05716 (19)	0.69918 (9)	0.0174 (3)
C2	0.74595 (10)	0.05677 (19)	0.65551 (9)	0.0173 (2)
C3	0.73580 (10)	0.10080 (19)	0.56198 (9)	0.0173 (2)
C4	0.82425 (10)	0.1503 (2)	0.50975 (9)	0.0188 (3)
C5	0.91673 (10)	0.1521 (2)	0.55390 (9)	0.0190 (3)
C6	0.63362 (11)	0.0948 (2)	0.51390 (11)	0.0233 (3)
O1	0.29640 (8)	0.07772 (17)	1.07382 (7)	0.0256 (2)
O2	0.14735 (7)	0.13709 (16)	1.00722 (7)	0.0220 (2)
H1O2	0.1249	0.1484	0.9510	0.033*
O3	0.07013 (7)	0.10883 (16)	0.85474 (7)	0.0232 (2)
O4	0.11341 (8)	0.01778 (17)	0.71187 (7)	0.0255 (2)
C7	0.25074 (10)	0.07219 (19)	0.81743 (9)	0.0169 (2)
C8	0.31459 (11)	0.0630 (2)	0.73921 (10)	0.0252 (3)
C9	0.42058 (12)	0.0674 (3)	0.74708 (11)	0.0343 (4)
C10	0.46574 (12)	0.0806 (3)	0.83501 (11)	0.0307 (4)
C11	0.40349 (10)	0.0909 (2)	0.91336 (10)	0.0212 (3)
C12	0.29652 (10)	0.08811 (18)	0.90749 (9)	0.0158 (2)
C13	0.24430 (10)	0.10053 (19)	1.00235 (9)	0.0178 (3)
C14	0.13713 (10)	0.0649 (2)	0.79293 (10)	0.0186 (3)
H2A	0.6866 (15)	0.030 (3)	0.6899 (13)	0.025 (5)*
H4A	0.8212 (13)	0.180 (3)	0.4489 (13)	0.020 (4)*
H5A	0.9801 (14)	0.181 (3)	0.5240 (13)	0.026 (5)*
H6A	0.6231 (16)	0.198 (3)	0.4689 (15)	0.038 (6)*
H6B	0.6280 (18)	−0.026 (4)	0.4780 (16)	0.044 (6)*
H6C	0.5785 (19)	0.100 (3)	0.5570 (18)	0.050 (7)*
H8A	0.2830 (17)	0.056 (3)	0.6805 (16)	0.038 (6)*
H9A	0.4616 (17)	0.062 (3)	0.6884 (16)	0.039 (6)*
H10A	0.5374 (18)	0.080 (3)	0.8406 (15)	0.037 (6)*
H11A	0.4322 (14)	0.106 (2)	0.9756 (13)	0.018 (4)*
H1N1	0.9896 (18)	0.087 (3)	0.6745 (15)	0.038 (6)*
H1N2	0.9214 (18)	0.022 (3)	0.8138 (15)	0.037 (6)*
H2N2	0.8067 (17)	−0.025 (3)	0.8207 (14)	0.028 (5)*

	U11	U22	U33	U12	U13	U23
N1	0.0148 (5)	0.0233 (6)	0.0174 (5)	−0.0020 (4)	−0.0001 (4)	0.0000 (4)
N2	0.0200 (6)	0.0340 (7)	0.0150 (5)	−0.0024 (5)	−0.0008 (4)	0.0032 (5)
C1	0.0176 (6)	0.0188 (6)	0.0159 (6)	−0.0008 (4)	0.0006 (4)	−0.0010 (4)
C2	0.0148 (5)	0.0198 (6)	0.0172 (6)	−0.0013 (4)	0.0019 (4)	−0.0013 (5)
C3	0.0169 (6)	0.0176 (6)	0.0175 (6)	0.0003 (4)	−0.0015 (4)	−0.0015 (4)
C4	0.0204 (6)	0.0204 (6)	0.0156 (6)	−0.0002 (5)	0.0010 (5)	0.0009 (5)
C5	0.0184 (6)	0.0208 (6)	0.0178 (6)	−0.0020 (5)	0.0031 (5)	0.0009 (5)
C6	0.0176 (6)	0.0309 (7)	0.0212 (6)	−0.0006 (5)	−0.0036 (5)	0.0001 (6)
O1	0.0203 (5)	0.0412 (6)	0.0153 (4)	−0.0024 (4)	−0.0015 (4)	−0.0009 (4)
O2	0.0181 (5)	0.0317 (5)	0.0163 (4)	0.0040 (4)	0.0016 (3)	−0.0018 (4)
O3	0.0147 (4)	0.0350 (6)	0.0199 (5)	0.0033 (4)	−0.0001 (4)	0.0006 (4)
O4	0.0199 (5)	0.0366 (6)	0.0201 (5)	0.0000 (4)	−0.0039 (4)	−0.0031 (4)
C7	0.0149 (5)	0.0197 (6)	0.0160 (5)	0.0004 (4)	−0.0009 (4)	0.0009 (4)
C8	0.0204 (6)	0.0397 (8)	0.0156 (6)	0.0001 (6)	0.0003 (5)	−0.0003 (6)
C9	0.0196 (7)	0.0636 (12)	0.0197 (7)	−0.0003 (7)	0.0047 (5)	−0.0031 (7)
C10	0.0152 (6)	0.0530 (10)	0.0239 (7)	0.0010 (6)	0.0017 (5)	−0.0021 (7)
C11	0.0164 (6)	0.0292 (7)	0.0181 (6)	0.0014 (5)	−0.0014 (5)	−0.0003 (5)
C12	0.0155 (5)	0.0170 (6)	0.0150 (5)	0.0004 (4)	0.0003 (4)	0.0006 (4)
C13	0.0172 (6)	0.0199 (6)	0.0163 (6)	−0.0019 (5)	0.0010 (4)	−0.0013 (5)
C14	0.0169 (6)	0.0202 (6)	0.0188 (6)	−0.0004 (5)	−0.0012 (5)	0.0026 (5)

N1—C1	1.3535 (17)	O1—C13	1.2331 (16)
N1—C5	1.3599 (17)	O2—C13	1.2929 (16)
N1—H1N1	0.94 (2)	O2—H1O2	0.8555
N2—C1	1.3332 (17)	O3—C14	1.2807 (17)
N2—H1N2	0.89 (2)	O4—C14	1.2391 (17)
N2—H2N2	0.86 (2)	C7—C8	1.3963 (19)
C1—C2	1.4136 (18)	C7—C12	1.4186 (17)
C2—C3	1.3738 (18)	C7—C14	1.5233 (18)
C2—H2A	0.94 (2)	C8—C9	1.388 (2)
C3—C4	1.4183 (19)	C8—H8A	0.93 (2)
C3—C6	1.4981 (18)	C9—C10	1.386 (2)
C4—C5	1.3596 (19)	C9—H9A	1.00 (2)
C4—H4A	0.892 (18)	C10—C11	1.386 (2)
C5—H5A	0.953 (19)	C10—H10A	0.94 (2)
C6—H6A	0.97 (2)	C11—C12	1.3988 (18)
C6—H6B	0.98 (2)	C11—H11A	0.967 (18)
C6—H6C	0.95 (3)	C12—C13	1.5195 (18)
C1—N1—C5	122.43 (12)	H6B—C6—H6C	108 (2)
C1—N1—H1N1	115.9 (14)	C13—O2—H1O2	107.5
C5—N1—H1N1	121.3 (14)	C8—C7—C12	118.39 (12)
C1—N2—H1N2	119.7 (14)	C8—C7—C14	113.53 (12)
C1—N2—H2N2	117.3 (13)	C12—C7—C14	128.08 (12)
H1N2—N2—H2N2	122.9 (19)	C9—C8—C7	122.17 (13)
N2—C1—N1	118.46 (12)	C9—C8—H8A	120.7 (14)
N2—C1—C2	123.73 (13)	C7—C8—H8A	117.1 (14)
N1—C1—C2	117.80 (12)	C10—C9—C8	119.66 (14)
C3—C2—C1	120.69 (12)	C10—C9—H9A	122.3 (13)
C3—C2—H2A	118.3 (12)	C8—C9—H9A	118.0 (13)
C1—C2—H2A	121.0 (12)	C11—C10—C9	118.92 (14)
C2—C3—C4	119.17 (12)	C11—C10—H10A	121.3 (13)
C2—C3—C6	121.37 (12)	C9—C10—H10A	119.8 (13)
C4—C3—C6	119.46 (12)	C10—C11—C12	122.65 (13)
C5—C4—C3	118.86 (12)	C10—C11—H11A	121.2 (11)
C5—C4—H4A	119.0 (11)	C12—C11—H11A	116.1 (11)
C3—C4—H4A	122.2 (11)	C11—C12—C7	118.20 (12)
C4—C5—N1	121.03 (12)	C11—C12—C13	113.40 (11)
C4—C5—H5A	124.5 (11)	C7—C12—C13	128.40 (12)
N1—C5—H5A	114.4 (11)	O1—C13—O2	121.18 (12)
C3—C6—H6A	114.0 (12)	O1—C13—C12	118.71 (12)
C3—C6—H6B	109.1 (14)	O2—C13—C12	120.10 (12)
H6A—C6—H6B	105.8 (19)	O4—C14—O3	122.37 (12)
C3—C6—H6C	112.3 (15)	O4—C14—C7	117.53 (12)
H6A—C6—H6C	107.2 (19)	O3—C14—C7	120.09 (12)
C5—N1—C1—N2	179.65 (13)	C10—C11—C12—C7	0.6 (2)
C5—N1—C1—C2	0.7 (2)	C10—C11—C12—C13	179.86 (15)
N2—C1—C2—C3	−178.20 (13)	C8—C7—C12—C11	−0.9 (2)
N1—C1—C2—C3	0.7 (2)	C14—C7—C12—C11	179.59 (13)
C1—C2—C3—C4	−1.1 (2)	C8—C7—C12—C13	179.96 (13)
C1—C2—C3—C6	178.00 (13)	C14—C7—C12—C13	0.5 (2)
C2—C3—C4—C5	0.2 (2)	C11—C12—C13—O1	−12.47 (18)
C6—C3—C4—C5	−178.95 (13)	C7—C12—C13—O1	166.68 (13)
C3—C4—C5—N1	1.2 (2)	C11—C12—C13—O2	166.57 (13)
C1—N1—C5—C4	−1.6 (2)	C7—C12—C13—O2	−14.3 (2)
C12—C7—C8—C9	0.5 (2)	C8—C7—C14—O4	12.57 (19)
C14—C7—C8—C9	−179.94 (16)	C12—C7—C14—O4	−167.93 (14)
C7—C8—C9—C10	0.3 (3)	C8—C7—C14—O3	−166.62 (14)
C8—C9—C10—C11	−0.6 (3)	C12—C7—C14—O3	12.9 (2)
C9—C10—C11—C12	0.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1O2···O3	0.86	1.57	2.4009 (14)	163
N1—H1N1···O4i	0.94 (2)	1.77 (2)	2.6919 (16)	169 (2)
N2—H1N2···O3i	0.89 (2)	2.11 (2)	2.9881 (16)	166.6 (19)
N2—H2N2···O1ii	0.86 (2)	2.06 (2)	2.8888 (16)	164.5 (19)
C5—H5A···O2iii	0.953 (19)	2.532 (19)	3.4133 (17)	153.7 (16)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H1O2⋯O3	0.86	1.57	2.4009 (14)	163
N1—H1N1⋯O4i	0.94 (2)	1.77 (2)	2.6919 (16)	169 (2)
N2—H1N2⋯O3i	0.89 (2)	2.11 (2)	2.9881 (16)	166.6 (19)
N2—H2N2⋯O1ii	0.86 (2)	2.06 (2)	2.8888 (16)	164.5 (19)
C5—H5A⋯O2iii	0.953 (19)	2.532 (19)	3.4133 (17)	153.7 (16)

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