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

The 4-methyl-benzoate anion of the title salt, C6H9N2(+)·C8H7O2(-), is nearly planar, with a dihedral angle of 6.26 (10)° between the benzene ring and the carboxyl-ate group. In the crystal, the protonated N atom and the 2-amino group of the cation are hydrogen bonded to the carboxyl-ate O atoms of the anion via a pair of N-H⋯O hydrogen bonds with an R2(2)(8) ring motif, forming an approximately planar ion pair with a dihedral angle of 9.63 (4)° between the pyridinium and benzene rings. The ion pairs are further connected via N-H⋯O and weak C-H⋯O hydrogen bonds, forming a two-dimensional network parallel to the bc plane.

Related literature

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997 ▶); Katritzky et al. (1996 ▶). For related structures, see: Nahringbauer & Kvick (1977 ▶); Thanigaimani et al. (2012a ▶,b ▶,c ▶). 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 +·C8H7O2 −

M = 244.29

Monoclinic,

a = 9.6315 (5) Å

b = 10.8713 (6) Å

c = 12.1481 (7) Å

β = 104.093 (1)°

V = 1233.71 (12) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 100 K

0.52 × 0.32 × 0.15 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.955, T max = 0.987

18139 measured reflections

4493 independent reflections

3783 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.125

S = 1.03

4493 reflections

177 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.43 e Å−3

Δρmin = −0.29 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 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812050374/is5229sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812050374/is5229Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812050374/is5229Isup3.cml

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

C6H9N2+·C8H7O2−	F(000) = 520
Mr = 244.29	Dx = 1.315 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6272 reflections
a = 9.6315 (5) Å	θ = 2.6–32.6°
b = 10.8713 (6) Å	µ = 0.09 mm−1
c = 12.1481 (7) Å	T = 100 K
β = 104.093 (1)°	Block, colourless
V = 1233.71 (12) Å3	0.52 × 0.32 × 0.15 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	4493 independent reflections
Radiation source: fine-focus sealed tube	3783 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
φ and ω scans	θmax = 32.7°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −14→14
Tmin = 0.955, Tmax = 0.987	k = −16→16
18139 measured reflections	l = −18→18

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) = 0.125	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0678P)2 + 0.3153P] where P = (Fo2 + 2Fc2)/3
4493 reflections	(Δ/σ)max = 0.001
177 parameters	Δρmax = 0.43 e Å−3
0 restraints	Δρmin = −0.29 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	0.07967 (7)	1.13827 (6)	0.07082 (5)	0.01774 (14)
O2	0.20480 (8)	1.12140 (6)	−0.06122 (6)	0.01914 (15)
C1	0.23323 (9)	0.93283 (8)	0.19086 (7)	0.01486 (16)
H1A	0.1613	0.9680	0.2224	0.018*
C2	0.31890 (10)	0.83760 (8)	0.24780 (7)	0.01618 (16)
H2A	0.3048	0.8090	0.3182	0.019*
C3	0.42490 (9)	0.78366 (8)	0.20317 (7)	0.01589 (16)
C4	0.44248 (10)	0.82614 (9)	0.09878 (8)	0.01896 (18)
H4A	0.5132	0.7900	0.0665	0.023*
C5	0.35734 (10)	0.92094 (9)	0.04167 (7)	0.01693 (17)
H5A	0.3702	0.9484	−0.0294	0.020*
C6	0.25310 (9)	0.97626 (8)	0.08768 (7)	0.01277 (15)
C7	0.17236 (9)	1.08592 (8)	0.02773 (7)	0.01374 (15)
C8	0.51917 (10)	0.68238 (9)	0.26587 (8)	0.02109 (19)
H8A	0.5215	0.6869	0.3469	0.032*
H8B	0.6164	0.6921	0.2556	0.032*
H8C	0.4808	0.6024	0.2358	0.032*
N1	0.94348 (8)	0.32387 (7)	0.93651 (6)	0.01462 (15)
N2	1.04273 (9)	0.28128 (8)	0.78450 (7)	0.01928 (16)
C9	0.95687 (9)	0.35009 (8)	0.83058 (7)	0.01471 (16)
C10	0.87654 (10)	0.45002 (9)	0.77234 (7)	0.01714 (17)
H10A	0.8825	0.4703	0.6976	0.021*
C11	0.79056 (10)	0.51697 (8)	0.82424 (8)	0.01771 (17)
H11A	0.7373	0.5839	0.7847	0.021*
C12	0.77883 (9)	0.48901 (8)	0.93576 (8)	0.01643 (16)
C13	0.85738 (9)	0.39091 (8)	0.98802 (7)	0.01558 (16)
H13A	0.8517	0.3689	1.0625	0.019*
C14	0.68490 (11)	0.56433 (9)	0.99240 (9)	0.02191 (19)
H14A	0.6859	0.5287	1.0667	0.033*
H14B	0.5867	0.5644	0.9450	0.033*
H14C	0.7209	0.6489	1.0024	0.033*
H1N2	1.0977 (16)	0.2237 (15)	0.8310 (13)	0.035 (4)*
H2N2	1.0599 (17)	0.3085 (15)	0.7168 (14)	0.035 (4)*
H1N1	0.9942 (18)	0.2547 (17)	0.9795 (15)	0.046 (5)*

	U11	U22	U33	U12	U13	U23
O1	0.0208 (3)	0.0182 (3)	0.0149 (3)	0.0068 (2)	0.0055 (2)	0.0002 (2)
O2	0.0245 (3)	0.0186 (3)	0.0158 (3)	0.0042 (2)	0.0075 (2)	0.0036 (2)
C1	0.0150 (4)	0.0143 (4)	0.0157 (4)	0.0013 (3)	0.0046 (3)	0.0008 (3)
C2	0.0175 (4)	0.0155 (4)	0.0156 (4)	0.0011 (3)	0.0041 (3)	0.0021 (3)
C3	0.0149 (4)	0.0135 (4)	0.0182 (4)	0.0011 (3)	0.0021 (3)	0.0004 (3)
C4	0.0179 (4)	0.0184 (4)	0.0221 (4)	0.0052 (3)	0.0076 (3)	0.0013 (3)
C5	0.0184 (4)	0.0174 (4)	0.0162 (4)	0.0030 (3)	0.0064 (3)	0.0015 (3)
C6	0.0129 (3)	0.0119 (3)	0.0131 (3)	0.0002 (3)	0.0023 (3)	−0.0007 (3)
C7	0.0157 (4)	0.0127 (3)	0.0122 (3)	0.0002 (3)	0.0021 (3)	−0.0012 (3)
C8	0.0197 (4)	0.0171 (4)	0.0249 (4)	0.0044 (3)	0.0024 (3)	0.0035 (3)
N1	0.0161 (3)	0.0144 (3)	0.0134 (3)	0.0003 (2)	0.0037 (2)	0.0022 (2)
N2	0.0229 (4)	0.0206 (4)	0.0159 (3)	0.0040 (3)	0.0076 (3)	0.0036 (3)
C9	0.0158 (4)	0.0146 (4)	0.0135 (3)	−0.0019 (3)	0.0032 (3)	0.0012 (3)
C10	0.0187 (4)	0.0170 (4)	0.0151 (4)	0.0001 (3)	0.0028 (3)	0.0044 (3)
C11	0.0172 (4)	0.0149 (4)	0.0203 (4)	0.0003 (3)	0.0032 (3)	0.0036 (3)
C12	0.0149 (4)	0.0144 (4)	0.0198 (4)	−0.0014 (3)	0.0041 (3)	0.0001 (3)
C13	0.0165 (4)	0.0160 (4)	0.0146 (4)	−0.0012 (3)	0.0043 (3)	0.0003 (3)
C14	0.0203 (4)	0.0207 (4)	0.0259 (4)	0.0030 (3)	0.0077 (3)	−0.0002 (3)

O1—C7	1.2737 (10)	N1—C9	1.3545 (11)
O2—C7	1.2564 (11)	N1—C13	1.3649 (11)
C1—C6	1.3956 (12)	N1—H1N1	0.976 (18)
C1—C2	1.3975 (12)	N2—C9	1.3351 (12)
C1—H1A	0.9500	N2—H1N2	0.920 (16)
C2—C3	1.3962 (13)	N2—H2N2	0.926 (16)
C2—H2A	0.9500	C9—C10	1.4187 (12)
C3—C4	1.3981 (13)	C10—C11	1.3665 (13)
C3—C8	1.5100 (12)	C10—H10A	0.9500
C4—C5	1.3924 (12)	C11—C12	1.4195 (13)
C4—H4A	0.9500	C11—H11A	0.9500
C5—C6	1.3984 (12)	C12—C13	1.3708 (12)
C5—H5A	0.9500	C12—C14	1.5052 (13)
C6—C7	1.5101 (12)	C13—H13A	0.9500
C8—H8A	0.9800	C14—H14A	0.9800
C8—H8B	0.9800	C14—H14B	0.9800
C8—H8C	0.9800	C14—H14C	0.9800
C6—C1—C2	120.10 (8)	C9—N1—C13	122.15 (8)
C6—C1—H1A	120.0	C9—N1—H1N1	121.3 (10)
C2—C1—H1A	120.0	C13—N1—H1N1	116.6 (10)
C3—C2—C1	121.23 (8)	C9—N2—H1N2	116.5 (10)
C3—C2—H2A	119.4	C9—N2—H2N2	117.1 (10)
C1—C2—H2A	119.4	H1N2—N2—H2N2	124.3 (14)
C2—C3—C4	118.36 (8)	N2—C9—N1	119.50 (8)
C2—C3—C8	121.14 (8)	N2—C9—C10	122.56 (8)
C4—C3—C8	120.51 (8)	N1—C9—C10	117.94 (8)
C5—C4—C3	120.64 (8)	C11—C10—C9	119.73 (8)
C5—C4—H4A	119.7	C11—C10—H10A	120.1
C3—C4—H4A	119.7	C9—C10—H10A	120.1
C4—C5—C6	120.81 (8)	C10—C11—C12	121.62 (8)
C4—C5—H5A	119.6	C10—C11—H11A	119.2
C6—C5—H5A	119.6	C12—C11—H11A	119.2
C1—C6—C5	118.84 (8)	C13—C12—C11	116.45 (8)
C1—C6—C7	122.21 (7)	C13—C12—C14	122.48 (8)
C5—C6—C7	118.84 (7)	C11—C12—C14	121.08 (8)
O2—C7—O1	124.21 (8)	N1—C13—C12	122.11 (8)
O2—C7—C6	116.77 (8)	N1—C13—H13A	118.9
O1—C7—C6	118.99 (7)	C12—C13—H13A	118.9
C3—C8—H8A	109.5	C12—C14—H14A	109.5
C3—C8—H8B	109.5	C12—C14—H14B	109.5
H8A—C8—H8B	109.5	H14A—C14—H14B	109.5
C3—C8—H8C	109.5	C12—C14—H14C	109.5
H8A—C8—H8C	109.5	H14A—C14—H14C	109.5
H8B—C8—H8C	109.5	H14B—C14—H14C	109.5
C6—C1—C2—C3	−0.32 (13)	C1—C6—C7—O1	−2.27 (12)
C1—C2—C3—C4	−0.82 (13)	C5—C6—C7—O1	−178.40 (8)
C1—C2—C3—C8	178.86 (8)	C13—N1—C9—N2	179.99 (8)
C2—C3—C4—C5	0.77 (14)	C13—N1—C9—C10	−0.73 (13)
C8—C3—C4—C5	−178.91 (9)	N2—C9—C10—C11	−179.98 (9)
C3—C4—C5—C6	0.41 (14)	N1—C9—C10—C11	0.77 (13)
C2—C1—C6—C5	1.49 (13)	C9—C10—C11—C12	−0.17 (14)
C2—C1—C6—C7	−174.64 (8)	C10—C11—C12—C13	−0.48 (13)
C4—C5—C6—C1	−1.54 (13)	C10—C11—C12—C14	179.36 (9)
C4—C5—C6—C7	174.72 (8)	C9—N1—C13—C12	0.07 (13)
C1—C6—C7—O2	175.94 (8)	C11—C12—C13—N1	0.54 (13)
C5—C6—C7—O2	−0.19 (12)	C14—C12—C13—N1	−179.30 (8)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O2i	0.920 (16)	1.832 (16)	2.7469 (11)	172.7 (15)
N2—H2N2···O1ii	0.926 (16)	1.919 (17)	2.8424 (11)	175.4 (15)
N1—H1N1···O1i	0.976 (18)	1.751 (18)	2.7224 (10)	173.1 (16)
C10—H10A···O2iii	0.95	2.34	3.1120 (11)	138

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯O2i	0.920 (16)	1.832 (16)	2.7469 (11)	172.7 (15)
N2—H2N2⋯O1ii	0.926 (16)	1.919 (17)	2.8424 (11)	175.4 (15)
N1—H1N1⋯O1i	0.976 (18)	1.751 (18)	2.7224 (10)	173.1 (16)
C10—H10A⋯O2iii	0.95	2.34	3.1120 (11)	138

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