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

In the 2-amino-benzoate anion of the title salt, C(6)H(9)N(2) (+)·C(7)H(6)NO(2) (-), an intra-molecular N-H⋯O hydrogen bond is observed. The dihedral angle between the ring and the CO(2) group is 8.41 (13)°. In the crystal, the protonated N atom and the 2-amino group of the cation are hydrogen bonded to the carboxyl-ate O atoms via a pair of N-H⋯O hydrogen bonds, forming an R(2) (2)(8) ring motif. The ion pairs are further connected via N-H⋯O hydrogen bonds, resulting in a donor-donor-acceptor-acceptor (DDAA) array of quadruple hydrogen bonds. The crystal structure also features a weak N-H⋯O hydrogen bond and a C-H⋯π inter-action, resulting in a three-dimensional network.

Related literature

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997 ▶); Katritzky et al. (1996 ▶). For details of hydrogen bonding, see: Jeffrey (1997 ▶); Scheiner (1997 ▶). For related structures, see: Nahringbauer & Kvick (1977 ▶); Hemamalini & Fun (2010a ▶,b ▶); Bis & Zaworotko (2005 ▶); Thanigaimani et al. (2012 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For hydrogen-bonding patterns in organic salts, see: Baskar Raj et al. (2003 ▶). 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 +·C7H6NO2 −

M = 245.28

Monoclinic,

a = 9.2394 (8) Å

b = 13.9200 (11) Å

c = 12.1514 (8) Å

β = 129.850 (4)°

V = 1199.82 (16) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 100 K

0.35 × 0.33 × 0.14 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.968, T max = 0.987

11650 measured reflections

2707 independent reflections

2361 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.101

S = 1.07

2707 reflections

184 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.27 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 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812043243/is5202sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812043243/is5202Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812043243/is5202Isup3.cml

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

C6H9N2+·C7H6NO2−	F(000) = 520
Mr = 245.28	Dx = 1.358 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4117 reflections
a = 9.2394 (8) Å	θ = 2.6–32.5°
b = 13.9200 (11) Å	µ = 0.09 mm−1
c = 12.1514 (8) Å	T = 100 K
β = 129.850 (4)°	Block, pink
V = 1199.82 (16) Å3	0.35 × 0.33 × 0.14 mm
Z = 4

Bruker SMART APEXII DUO CCD area-detector diffractometer	2707 independent reflections
Radiation source: fine-focus sealed tube	2361 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
φ and ω scans	θmax = 27.5°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −12→12
Tmin = 0.968, Tmax = 0.987	k = −18→18
11650 measured reflections	l = −15→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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0457P)2 + 0.4478P] where P = (Fo2 + 2Fc2)/3
2707 reflections	(Δ/σ)max < 0.001
184 parameters	Δρmax = 0.27 e Å−3
0 restraints	Δρmin = −0.24 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
N1	−0.05463 (13)	0.58465 (7)	0.37647 (10)	0.0151 (2)
N2	−0.25399 (14)	0.50164 (8)	0.16340 (12)	0.0204 (2)
C1	0.11839 (16)	0.60745 (8)	0.50265 (12)	0.0151 (2)
H1A	0.1274	0.6549	0.5629	0.018*
C2	0.27885 (15)	0.56356 (8)	0.54419 (12)	0.0155 (2)
C3	0.25605 (16)	0.49221 (8)	0.45170 (13)	0.0171 (2)
H3A	0.3639	0.4586	0.4784	0.020*
C4	0.08252 (16)	0.47011 (9)	0.32426 (13)	0.0177 (3)
H4A	0.0711	0.4225	0.2631	0.021*
C5	−0.07917 (16)	0.51858 (8)	0.28449 (12)	0.0159 (2)
C6	0.47064 (16)	0.59045 (9)	0.68135 (13)	0.0196 (3)
H6A	0.4574	0.6181	0.7487	0.029*
H6B	0.5289	0.6378	0.6607	0.029*
H6C	0.5502	0.5330	0.7238	0.029*
O1	0.43909 (11)	0.88549 (6)	0.58761 (9)	0.0185 (2)
O2	0.63811 (11)	0.83318 (6)	0.81350 (9)	0.0196 (2)
N3	0.50078 (14)	0.75894 (8)	0.93299 (11)	0.0194 (2)
C7	0.12951 (16)	0.86387 (9)	0.57403 (13)	0.0182 (2)
H7A	0.1169	0.8984	0.5008	0.022*
C8	−0.03024 (16)	0.84480 (9)	0.55754 (13)	0.0205 (3)
H8A	−0.1507	0.8658	0.4747	0.025*
C9	−0.01034 (16)	0.79390 (9)	0.66560 (13)	0.0194 (3)
H9A	−0.1190	0.7788	0.6550	0.023*
C10	0.16495 (16)	0.76523 (9)	0.78755 (13)	0.0171 (2)
H10A	0.1751	0.7310	0.8599	0.021*
C11	0.32976 (15)	0.78581 (8)	0.80692 (12)	0.0149 (2)
C12	0.31006 (15)	0.83401 (8)	0.69541 (12)	0.0147 (2)
C13	0.47372 (15)	0.85226 (8)	0.69945 (12)	0.0150 (2)
H1	−0.280 (2)	0.4597 (12)	0.0936 (19)	0.032 (4)*
H2	0.500 (2)	0.7164 (12)	0.9882 (18)	0.027 (4)*
H3	0.605 (2)	0.7676 (13)	0.9397 (18)	0.034 (4)*
H4	−0.165 (2)	0.6175 (13)	0.3487 (19)	0.038 (5)*
H5	−0.354 (2)	0.5383 (12)	0.1417 (18)	0.031 (4)*

	U11	U22	U33	U12	U13	U23
N1	0.0141 (5)	0.0158 (5)	0.0159 (5)	0.0000 (4)	0.0099 (4)	−0.0003 (4)
N2	0.0149 (5)	0.0239 (5)	0.0183 (5)	−0.0009 (4)	0.0088 (4)	−0.0060 (4)
C1	0.0171 (5)	0.0140 (5)	0.0147 (5)	−0.0024 (4)	0.0104 (5)	−0.0017 (4)
C2	0.0150 (5)	0.0156 (5)	0.0153 (5)	−0.0013 (4)	0.0094 (5)	0.0012 (4)
C3	0.0158 (5)	0.0169 (5)	0.0201 (6)	0.0007 (4)	0.0123 (5)	0.0013 (5)
C4	0.0190 (6)	0.0167 (5)	0.0191 (6)	−0.0009 (4)	0.0130 (5)	−0.0028 (5)
C5	0.0163 (5)	0.0162 (5)	0.0156 (5)	−0.0018 (4)	0.0105 (5)	−0.0002 (4)
C6	0.0156 (5)	0.0200 (6)	0.0184 (6)	−0.0007 (4)	0.0087 (5)	−0.0018 (5)
O1	0.0187 (4)	0.0220 (4)	0.0151 (4)	−0.0006 (3)	0.0109 (4)	0.0014 (3)
O2	0.0132 (4)	0.0241 (5)	0.0180 (4)	−0.0006 (3)	0.0084 (4)	0.0046 (3)
N3	0.0150 (5)	0.0256 (5)	0.0152 (5)	−0.0005 (4)	0.0085 (4)	0.0043 (4)
C7	0.0179 (5)	0.0189 (6)	0.0146 (5)	0.0009 (4)	0.0090 (5)	0.0006 (5)
C8	0.0135 (5)	0.0250 (6)	0.0164 (6)	0.0020 (4)	0.0065 (5)	−0.0009 (5)
C9	0.0148 (5)	0.0219 (6)	0.0216 (6)	−0.0031 (4)	0.0117 (5)	−0.0053 (5)
C10	0.0185 (5)	0.0173 (6)	0.0176 (6)	−0.0032 (4)	0.0125 (5)	−0.0025 (4)
C11	0.0147 (5)	0.0138 (5)	0.0136 (5)	−0.0010 (4)	0.0079 (5)	−0.0027 (4)
C12	0.0139 (5)	0.0142 (5)	0.0144 (5)	−0.0017 (4)	0.0084 (5)	−0.0025 (4)
C13	0.0156 (5)	0.0124 (5)	0.0153 (5)	−0.0010 (4)	0.0091 (5)	−0.0013 (4)

N1—C5	1.3498 (15)	O1—C13	1.2672 (14)
N1—C1	1.3660 (14)	O2—C13	1.2651 (14)
N1—H4	0.959 (18)	N3—C11	1.3717 (15)
N2—C5	1.3356 (15)	N3—H2	0.897 (17)
N2—H1	0.926 (18)	N3—H3	0.923 (18)
N2—H5	0.933 (17)	C7—C8	1.3821 (17)
C1—C2	1.3664 (16)	C7—C12	1.4064 (16)
C1—H1A	0.9500	C7—H7A	0.9500
C2—C3	1.4108 (17)	C8—C9	1.3966 (18)
C2—C6	1.5077 (16)	C8—H8A	0.9500
C3—C4	1.3716 (16)	C9—C10	1.3793 (16)
C3—H3A	0.9500	C9—H9A	0.9500
C4—C5	1.4125 (16)	C10—C11	1.4131 (16)
C4—H4A	0.9500	C10—H10A	0.9500
C6—H6A	0.9800	C11—C12	1.4153 (16)
C6—H6B	0.9800	C12—C13	1.5029 (15)
C6—H6C	0.9800
C5—N1—C1	122.86 (10)	H6B—C6—H6C	109.5
C5—N1—H4	117.1 (11)	C11—N3—H2	117.4 (10)
C1—N1—H4	120.0 (11)	C11—N3—H3	117.0 (11)
C5—N2—H1	122.7 (10)	H2—N3—H3	121.8 (15)
C5—N2—H5	119.6 (10)	C8—C7—C12	122.28 (11)
H1—N2—H5	117.2 (15)	C8—C7—H7A	118.9
N1—C1—C2	121.54 (11)	C12—C7—H7A	118.9
N1—C1—H1A	119.2	C7—C8—C9	118.44 (11)
C2—C1—H1A	119.2	C7—C8—H8A	120.8
C1—C2—C3	116.59 (10)	C9—C8—H8A	120.8
C1—C2—C6	121.72 (11)	C10—C9—C8	120.90 (11)
C3—C2—C6	121.68 (10)	C10—C9—H9A	119.6
C4—C3—C2	121.81 (11)	C8—C9—H9A	119.6
C4—C3—H3A	119.1	C9—C10—C11	121.22 (11)
C2—C3—H3A	119.1	C9—C10—H10A	119.4
C3—C4—C5	119.61 (11)	C11—C10—H10A	119.4
C3—C4—H4A	120.2	N3—C11—C10	118.55 (11)
C5—C4—H4A	120.2	N3—C11—C12	123.23 (10)
N2—C5—N1	118.38 (10)	C10—C11—C12	118.22 (10)
N2—C5—C4	124.05 (11)	C7—C12—C11	118.86 (10)
N1—C5—C4	117.55 (10)	C7—C12—C13	118.47 (10)
C2—C6—H6A	109.5	C11—C12—C13	122.65 (10)
C2—C6—H6B	109.5	O2—C13—O1	123.53 (10)
H6A—C6—H6B	109.5	O2—C13—C12	118.48 (10)
C2—C6—H6C	109.5	O1—C13—C12	117.99 (10)
H6A—C6—H6C	109.5
C5—N1—C1—C2	−0.49 (17)	C9—C10—C11—N3	177.35 (11)
N1—C1—C2—C3	−1.33 (17)	C9—C10—C11—C12	−2.10 (17)
N1—C1—C2—C6	178.25 (11)	C8—C7—C12—C11	−2.35 (18)
C1—C2—C3—C4	2.07 (17)	C8—C7—C12—C13	175.98 (11)
C6—C2—C3—C4	−177.52 (11)	N3—C11—C12—C7	−176.04 (11)
C2—C3—C4—C5	−1.02 (18)	C10—C11—C12—C7	3.38 (16)
C1—N1—C5—N2	−179.68 (11)	N3—C11—C12—C13	5.71 (18)
C1—N1—C5—C4	1.58 (16)	C10—C11—C12—C13	−174.87 (10)
C3—C4—C5—N2	−179.47 (11)	C7—C12—C13—O2	173.86 (10)
C3—C4—C5—N1	−0.81 (17)	C11—C12—C13—O2	−7.88 (17)
C12—C7—C8—C9	−0.13 (18)	C7—C12—C13—O1	−6.58 (16)
C7—C8—C9—C10	1.51 (18)	C11—C12—C13—O1	171.69 (10)
C8—C9—C10—C11	−0.38 (18)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O2	0.92 (2)	1.97 (2)	2.6734 (18)	131.8 (15)
N2—H1···O1i	0.926 (18)	1.982 (18)	2.8561 (14)	157 (2)
N3—H2···O1ii	0.897 (17)	2.159 (18)	3.0445 (14)	168.7 (14)
N1—H4···O2iii	0.959 (18)	1.723 (18)	2.6776 (13)	172.7 (17)
N2—H5···O1iii	0.933 (17)	1.899 (18)	2.8305 (14)	176.8 (16)
C1—H1A···Cg1	0.95	2.58	3.5094 (13)	165

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C7–C12 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯O2	0.92 (2)	1.97 (2)	2.6734 (18)	131.8 (15)
N2—H1⋯O1i	0.926 (18)	1.982 (18)	2.8561 (14)	157 (2)
N3—H2⋯O1ii	0.897 (17)	2.159 (18)	3.0445 (14)	168.7 (14)
N1—H4⋯O2iii	0.959 (18)	1.723 (18)	2.6776 (13)	172.7 (17)
N2—H5⋯O1iii	0.933 (17)	1.899 (18)	2.8305 (14)	176.8 (16)
C1—H1A⋯Cg1	0.95	2.58	3.5094 (13)	165

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