2-Amino-6-methyl-pyridinium 2-carb-oxy-benzoate.

In the title mol-ecular salt, C(6)H(9)N(2) (+)·C(8)H(5)O(4) (-), an intra-molecular O-H⋯O hydrogen bond occurs within the anion, thereby generating an S(7) ring, which may correlate with the fact that both the carb-oxy-lic acid and carboxyl-ate groups are almost coplanar with their attached rings [dihedral angles = 2.9 (3) and 5.2 (3)°, respectively]. In the crystal, each cation is linked to its adjacent anion by two N-H⋯O hydrogen bonds; the dihedral angle between the pyridine and benzene rings is 2.22 (10)°. The ion pairs are linked by further N-H⋯O inter-actions.

Related literature

For related structures, see: Navarro Ranninger et al. (1985 ▶); Luque et al. (1997 ▶); Jin et al. (2000 ▶); Schuckmann et al. (1978 ▶); Küppers et al. (1985 ▶); Jessen (1990 ▶); Hemamalini & Fun (2010 ▶); Quah et al. (2010 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C6H9N2 +·C8H5O4 −

M = 274.27

Triclinic,

a = 7.473 (2) Å

b = 8.386 (3) Å

c = 11.818 (4) Å

α = 97.401 (6)°

β = 102.940 (7)°

γ = 109.616 (6)°

V = 662.9 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.10 mm−1

T = 296 K

1.00 × 0.20 × 0.10 mm

Data collection

Bruker APEXII DUO CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.905, T max = 0.990

12166 measured reflections

3706 independent reflections

2219 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.055

wR(F 2) = 0.190

S = 1.05

3706 reflections

194 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.20 e Å−3

Δρmin = −0.24 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/S1600536811033174/hb6359sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811033174/hb6359Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811033174/hb6359Isup3.cml

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

C6H9N2+·C8H5O4−	Z = 2
Mr = 274.27	F(000) = 288
Triclinic, P1	Dx = 1.374 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.473 (2) Å	Cell parameters from 3645 reflections
b = 8.386 (3) Å	θ = 2.6–27.4°
c = 11.818 (4) Å	µ = 0.10 mm−1
α = 97.401 (6)°	T = 296 K
β = 102.940 (7)°	Needle, colourless
γ = 109.616 (6)°	1.00 × 0.20 × 0.10 mm
V = 662.9 (4) Å3

Bruker APEXII DUO CCD diffractometer	3706 independent reflections
Radiation source: fine-focus sealed tube	2219 reflections with I > 2σ(I)
graphite	Rint = 0.044
φ and ω scans	θmax = 29.9°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→10
Tmin = 0.905, Tmax = 0.990	k = −11→11
12166 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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.190	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.1052P)2 + 0.0321P] where P = (Fo2 + 2Fc2)/3
3706 reflections	(Δ/σ)max < 0.001
194 parameters	Δρmax = 0.20 e Å−3
0 restraints	Δρmin = −0.24 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.3997 (3)	0.99186 (18)	0.64341 (12)	0.0720 (5)
H1O1	0.3652	0.8964	0.5951	0.108*
O2	0.4150 (3)	1.09584 (17)	0.82518 (13)	0.0727 (5)
O3	0.3231 (2)	0.71890 (18)	0.51427 (12)	0.0682 (4)
O4	0.2170 (2)	0.44177 (18)	0.51346 (12)	0.0694 (4)
N1	0.2619 (2)	0.33871 (18)	0.29978 (13)	0.0452 (3)
N2	0.3912 (3)	0.6236 (2)	0.28428 (16)	0.0562 (4)
C1	0.3333 (2)	0.4560 (2)	0.23665 (14)	0.0441 (4)
C2	0.3430 (3)	0.3937 (2)	0.12220 (15)	0.0504 (4)
H2A	0.3931	0.4707	0.0766	0.060*
C3	0.2783 (3)	0.2199 (3)	0.07971 (17)	0.0574 (5)
H3A	0.2823	0.1782	0.0039	0.069*
C4	0.2057 (3)	0.1023 (3)	0.14768 (18)	0.0584 (5)
H4A	0.1623	−0.0164	0.1174	0.070*
C5	0.1989 (3)	0.1630 (2)	0.25911 (17)	0.0503 (4)
C6	0.1328 (4)	0.0531 (3)	0.3429 (2)	0.0694 (6)
H6A	0.0575	−0.0647	0.2996	0.104*
H6B	0.0516	0.0958	0.3808	0.104*
H6C	0.2465	0.0575	0.4023	0.104*
C7	0.2521 (3)	0.7860 (2)	0.87715 (15)	0.0481 (4)
H7A	0.2875	0.8912	0.9299	0.058*
C8	0.1716 (3)	0.6332 (3)	0.91302 (16)	0.0539 (4)
H8A	0.1541	0.6364	0.9886	0.065*
C9	0.1182 (3)	0.4775 (3)	0.83617 (17)	0.0561 (5)
H9A	0.0626	0.3742	0.8589	0.067*
C10	0.1472 (3)	0.4744 (2)	0.72467 (16)	0.0511 (4)
H10A	0.1106	0.3678	0.6733	0.061*
C11	0.2297 (2)	0.6265 (2)	0.68645 (13)	0.0419 (4)
C12	0.2586 (3)	0.5937 (2)	0.56344 (15)	0.0481 (4)
C13	0.2820 (2)	0.7880 (2)	0.76533 (14)	0.0424 (4)
C14	0.3712 (3)	0.9700 (2)	0.74459 (16)	0.0498 (4)
H1N1	0.251 (3)	0.383 (3)	0.378 (2)	0.068 (6)*
H1N2	0.454 (4)	0.707 (3)	0.243 (2)	0.075 (7)*
H2N2	0.394 (3)	0.663 (3)	0.361 (2)	0.074 (7)*

	U11	U22	U33	U12	U13	U23
O1	0.1160 (13)	0.0466 (8)	0.0533 (8)	0.0208 (7)	0.0380 (8)	0.0130 (6)
O2	0.1115 (13)	0.0458 (8)	0.0560 (8)	0.0212 (8)	0.0330 (8)	0.0025 (6)
O3	0.0998 (11)	0.0543 (8)	0.0468 (8)	0.0175 (7)	0.0337 (7)	0.0086 (6)
O4	0.1065 (12)	0.0497 (8)	0.0519 (8)	0.0250 (8)	0.0338 (8)	0.0029 (6)
N1	0.0491 (8)	0.0417 (8)	0.0408 (7)	0.0147 (6)	0.0123 (6)	0.0028 (6)
N2	0.0740 (10)	0.0417 (8)	0.0501 (9)	0.0160 (7)	0.0239 (8)	0.0053 (7)
C1	0.0449 (8)	0.0456 (9)	0.0404 (8)	0.0185 (7)	0.0096 (6)	0.0052 (7)
C2	0.0558 (10)	0.0596 (11)	0.0411 (9)	0.0285 (8)	0.0149 (7)	0.0089 (8)
C3	0.0618 (11)	0.0663 (12)	0.0447 (9)	0.0328 (9)	0.0114 (8)	−0.0023 (8)
C4	0.0616 (11)	0.0504 (10)	0.0579 (11)	0.0235 (8)	0.0119 (9)	−0.0037 (8)
C5	0.0488 (9)	0.0428 (9)	0.0540 (10)	0.0153 (7)	0.0118 (7)	0.0038 (7)
C6	0.0795 (14)	0.0504 (11)	0.0794 (15)	0.0201 (10)	0.0301 (11)	0.0171 (10)
C7	0.0554 (10)	0.0511 (10)	0.0409 (9)	0.0231 (8)	0.0168 (7)	0.0065 (7)
C8	0.0629 (11)	0.0627 (12)	0.0449 (9)	0.0269 (9)	0.0250 (8)	0.0165 (8)
C9	0.0638 (11)	0.0508 (10)	0.0538 (11)	0.0150 (8)	0.0236 (8)	0.0184 (8)
C10	0.0577 (10)	0.0441 (9)	0.0453 (9)	0.0130 (7)	0.0149 (7)	0.0065 (7)
C11	0.0411 (8)	0.0473 (9)	0.0355 (8)	0.0165 (6)	0.0096 (6)	0.0062 (6)
C12	0.0519 (9)	0.0511 (10)	0.0378 (8)	0.0168 (7)	0.0120 (7)	0.0063 (7)
C13	0.0442 (8)	0.0451 (9)	0.0382 (8)	0.0183 (7)	0.0114 (6)	0.0072 (7)
C14	0.0596 (10)	0.0451 (9)	0.0452 (9)	0.0190 (7)	0.0171 (7)	0.0097 (7)

O1—C14	1.286 (2)	C4—H4A	0.9300
O1—H1O1	0.8434	C5—C6	1.491 (3)
O2—C14	1.223 (2)	C6—H6A	0.9600
O3—C12	1.271 (2)	C6—H6B	0.9600
O4—C12	1.236 (2)	C6—H6C	0.9600
N1—C1	1.350 (2)	C7—C8	1.386 (3)
N1—C5	1.369 (2)	C7—C13	1.390 (2)
N1—H1N1	0.99 (3)	C7—H7A	0.9300
N2—C1	1.326 (2)	C8—C9	1.367 (3)
N2—H1N2	0.95 (3)	C8—H8A	0.9300
N2—H2N2	0.92 (3)	C9—C10	1.381 (3)
C1—C2	1.413 (2)	C9—H9A	0.9300
C2—C3	1.356 (3)	C10—C11	1.398 (2)
C2—H2A	0.9300	C10—H10A	0.9300
C3—C4	1.397 (3)	C11—C13	1.418 (2)
C3—H3A	0.9300	C11—C12	1.521 (2)
C4—C5	1.368 (3)	C13—C14	1.524 (3)
C14—O1—H1O1	111.8	H6A—C6—H6C	109.5
C1—N1—C5	123.64 (16)	H6B—C6—H6C	109.5
C1—N1—H1N1	117.4 (13)	C8—C7—C13	122.48 (17)
C5—N1—H1N1	118.9 (13)	C8—C7—H7A	118.8
C1—N2—H1N2	119.1 (15)	C13—C7—H7A	118.8
C1—N2—H2N2	122.3 (15)	C9—C8—C7	119.37 (17)
H1N2—N2—H2N2	118 (2)	C9—C8—H8A	120.3
N2—C1—N1	118.97 (16)	C7—C8—H8A	120.3
N2—C1—C2	122.93 (17)	C8—C9—C10	119.76 (17)
N1—C1—C2	118.09 (15)	C8—C9—H9A	120.1
C3—C2—C1	119.05 (18)	C10—C9—H9A	120.1
C3—C2—H2A	120.5	C9—C10—C11	122.13 (17)
C1—C2—H2A	120.5	C9—C10—H10A	118.9
C2—C3—C4	121.27 (18)	C11—C10—H10A	118.9
C2—C3—H3A	119.4	C10—C11—C13	118.15 (15)
C4—C3—H3A	119.4	C10—C11—C12	113.54 (15)
C5—C4—C3	119.58 (17)	C13—C11—C12	128.27 (15)
C5—C4—H4A	120.2	O4—C12—O3	121.50 (17)
C3—C4—H4A	120.2	O4—C12—C11	117.68 (15)
C4—C5—N1	118.35 (17)	O3—C12—C11	120.82 (16)
C4—C5—C6	125.27 (18)	C7—C13—C11	118.09 (15)
N1—C5—C6	116.36 (17)	C7—C13—C14	113.65 (15)
C5—C6—H6A	109.5	C11—C13—C14	128.25 (15)
C5—C6—H6B	109.5	O2—C14—O1	120.10 (17)
H6A—C6—H6B	109.5	O2—C14—C13	119.35 (16)
C5—C6—H6C	109.5	O1—C14—C13	120.55 (16)
C5—N1—C1—N2	−179.76 (16)	C10—C11—C12—O4	−3.4 (2)
C5—N1—C1—C2	0.1 (2)	C13—C11—C12—O4	174.11 (17)
N2—C1—C2—C3	−179.19 (17)	C10—C11—C12—O3	176.56 (16)
N1—C1—C2—C3	0.9 (2)	C13—C11—C12—O3	−5.9 (3)
C1—C2—C3—C4	−1.1 (3)	C8—C7—C13—C11	−0.8 (3)
C2—C3—C4—C5	0.2 (3)	C8—C7—C13—C14	179.70 (16)
C3—C4—C5—N1	0.8 (3)	C10—C11—C13—C7	1.3 (2)
C3—C4—C5—C6	−177.48 (18)	C12—C11—C13—C7	−176.07 (15)
C1—N1—C5—C4	−1.0 (3)	C10—C11—C13—C14	−179.27 (16)
C1—N1—C5—C6	177.44 (16)	C12—C11—C13—C14	3.3 (3)
C13—C7—C8—C9	−0.2 (3)	C7—C13—C14—O2	2.5 (3)
C7—C8—C9—C10	0.8 (3)	C11—C13—C14—O2	−176.88 (17)
C8—C9—C10—C11	−0.2 (3)	C7—C13—C14—O1	−177.23 (17)
C9—C10—C11—C13	−0.9 (3)	C11—C13—C14—O1	3.4 (3)
C9—C10—C11—C12	176.92 (17)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···O3	0.84	1.55	2.393 (2)	174
N1—H1N1···O4	0.98 (2)	1.71 (2)	2.692 (2)	175 (2)
N2—H1N2···O2i	0.96 (3)	1.99 (2)	2.940 (3)	172 (2)
N2—H2N2···O3	0.92 (2)	2.04 (2)	2.936 (3)	165 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯O3	0.84	1.55	2.393 (2)	174
N1—H1N1⋯O4	0.98 (2)	1.71 (2)	2.692 (2)	175 (2)
N2—H1N2⋯O2i	0.96 (3)	1.99 (2)	2.940 (3)	172 (2)
N2—H2N2⋯O3	0.92 (2)	2.04 (2)	2.936 (3)	165 (2)

Symmetry code: (i) .