2-Amino-5-methyl-pyridinium 2-hy-droxy-benzoate.

In the title compound, C(6)H(9)N(2) (+)·C(7)H(5)O(3) (-), the protonated 2-amino-5-methyl-pyridinium cation and the 2-hy-droxy-benzoate anion are both essentially planar, with maximum deviations of 0.026 (2) and 0.034 (1) Å, respectively. The anion is stabilized by an intra-molecular O-H⋯O hydrogen bond, which forms an S(6) ring motif. In the solid state, the anions are linked to the cations via pairs of inter-molecular N-H⋯O hydrogen bonds forming R(2) (2)(8) ring motifs. The crystal structure is further stabilized by N-H⋯O and C-H⋯O inter-actions which link the mol-ecules into chains along [010]. A π-π stacking inter-action [centroid-centroid-distance = 3.740 (2) Å] is also observed.

Related literature

For background to and the applications of carb­oxy­lic acids, see: Miller & Orgel (1974 ▶); Kvenvolden et al. (1971 ▶); Desiraju (1989 ▶); MacDonald & Whitesides (1994 ▶). For applications of salicylic acid, see: Singh & Vijayan (1974 ▶); Patel et al. (1988 ▶). For related structures, see: Quah et al. (2008 ▶; 2010a ▶,b ▶). For bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C6H9N2 +·C7H5O3 −

M = 246.26

Monoclinic,

a = 13.211 (7) Å

b = 7.170 (4) Å

c = 14.324 (7) Å

β = 104.668 (11)°

V = 1312.6 (12) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 297 K

0.42 × 0.19 × 0.10 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.963, T max = 0.991

14312 measured reflections

3797 independent reflections

2233 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.134

S = 1.01

3797 reflections

219 parameters

All H-atom parameters refined

Δρmax = 0.14 e Å−3

Δρmin = −0.15 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/S1600536810030928/bt5314sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810030928/bt5314Isup2.hkl

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

C6H9N2+·C7H5O3−	F(000) = 520
Mr = 246.26	Dx = 1.246 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3026 reflections
a = 13.211 (7) Å	θ = 3.2–26.8°
b = 7.170 (4) Å	µ = 0.09 mm−1
c = 14.324 (7) Å	T = 297 K
β = 104.668 (11)°	Block, yellow
V = 1312.6 (12) Å3	0.42 × 0.19 × 0.10 mm
Z = 4

Bruker SMART APEXII DUO CCD area-detector diffractometer	3797 independent reflections
Radiation source: fine-focus sealed tube	2233 reflections with I > 2σ(I)
graphite	Rint = 0.028
φ and ω scans	θmax = 30.0°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −18→18
Tmin = 0.963, Tmax = 0.991	k = −10→10
14312 measured reflections	l = −20→19

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.134	All H-atom parameters refined
S = 1.01	w = 1/[σ2(Fo2) + (0.0607P)2 + 0.0959P] where P = (Fo2 + 2Fc2)/3
3797 reflections	(Δ/σ)max < 0.001
219 parameters	Δρmax = 0.14 e Å−3
0 restraints	Δρmin = −0.15 e Å−3

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	0.25056 (7)	0.79968 (17)	0.30963 (8)	0.0491 (3)
N2	0.07534 (9)	0.7373 (2)	0.28908 (10)	0.0664 (4)
C1	0.15649 (8)	0.84904 (19)	0.32288 (9)	0.0485 (3)
C2	0.15072 (10)	1.0168 (2)	0.37198 (9)	0.0542 (3)
C3	0.23752 (10)	1.1242 (2)	0.40264 (10)	0.0561 (3)
C4	0.33511 (10)	1.0709 (2)	0.38749 (9)	0.0544 (3)
C5	0.33759 (9)	0.9075 (2)	0.34103 (9)	0.0523 (3)
C6	0.43050 (14)	1.1912 (3)	0.41915 (16)	0.0791 (5)
O1	0.40974 (7)	0.27586 (19)	0.17167 (9)	0.0806 (4)
O2	0.10956 (7)	0.41138 (14)	0.18462 (8)	0.0703 (3)
O3	0.27788 (7)	0.48394 (15)	0.21915 (9)	0.0710 (3)
C7	0.32912 (10)	0.1574 (2)	0.13606 (10)	0.0581 (4)
C8	0.35051 (15)	−0.0109 (3)	0.09641 (12)	0.0760 (5)
C9	0.27204 (17)	−0.1348 (3)	0.05976 (13)	0.0830 (5)
C10	0.17009 (17)	−0.0959 (3)	0.06012 (13)	0.0799 (5)
C11	0.14807 (12)	0.0712 (2)	0.09921 (11)	0.0635 (4)
C12	0.22624 (9)	0.19952 (19)	0.13827 (9)	0.0494 (3)
C13	0.20156 (9)	0.37630 (19)	0.18311 (10)	0.0529 (3)
H2A	0.0850 (11)	1.050 (2)	0.3827 (10)	0.067 (4)*
H3A	0.2348 (12)	1.246 (3)	0.4373 (11)	0.074 (5)*
H5A	0.3970 (10)	0.854 (2)	0.3237 (9)	0.053 (3)*
H6A	0.4887 (16)	1.146 (3)	0.3935 (14)	0.107 (7)*
H6B	0.4150 (17)	1.318 (4)	0.3879 (17)	0.131 (9)*
H6C	0.4491 (16)	1.208 (3)	0.4862 (19)	0.123 (8)*
H8A	0.4216 (15)	−0.033 (3)	0.1009 (13)	0.097 (6)*
H9A	0.2895 (14)	−0.256 (3)	0.0343 (13)	0.098 (6)*
H10A	0.1156 (15)	−0.181 (3)	0.0375 (14)	0.102 (6)*
H11A	0.0773 (12)	0.101 (2)	0.1003 (10)	0.068 (4)*
H1N1	0.2564 (11)	0.678 (3)	0.2733 (11)	0.073 (4)*
H1N2	0.0141 (13)	0.771 (2)	0.2980 (12)	0.078 (5)*
H2N2	0.0862 (13)	0.626 (3)	0.2540 (13)	0.087 (5)*
H1O1	0.3730 (16)	0.382 (3)	0.1984 (15)	0.116 (7)*

	U11	U22	U33	U12	U13	U23
N1	0.0397 (5)	0.0494 (7)	0.0589 (6)	0.0009 (5)	0.0137 (4)	−0.0009 (5)
N2	0.0401 (5)	0.0620 (9)	0.0988 (9)	−0.0039 (5)	0.0209 (6)	−0.0157 (7)
C1	0.0396 (5)	0.0504 (8)	0.0560 (7)	0.0017 (5)	0.0131 (5)	0.0018 (6)
C2	0.0480 (6)	0.0565 (9)	0.0592 (7)	0.0039 (6)	0.0158 (6)	−0.0028 (6)
C3	0.0614 (7)	0.0537 (9)	0.0520 (7)	−0.0011 (7)	0.0121 (6)	−0.0041 (7)
C4	0.0524 (7)	0.0579 (9)	0.0508 (7)	−0.0090 (6)	0.0092 (5)	0.0044 (6)
C5	0.0401 (6)	0.0607 (9)	0.0574 (7)	−0.0017 (6)	0.0143 (5)	0.0045 (7)
C6	0.0653 (9)	0.0833 (14)	0.0848 (12)	−0.0264 (10)	0.0118 (9)	−0.0071 (11)
O1	0.0495 (5)	0.0882 (9)	0.1105 (9)	0.0064 (5)	0.0323 (5)	−0.0146 (7)
O2	0.0473 (5)	0.0544 (7)	0.1169 (8)	0.0028 (4)	0.0349 (5)	−0.0095 (6)
O3	0.0502 (5)	0.0530 (6)	0.1159 (8)	−0.0031 (5)	0.0324 (5)	−0.0166 (6)
C7	0.0549 (7)	0.0635 (10)	0.0597 (7)	0.0154 (7)	0.0216 (6)	0.0049 (7)
C8	0.0784 (10)	0.0775 (13)	0.0775 (10)	0.0292 (10)	0.0297 (8)	−0.0028 (9)
C9	0.1128 (15)	0.0655 (12)	0.0739 (10)	0.0248 (11)	0.0296 (10)	−0.0121 (9)
C10	0.0967 (13)	0.0645 (12)	0.0772 (11)	−0.0022 (10)	0.0198 (9)	−0.0197 (9)
C11	0.0634 (8)	0.0604 (10)	0.0672 (9)	0.0032 (7)	0.0177 (7)	−0.0063 (7)
C12	0.0505 (6)	0.0480 (8)	0.0521 (6)	0.0086 (6)	0.0176 (5)	0.0059 (6)
C13	0.0471 (6)	0.0451 (8)	0.0719 (8)	0.0040 (6)	0.0252 (6)	0.0047 (7)

N1—C1	1.3510 (15)	C6—H6C	0.94 (3)
N1—C5	1.3638 (17)	O1—C7	1.3567 (19)
N1—H1N1	1.030 (18)	O1—H1O1	1.03 (2)
N2—C1	1.3279 (18)	O2—C13	1.2467 (15)
N2—H1N2	0.884 (18)	O3—C13	1.2710 (16)
N2—H2N2	0.97 (2)	C7—C8	1.393 (2)
C1—C2	1.405 (2)	C7—C12	1.4006 (18)
C2—C3	1.359 (2)	C8—C9	1.365 (3)
C2—H2A	0.950 (15)	C8—H8A	0.938 (19)
C3—C4	1.413 (2)	C9—C10	1.377 (3)
C3—H3A	1.011 (18)	C9—H9A	0.99 (2)
C4—C5	1.352 (2)	C10—C11	1.384 (2)
C4—C6	1.500 (2)	C10—H10A	0.94 (2)
C5—H5A	0.960 (13)	C11—C12	1.391 (2)
C6—H6A	0.99 (2)	C11—H11A	0.962 (15)
C6—H6B	1.01 (3)	C12—C13	1.494 (2)
C1—N1—C5	122.26 (13)	H6A—C6—H6C	113.4 (17)
C1—N1—H1N1	118.8 (8)	H6B—C6—H6C	108 (2)
C5—N1—H1N1	118.9 (8)	C7—O1—H1O1	101.7 (11)
C1—N2—H1N2	117.6 (11)	O1—C7—C8	118.34 (13)
C1—N2—H2N2	118.2 (10)	O1—C7—C12	122.04 (13)
H1N2—N2—H2N2	124.1 (15)	C8—C7—C12	119.62 (15)
N2—C1—N1	118.50 (13)	C9—C8—C7	120.52 (16)
N2—C1—C2	123.91 (12)	C9—C8—H8A	124.5 (13)
N1—C1—C2	117.58 (11)	C7—C8—H8A	114.8 (13)
C3—C2—C1	119.91 (12)	C8—C9—C10	121.02 (18)
C3—C2—H2A	122.5 (9)	C8—C9—H9A	119.2 (11)
C1—C2—H2A	117.6 (9)	C10—C9—H9A	119.8 (11)
C2—C3—C4	121.70 (14)	C9—C10—C11	118.87 (18)
C2—C3—H3A	121.2 (9)	C9—C10—H10A	122.2 (13)
C4—C3—H3A	117.1 (9)	C11—C10—H10A	118.9 (13)
C5—C4—C3	116.52 (12)	C10—C11—C12	121.65 (15)
C5—C4—C6	121.61 (14)	C10—C11—H11A	120.0 (10)
C3—C4—C6	121.86 (16)	C12—C11—H11A	118.3 (9)
C4—C5—N1	122.02 (12)	C11—C12—C7	118.32 (13)
C4—C5—H5A	126.5 (8)	C11—C12—C13	120.92 (12)
N1—C5—H5A	111.4 (8)	C7—C12—C13	120.75 (12)
C4—C6—H6A	111.8 (13)	O2—C13—O3	123.17 (13)
C4—C6—H6B	108.9 (13)	O2—C13—C12	119.90 (12)
H6A—C6—H6B	102.8 (18)	O3—C13—C12	116.93 (11)
C4—C6—H6C	111.5 (14)
C5—N1—C1—N2	179.21 (12)	C8—C9—C10—C11	−0.5 (3)
C5—N1—C1—C2	−0.82 (18)	C9—C10—C11—C12	−0.3 (3)
N2—C1—C2—C3	−178.87 (13)	C10—C11—C12—C7	1.0 (2)
N1—C1—C2—C3	1.16 (19)	C10—C11—C12—C13	−177.95 (14)
C1—C2—C3—C4	−0.7 (2)	O1—C7—C12—C11	179.29 (13)
C2—C3—C4—C5	−0.1 (2)	C8—C7—C12—C11	−0.8 (2)
C2—C3—C4—C6	178.54 (15)	O1—C7—C12—C13	−1.8 (2)
C3—C4—C5—N1	0.46 (19)	C8—C7—C12—C13	178.09 (13)
C6—C4—C5—N1	−178.17 (14)	C11—C12—C13—O2	−1.0 (2)
C1—N1—C5—C4	0.00 (19)	C7—C12—C13—O2	−179.86 (12)
O1—C7—C8—C9	179.92 (15)	C11—C12—C13—O3	178.39 (13)
C12—C7—C8—C9	0.0 (2)	C7—C12—C13—O3	−0.49 (19)
C7—C8—C9—C10	0.7 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O3	1.03 (2)	1.65 (2)	2.678 (2)	174.6 (13)
N2—H1N2···O2i	0.884 (18)	1.987 (17)	2.852 (2)	165.4 (14)
N2—H2N2···O2	0.97 (2)	1.90 (2)	2.872 (2)	179 (2)
O1—H1O1···O3	1.03 (2)	1.55 (2)	2.515 (2)	155 (2)
C5—H5A···O1ii	0.961 (14)	2.598 (14)	3.518 (3)	160.2 (10)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O3	1.03 (2)	1.65 (2)	2.678 (2)	174.6 (13)
N2—H1N2⋯O2i	0.884 (18)	1.987 (17)	2.852 (2)	165.4 (14)
N2—H2N2⋯O2	0.97 (2)	1.90 (2)	2.872 (2)	179 (2)
O1—H1O1⋯O3	1.03 (2)	1.55 (2)	2.515 (2)	155 (2)
C5—H5A⋯O1ii	0.961 (14)	2.598 (14)	3.518 (3)	160.2 (10)

Symmetry codes: (i) ; (ii) .