2-Amino-5-methyl-pyridinium 3-amino-benzoate.

In the title compound, C(6)H(9)N(2) (+)·C(7)H(6)NO(2) (-), the H atom of the N-H group and an H atom of the 2-amino group from the cation are involved in inter-molecular N-H⋯O hydrogen bonds with the O atoms of the carboxyl-ate group of the anion, forming an R(2) (2)(8) ring motif. These ring motifs are, in turn, connected by further N-H⋯O hydrogen bonds, forming a two-dimensional network. The crystal structure is further stabilized by π⋯π stacking inter-actions involving the benzene and pyridinium rings with a centroid-centroid distance of 3.7594 (8) Å.

Related literature

For background to the chemistry of substituted pyridines see: Pozharski et al. (1997 ▶); Katritzky et al. (1996 ▶). For related structures, see: n class="Chemical">Nahringbauer & Kvick (1977 ▶); Feng et al. (2005 ▶); Xuan et al. (2003 ▶); Jin et al. (2005 ▶). For details of hydrogen bonding, see: Jeffrey & Saenger (1991 ▶); Jeffrey (1997 ▶); Scheiner (1997 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C6H9N2 +·n class="Chemical">C7H6NO2 −

M = 245.28

Monoclinic,

a = 10.0739 (2) Å

b = 10.9620 (2) Å

c = 11.9641 (2) Å

β = 113.148 (1)°

V = 1214.83 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 296 K

0.72 × 0.34 × 0.13 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.936, T max = 0.988

13305 measured reflections

3541 independent reflections

2576 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.138

S = 1.07

3541 reflections

212 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.20 e Å−3

Δρmin = −0.26 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAIn class="Chemical">NT; 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/S1600536810005180/lh2994sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810005180/lh2994Isup2.hkl

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

C6H9N2+·C7H6NO2−	F(000) = 520
Mr = 245.28	Dx = 1.341 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3778 reflections
a = 10.0739 (2) Å	θ = 2.6–29.9°
b = 10.9620 (2) Å	µ = 0.09 mm−1
c = 11.9641 (2) Å	T = 296 K
β = 113.148 (1)°	Plate, brown
V = 1214.83 (4) Å3	0.72 × 0.34 × 0.13 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	3541 independent reflections
Radiation source: fine-focus sealed tube	2576 reflections with I > 2σ(I)
graphite	Rint = 0.029
φ and ω scans	θmax = 30.1°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→14
Tmin = 0.936, Tmax = 0.988	k = −15→13
13305 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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.138	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0676P)2 + 0.1203P] where P = (Fo2 + 2Fc2)/3
3541 reflections	(Δ/σ)max = 0.001
212 parameters	Δρmax = 0.20 e Å−3
0 restraints	Δρmin = −0.26 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 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
N1	0.03024 (11)	0.31395 (9)	0.56765 (8)	0.0363 (2)
N2	−0.07229 (13)	0.27732 (11)	0.70650 (10)	0.0477 (3)
C1	0.12267 (13)	0.37351 (11)	0.52889 (10)	0.0377 (3)
C2	0.01813 (13)	0.34187 (11)	0.67327 (10)	0.0364 (3)
C3	0.10505 (14)	0.43720 (12)	0.74341 (10)	0.0418 (3)
C4	0.19709 (14)	0.49686 (12)	0.70412 (11)	0.0430 (3)
C5	0.20896 (13)	0.46594 (11)	0.59348 (10)	0.0390 (3)
C6	0.31252 (16)	0.53099 (14)	0.55236 (13)	0.0546 (4)
H6A	0.2979	0.5045	0.4719	0.082*
H6B	0.4097	0.5128	0.6069	0.082*
H6C	0.2964	0.6173	0.5519	0.082*
O1	0.74312 (11)	0.37847 (9)	1.02381 (8)	0.0506 (3)
O2	0.87300 (12)	0.35863 (9)	0.91200 (8)	0.0552 (3)
N3	0.44474 (16)	0.75758 (13)	0.87306 (15)	0.0620 (4)
C7	0.61001 (13)	0.58920 (11)	0.90248 (10)	0.0380 (3)
C8	0.54279 (13)	0.69494 (11)	0.84017 (11)	0.0396 (3)
C9	0.57809 (14)	0.73551 (12)	0.74452 (11)	0.0415 (3)
C10	0.67681 (15)	0.67294 (12)	0.71301 (11)	0.0424 (3)
C11	0.74400 (14)	0.56839 (12)	0.77538 (10)	0.0392 (3)
C12	0.70967 (12)	0.52632 (10)	0.87065 (9)	0.0343 (3)
C13	0.78005 (13)	0.41271 (11)	0.94066 (9)	0.0371 (3)
H1	0.1227 (15)	0.3450 (13)	0.4509 (14)	0.049 (4)*
H3	0.0993 (15)	0.4581 (13)	0.8200 (13)	0.048 (4)*
H4	0.2602 (17)	0.5628 (15)	0.7561 (14)	0.061 (4)*
H7	0.5865 (15)	0.5593 (13)	0.9703 (13)	0.046 (4)*
H9	0.5270 (16)	0.8131 (14)	0.6969 (14)	0.056 (4)*
H10	0.7025 (16)	0.7023 (13)	0.6453 (14)	0.053 (4)*
H11	0.8116 (16)	0.5214 (14)	0.7520 (13)	0.050 (4)*
H1N1	−0.0365 (17)	0.2494 (16)	0.5130 (15)	0.062 (5)*
H1N2	−0.1357 (17)	0.2226 (15)	0.6504 (14)	0.056 (4)*
H2N2	−0.0953 (16)	0.3031 (14)	0.7699 (15)	0.055 (4)*
H1N3	0.4107 (18)	0.7223 (17)	0.9247 (17)	0.067 (5)*
H2N3	0.395 (2)	0.8179 (18)	0.8245 (18)	0.077 (6)*

	U11	U22	U33	U12	U13	U23
N1	0.0421 (5)	0.0357 (5)	0.0327 (4)	−0.0030 (4)	0.0163 (4)	−0.0047 (4)
N2	0.0578 (7)	0.0513 (7)	0.0429 (5)	−0.0101 (6)	0.0294 (5)	−0.0079 (5)
C1	0.0405 (6)	0.0398 (6)	0.0341 (5)	−0.0004 (5)	0.0162 (5)	−0.0022 (4)
C2	0.0412 (6)	0.0359 (6)	0.0336 (5)	0.0034 (5)	0.0163 (4)	−0.0009 (4)
C3	0.0457 (7)	0.0433 (7)	0.0359 (5)	0.0016 (6)	0.0156 (5)	−0.0092 (5)
C4	0.0420 (7)	0.0386 (6)	0.0448 (6)	−0.0020 (5)	0.0132 (5)	−0.0103 (5)
C5	0.0372 (6)	0.0371 (6)	0.0421 (6)	0.0004 (5)	0.0148 (5)	−0.0003 (5)
C6	0.0516 (8)	0.0563 (9)	0.0584 (8)	−0.0131 (7)	0.0242 (6)	−0.0058 (6)
O1	0.0655 (6)	0.0505 (6)	0.0456 (5)	0.0114 (5)	0.0323 (4)	0.0126 (4)
O2	0.0757 (7)	0.0558 (6)	0.0455 (5)	0.0294 (5)	0.0362 (5)	0.0148 (4)
N3	0.0660 (9)	0.0531 (8)	0.0837 (9)	0.0201 (7)	0.0475 (8)	0.0152 (7)
C7	0.0419 (6)	0.0377 (6)	0.0380 (5)	0.0000 (5)	0.0197 (5)	0.0003 (5)
C8	0.0363 (6)	0.0370 (6)	0.0461 (6)	−0.0003 (5)	0.0169 (5)	−0.0025 (5)
C9	0.0404 (7)	0.0366 (6)	0.0441 (6)	0.0001 (5)	0.0130 (5)	0.0053 (5)
C10	0.0463 (7)	0.0442 (7)	0.0387 (5)	−0.0021 (6)	0.0187 (5)	0.0062 (5)
C11	0.0426 (7)	0.0414 (7)	0.0376 (5)	0.0025 (5)	0.0200 (5)	0.0007 (5)
C12	0.0378 (6)	0.0339 (6)	0.0308 (5)	−0.0006 (5)	0.0130 (4)	−0.0014 (4)
C13	0.0465 (7)	0.0354 (6)	0.0300 (5)	0.0033 (5)	0.0156 (4)	−0.0008 (4)

N1—C2	1.3515 (14)	O1—C13	1.2490 (14)
N1—C1	1.3593 (16)	O2—C13	1.2642 (15)
N1—H1N1	1.018 (17)	N3—C8	1.3811 (18)
N2—C2	1.3316 (16)	N3—H1N3	0.904 (19)
N2—H1N2	0.938 (17)	N3—H2N3	0.89 (2)
N2—H2N2	0.921 (17)	C7—C12	1.3888 (17)
C1—C5	1.3607 (17)	C7—C8	1.4003 (17)
C1—H1	0.984 (15)	C7—H7	0.986 (15)
C2—C3	1.4090 (17)	C8—C9	1.3977 (18)
C3—C4	1.3605 (19)	C9—C10	1.3771 (19)
C3—H3	0.968 (14)	C9—H9	1.040 (16)
C4—C5	1.4163 (17)	C10—C11	1.3897 (18)
C4—H4	1.001 (16)	C10—H10	0.995 (15)
C5—C6	1.4974 (19)	C11—C12	1.3933 (16)
C6—H6A	0.9600	C11—H11	0.978 (15)
C6—H6B	0.9600	C12—C13	1.5126 (16)
C6—H6C	0.9600
C2—N1—C1	122.40 (10)	H6B—C6—H6C	109.5
C2—N1—H1N1	118.6 (9)	C8—N3—H1N3	119.2 (11)
C1—N1—H1N1	118.9 (9)	C8—N3—H2N3	117.7 (13)
C2—N2—H1N2	118.7 (10)	H1N3—N3—H2N3	119.6 (17)
C2—N2—H2N2	120.4 (10)	C12—C7—C8	121.01 (11)
H1N2—N2—H2N2	117.6 (13)	C12—C7—H7	119.6 (8)
N1—C1—C5	122.30 (11)	C8—C7—H7	119.4 (8)
N1—C1—H1	115.2 (8)	N3—C8—C9	121.04 (12)
C5—C1—H1	122.5 (8)	N3—C8—C7	120.67 (12)
N2—C2—N1	118.85 (11)	C9—C8—C7	118.28 (12)
N2—C2—C3	123.65 (11)	C10—C9—C8	120.61 (11)
N1—C2—C3	117.48 (11)	C10—C9—H9	120.8 (9)
C4—C3—C2	119.94 (11)	C8—C9—H9	118.6 (9)
C4—C3—H3	121.1 (8)	C9—C10—C11	121.03 (12)
C2—C3—H3	119.0 (8)	C9—C10—H10	120.6 (9)
C3—C4—C5	121.83 (11)	C11—C10—H10	118.4 (9)
C3—C4—H4	119.0 (9)	C10—C11—C12	119.16 (12)
C5—C4—H4	119.1 (9)	C10—C11—H11	121.8 (8)
C1—C5—C4	116.05 (12)	C12—C11—H11	119.0 (8)
C1—C5—C6	122.69 (11)	C7—C12—C11	119.91 (11)
C4—C5—C6	121.25 (11)	C7—C12—C13	119.26 (10)
C5—C6—H6A	109.5	C11—C12—C13	120.83 (11)
C5—C6—H6B	109.5	O1—C13—O2	124.01 (11)
H6A—C6—H6B	109.5	O1—C13—C12	117.84 (11)
C5—C6—H6C	109.5	O2—C13—C12	118.15 (10)
H6A—C6—H6C	109.5
C2—N1—C1—C5	−0.37 (18)	N3—C8—C9—C10	179.50 (12)
C1—N1—C2—N2	−178.35 (11)	C7—C8—C9—C10	−0.18 (18)
C1—N1—C2—C3	0.48 (17)	C8—C9—C10—C11	−0.16 (19)
N2—C2—C3—C4	178.51 (12)	C9—C10—C11—C12	0.43 (19)
N1—C2—C3—C4	−0.26 (18)	C8—C7—C12—C11	0.00 (18)
C2—C3—C4—C5	−0.1 (2)	C8—C7—C12—C13	179.81 (10)
N1—C1—C5—C4	0.01 (18)	C10—C11—C12—C7	−0.35 (18)
N1—C1—C5—C6	179.17 (12)	C10—C11—C12—C13	179.84 (11)
C3—C4—C5—C1	0.20 (19)	C7—C12—C13—O1	1.32 (17)
C3—C4—C5—C6	−178.97 (12)	C11—C12—C13—O1	−178.87 (11)
C12—C7—C8—N3	−179.42 (12)	C7—C12—C13—O2	−178.33 (10)
C12—C7—C8—C9	0.26 (18)	C11—C12—C13—O2	1.48 (17)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O2i	1.017 (17)	1.682 (17)	2.6901 (14)	170.6 (17)
N2—H1N2···O1i	0.939 (16)	1.886 (16)	2.8207 (15)	173.3 (14)
N2—H2N2···O2ii	0.920 (17)	1.947 (17)	2.8650 (16)	175.3 (16)
N3—H1N3···O1iii	0.903 (19)	2.18 (2)	3.027 (2)	156.0 (17)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O2i	1.017 (17)	1.682 (17)	2.6901 (14)	170.6 (17)
N2—H1N2⋯O1i	0.939 (16)	1.886 (16)	2.8207 (15)	173.3 (14)
N2—H2N2⋯O2ii	0.920 (17)	1.947 (17)	2.8650 (16)	175.3 (16)
N3—H1N3⋯O1iii	0.903 (19)	2.18 (2)	3.027 (2)	156.0 (17)

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