2-Amino-5-methyl-pyridinium 4-hydroxy-benzoate.

In the title salt, C(6)H(9)N(2) (+)·C(7)H(5)O(3) (-), the carboxyl-ate mean plane of the 4-hydroxy-benzoate anion is twisted by 13.07 (4)° from the attached ring. In the crystal structure, the ions are linked into a two-dimensional network by N-H⋯O, O-H⋯O and C-H⋯O hydrogen bonds. Within this network, the N-H⋯O hydrogen bonds generate R(2) (2)(8) ring motifs. In addition, π-π inter-actions involving the pyridinium rings, with a centroid-centroid distance of 3.7599 (4) Å, are observed.

Related literature

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997 ▶); Katritzky et al. (1996 ▶). For related structures, see: Hemamalini & Fun (2010a ▶,b ▶,c ▶). For 4-hydroxy­benzoic acid, see: Vishweshwar et al. (2003 ▶). For details of hydrogen bonding, see: Jeffrey & Saenger (1991 ▶); Jeffrey (1997 ▶); Scheiner (1997 ▶); Aakeröy et al. (2002 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C6H9N2 +·C7H5O3 −

M = 246.26

Monoclinic,

a = 12.9562 (6) Å

b = 8.7876 (4) Å

c = 11.3276 (5) Å

β = 108.397 (1)°

V = 1223.78 (10) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 100 K

0.39 × 0.33 × 0.27 mm

Data collection

Bruker APEX DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.963, T max = 0.975

20102 measured reflections

5326 independent reflections

4662 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.137

S = 1.15

5326 reflections

219 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.60 e Å−3

Δρmin = −0.32 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/S1600536810009396/rz2424sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810009396/rz2424Isup2.hkl

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

C6H9N2+·C7H5O3−	F(000) = 520
Mr = 246.26	Dx = 1.337 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9907 reflections
a = 12.9562 (6) Å	θ = 6.5–36.2°
b = 8.7876 (4) Å	µ = 0.10 mm−1
c = 11.3276 (5) Å	T = 100 K
β = 108.397 (1)°	Blcok, colourless
V = 1223.78 (10) Å3	0.39 × 0.33 × 0.27 mm
Z = 4

Bruker APEX DUO CCD area-detector diffractometer	5326 independent reflections
Radiation source: fine-focus sealed tube	4662 reflections with I > 2σ(I)
graphite	Rint = 0.019
φ and ω scans	θmax = 35.0°, θmin = 6.2°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −19→20
Tmin = 0.963, Tmax = 0.975	k = −14→11
20102 measured reflections	l = −18→15

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) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.15	w = 1/[σ2(Fo2) + (0.0859P)2 + 0.1288P] where P = (Fo2 + 2Fc2)/3
5326 reflections	(Δ/σ)max = 0.001
219 parameters	Δρmax = 0.60 e Å−3
0 restraints	Δρmin = −0.32 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 s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	−0.07705 (4)	1.29454 (6)	0.44060 (5)	0.01923 (12)
O2	0.23879 (4)	0.85691 (6)	0.26656 (5)	0.01752 (11)
O3	0.34273 (4)	0.90704 (7)	0.45979 (5)	0.02001 (12)
C7	0.17088 (6)	1.07237 (8)	0.50635 (6)	0.01751 (13)
C8	0.08861 (6)	1.16244 (9)	0.52300 (6)	0.01815 (13)
C9	0.00128 (5)	1.20628 (7)	0.42014 (6)	0.01493 (12)
C10	−0.00280 (5)	1.15864 (8)	0.30079 (6)	0.01519 (12)
C11	0.07897 (5)	1.06554 (8)	0.28576 (6)	0.01482 (12)
C12	0.16699 (5)	1.02150 (7)	0.38786 (6)	0.01410 (11)
C13	0.25438 (5)	0.92210 (8)	0.37051 (6)	0.01435 (12)
N1	0.48836 (5)	0.71343 (7)	0.42194 (5)	0.01544 (11)
N2	0.39201 (5)	0.66496 (8)	0.21647 (6)	0.01851 (12)
C1	0.48185 (5)	0.64504 (7)	0.31296 (6)	0.01461 (12)
C2	0.57195 (6)	0.55617 (8)	0.30846 (6)	0.01732 (13)
C3	0.65954 (6)	0.53911 (8)	0.41374 (7)	0.01848 (13)
C4	0.66298 (5)	0.60787 (8)	0.52806 (6)	0.01614 (12)
C5	0.57535 (5)	0.69542 (8)	0.52670 (6)	0.01641 (12)
C6	0.75785 (6)	0.58625 (10)	0.64330 (7)	0.02191 (14)
H2A	0.5718 (11)	0.5103 (16)	0.2257 (12)	0.027 (3)*
H3A	0.7256 (12)	0.4762 (18)	0.4148 (13)	0.034 (3)*
H5A	0.5712 (11)	0.7533 (16)	0.5988 (13)	0.027 (3)*
H6A	0.7657 (12)	0.4804 (19)	0.6662 (14)	0.039 (4)*
H6B	0.8244 (13)	0.6124 (18)	0.6294 (14)	0.038 (4)*
H6C	0.7483 (13)	0.6507 (19)	0.7124 (16)	0.040 (4)*
H7A	0.2334 (11)	1.0425 (17)	0.5794 (13)	0.029 (3)*
H8A	0.0899 (13)	1.2010 (18)	0.6068 (15)	0.038 (4)*
H10A	−0.0628 (12)	1.1968 (16)	0.2289 (14)	0.030 (3)*
H11A	0.0758 (10)	1.0333 (15)	0.2012 (11)	0.021 (3)*
H101	−0.1257 (15)	1.3172 (19)	0.3673 (16)	0.045 (4)*
H1N1	0.4304 (13)	0.7749 (19)	0.4310 (14)	0.038 (4)*
H1N2	0.3819 (12)	0.6231 (15)	0.1407 (13)	0.028 (3)*
H2N2	0.3394 (11)	0.7245 (15)	0.2326 (12)	0.025 (3)*

	U11	U22	U33	U12	U13	U23
O1	0.0165 (2)	0.0239 (3)	0.0175 (2)	0.00637 (17)	0.00561 (18)	0.00151 (18)
O2	0.0140 (2)	0.0240 (2)	0.0143 (2)	0.00056 (16)	0.00405 (16)	−0.00257 (17)
O3	0.0149 (2)	0.0292 (3)	0.0137 (2)	0.00667 (18)	0.00134 (16)	−0.00034 (18)
C7	0.0160 (3)	0.0233 (3)	0.0122 (2)	0.0047 (2)	0.0029 (2)	0.0015 (2)
C8	0.0176 (3)	0.0240 (3)	0.0124 (2)	0.0053 (2)	0.0041 (2)	0.0011 (2)
C9	0.0131 (2)	0.0166 (3)	0.0150 (2)	0.00114 (18)	0.00441 (19)	0.00139 (19)
C10	0.0128 (2)	0.0175 (3)	0.0136 (2)	0.00088 (19)	0.00182 (19)	0.00068 (19)
C11	0.0137 (2)	0.0171 (3)	0.0126 (2)	0.00074 (19)	0.00256 (19)	0.00033 (19)
C12	0.0123 (2)	0.0169 (2)	0.0127 (2)	0.00125 (18)	0.00344 (18)	0.00125 (19)
C13	0.0125 (2)	0.0180 (3)	0.0127 (2)	0.00072 (19)	0.00415 (19)	0.00162 (19)
N1	0.0147 (2)	0.0176 (2)	0.0136 (2)	0.00132 (17)	0.00391 (18)	−0.00160 (17)
N2	0.0164 (2)	0.0227 (3)	0.0144 (2)	0.00148 (19)	0.00197 (19)	−0.00235 (19)
C1	0.0152 (2)	0.0154 (2)	0.0135 (2)	−0.00101 (18)	0.0050 (2)	−0.00051 (19)
C2	0.0187 (3)	0.0187 (3)	0.0155 (3)	0.0024 (2)	0.0067 (2)	−0.0014 (2)
C3	0.0174 (3)	0.0202 (3)	0.0185 (3)	0.0030 (2)	0.0066 (2)	−0.0001 (2)
C4	0.0144 (2)	0.0177 (3)	0.0158 (3)	−0.0001 (2)	0.0041 (2)	0.0008 (2)
C5	0.0160 (3)	0.0193 (3)	0.0134 (2)	0.0003 (2)	0.0039 (2)	−0.0015 (2)
C6	0.0163 (3)	0.0271 (3)	0.0193 (3)	0.0001 (2)	0.0013 (2)	0.0036 (2)

O1—C9	1.3541 (8)	N1—C5	1.3636 (9)
O1—H101	0.893 (18)	N1—H1N1	0.956 (16)
O2—C13	1.2670 (8)	N2—C1	1.3331 (9)
O3—C13	1.2728 (8)	N2—H1N2	0.904 (14)
C7—C8	1.3875 (9)	N2—H2N2	0.922 (14)
C7—C12	1.4004 (9)	C1—C2	1.4187 (9)
C7—H7A	0.993 (14)	C2—C3	1.3705 (10)
C8—C9	1.3978 (9)	C2—H2A	1.020 (13)
C8—H8A	1.003 (15)	C3—C4	1.4169 (10)
C9—C10	1.4003 (9)	C3—H3A	1.016 (15)
C10—C11	1.3909 (9)	C4—C5	1.3675 (9)
C10—H10A	0.990 (15)	C4—C6	1.4962 (10)
C11—C12	1.3984 (9)	C5—H5A	0.978 (14)
C11—H11A	0.987 (12)	C6—H6A	0.963 (16)
C12—C13	1.4912 (9)	C6—H6B	0.952 (16)
N1—C1	1.3516 (8)	C6—H6C	1.006 (17)
C9—O1—H101	108.4 (11)	C1—N2—H1N2	123.5 (9)
C8—C7—C12	121.04 (6)	C1—N2—H2N2	114.9 (8)
C8—C7—H7A	119.8 (8)	H1N2—N2—H2N2	121.6 (12)
C12—C7—H7A	119.1 (8)	N2—C1—N1	118.50 (6)
C7—C8—C9	119.89 (6)	N2—C1—C2	123.94 (6)
C7—C8—H8A	122.5 (9)	N1—C1—C2	117.56 (6)
C9—C8—H8A	117.6 (9)	C3—C2—C1	119.59 (6)
O1—C9—C8	117.93 (6)	C3—C2—H2A	121.2 (8)
O1—C9—C10	122.31 (6)	C1—C2—H2A	119.2 (8)
C8—C9—C10	119.76 (6)	C2—C3—C4	121.81 (6)
C11—C10—C9	119.73 (6)	C2—C3—H3A	122.2 (8)
C11—C10—H10A	122.0 (9)	C4—C3—H3A	116.0 (8)
C9—C10—H10A	118.2 (9)	C5—C4—C3	116.31 (6)
C10—C11—C12	121.02 (6)	C5—C4—C6	122.13 (6)
C10—C11—H11A	119.2 (7)	C3—C4—C6	121.56 (6)
C12—C11—H11A	119.7 (7)	N1—C5—C4	122.03 (6)
C11—C12—C7	118.53 (6)	N1—C5—H5A	114.7 (8)
C11—C12—C13	120.53 (6)	C4—C5—H5A	123.2 (8)
C7—C12—C13	120.94 (6)	C4—C6—H6A	110.2 (9)
O2—C13—O3	122.08 (6)	C4—C6—H6B	111.2 (9)
O2—C13—C12	118.84 (6)	H6A—C6—H6B	104.7 (13)
O3—C13—C12	119.08 (6)	C4—C6—H6C	109.8 (9)
C1—N1—C5	122.65 (6)	H6A—C6—H6C	111.4 (13)
C1—N1—H1N1	121.6 (9)	H6B—C6—H6C	109.5 (13)
C5—N1—H1N1	115.7 (9)
C12—C7—C8—C9	−1.35 (11)	C11—C12—C13—O3	166.93 (6)
C7—C8—C9—O1	−179.81 (6)	C7—C12—C13—O3	−13.29 (10)
C7—C8—C9—C10	0.17 (11)	C5—N1—C1—N2	177.71 (6)
O1—C9—C10—C11	−178.73 (6)	C5—N1—C1—C2	−2.43 (10)
C8—C9—C10—C11	1.29 (10)	N2—C1—C2—C3	−178.20 (7)
C9—C10—C11—C12	−1.60 (10)	N1—C1—C2—C3	1.94 (10)
C10—C11—C12—C7	0.44 (10)	C1—C2—C3—C4	0.08 (11)
C10—C11—C12—C13	−179.77 (6)	C2—C3—C4—C5	−1.66 (11)
C8—C7—C12—C11	1.05 (11)	C2—C3—C4—C6	178.74 (7)
C8—C7—C12—C13	−178.74 (6)	C1—N1—C5—C4	0.83 (11)
C11—C12—C13—O2	−12.12 (10)	C3—C4—C5—N1	1.25 (10)
C7—C12—C13—O2	167.67 (6)	C6—C4—C5—N1	−179.16 (6)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O3	0.957 (17)	1.726 (17)	2.6738 (9)	170.4 (15)
N2—H1N2···O3i	0.905 (14)	1.967 (14)	2.8443 (9)	162.9 (13)
N2—H2N2···O2	0.922 (14)	1.876 (14)	2.7962 (9)	176.1 (13)
O1—H101···O2ii	0.892 (18)	1.779 (18)	2.6635 (8)	170.7 (19)
C3—H3A···O2iii	1.016 (16)	2.476 (15)	3.1887 (9)	126.7 (10)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O3	0.957 (17)	1.726 (17)	2.6738 (9)	170.4 (15)
N2—H1N2⋯O3i	0.905 (14)	1.967 (14)	2.8443 (9)	162.9 (13)
N2—H2N2⋯O2	0.922 (14)	1.876 (14)	2.7962 (9)	176.1 (13)
O1—H101⋯O2ii	0.892 (18)	1.779 (18)	2.6635 (8)	170.7 (19)
C3—H3A⋯O2iii	1.016 (16)	2.476 (15)	3.1887 (9)	126.7 (10)

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