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

In the title mol-ecular salt, C6H9N2 (+)·C7H4NO4 (-), the original pyridine N atom of 2-amino-4-methyl-pyridine is protonated and the carb-oxylic acid group of nitro-benzoic acid is deprotonated. In the crystal, the ions are linked by N-H⋯O hydrogen bonds, forming chains propagating along [001]. The chains are linked via C-H⋯O hydrogen bonds, forming two-dimensional networks lying parallel to the bc plane.

Related literature

For related structures, see: Navarro Ranninger et al. (1985 ▶); Luque et al. (1997 ▶); Qin et al. (1999 ▶); Jin et al. (2001 ▶); Albrecht et al. (2003 ▶); Kvick & Noordik (1977 ▶).

Experimental

Crystal data

C6H9N2 +·C7H4NO4 −

M = 275.26

Monoclinic,

a = 12.2049 (3) Å

b = 9.8463 (2) Å

c = 11.5405 (2) Å

β = 107.106 (1)°

V = 1325.51 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 293 K

0.30 × 0.25 × 0.20 mm

Data collection

Bruker SMART APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.969, T max = 0.979

12523 measured reflections

3289 independent reflections

2644 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.125

S = 1.06

3289 reflections

195 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.26 e Å−3

Δρmin = −0.18 e Å−3

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813012919/su2590sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813012919/su2590Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813012919/su2590Isup3.cml

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

C6H9N2+·C7H4NO4−	F(000) = 576
Mr = 275.26	Dx = 1.379 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3289 reflections
a = 12.2049 (3) Å	θ = 1.8–28.4°
b = 9.8463 (2) Å	µ = 0.11 mm−1
c = 11.5405 (2) Å	T = 293 K
β = 107.106 (1)°	Block, colourless
V = 1325.51 (5) Å3	0.30 × 0.25 × 0.20 mm
Z = 4

Bruker SMART APEXII area-detector diffractometer	3289 independent reflections
Radiation source: fine-focus sealed tube	2644 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
ω and φ scans	θmax = 28.4°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −13→16
Tmin = 0.969, Tmax = 0.979	k = −12→13
12523 measured reflections	l = −12→15

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.125	w = 1/[σ2(Fo2) + (0.0582P)2 + 0.2995P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.004
3289 reflections	Δρmax = 0.26 e Å−3
195 parameters	Δρmin = −0.18 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.031 (3)

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
C1	0.61383 (11)	0.04795 (13)	0.39832 (12)	0.0428 (3)
C2	0.53048 (13)	0.13768 (17)	0.40961 (15)	0.0577 (4)
H2	0.4606	0.1437	0.3494	0.069*
C3	0.55274 (15)	0.21813 (17)	0.51177 (17)	0.0631 (4)
H3	0.4979	0.2798	0.5202	0.076*
C4	0.65544 (15)	0.20749 (16)	0.60095 (15)	0.0578 (4)
H4	0.6694	0.2605	0.6705	0.069*
C5	0.73827 (12)	0.11780 (14)	0.58743 (12)	0.0469 (3)
H5	0.8076	0.1114	0.6484	0.056*
C6	0.72002 (10)	0.03729 (12)	0.48485 (10)	0.0367 (3)
C7	0.81856 (11)	−0.04361 (12)	0.46565 (11)	0.0383 (3)
C8	0.87671 (12)	0.30082 (14)	0.40898 (11)	0.0472 (3)
H8	0.8642	0.2544	0.3360	0.057*
C9	0.80301 (12)	0.39954 (14)	0.41863 (12)	0.0483 (3)
H9	0.7407	0.4216	0.3526	0.058*
C10	0.82151 (11)	0.46900 (13)	0.52995 (12)	0.0429 (3)
C11	0.91448 (12)	0.43446 (13)	0.62498 (11)	0.0423 (3)
H11	0.9278	0.4794	0.6987	0.051*
C12	0.99021 (11)	0.33137 (13)	0.61202 (11)	0.0399 (3)
C13	0.73825 (14)	0.57626 (16)	0.54149 (15)	0.0597 (4)
H13A	0.7559	0.6044	0.6246	0.090*
H13B	0.6618	0.5403	0.5153	0.090*
H13C	0.7437	0.6528	0.4920	0.090*
N1	0.58459 (11)	−0.04327 (14)	0.29302 (11)	0.0562 (3)
N3	0.96840 (10)	0.26833 (11)	0.50367 (9)	0.0417 (3)
N4	1.08159 (12)	0.29199 (15)	0.70053 (11)	0.0561 (3)
O1	0.53069 (14)	0.00397 (18)	0.19509 (11)	0.0954 (5)
O2	0.61421 (12)	−0.16147 (12)	0.30903 (11)	0.0771 (4)
O3	0.83221 (9)	−0.04027 (11)	0.36362 (9)	0.0547 (3)
O4	0.88257 (8)	−0.10404 (11)	0.55661 (8)	0.0518 (3)
H4B	1.0969 (15)	0.3317 (18)	0.7709 (17)	0.059 (5)*
H4A	1.1221 (15)	0.2174 (19)	0.6872 (16)	0.065 (5)*
H3A	1.0192 (15)	0.2040 (18)	0.4898 (16)	0.064 (5)*

	U11	U22	U33	U12	U13	U23
C1	0.0439 (7)	0.0438 (6)	0.0385 (6)	0.0005 (5)	0.0088 (5)	0.0079 (5)
C2	0.0448 (7)	0.0628 (9)	0.0619 (9)	0.0129 (6)	0.0101 (6)	0.0191 (7)
C3	0.0659 (10)	0.0565 (9)	0.0744 (11)	0.0243 (7)	0.0323 (9)	0.0124 (8)
C4	0.0738 (10)	0.0519 (8)	0.0533 (8)	0.0144 (7)	0.0272 (8)	−0.0016 (6)
C5	0.0513 (7)	0.0510 (7)	0.0379 (6)	0.0061 (6)	0.0122 (6)	−0.0011 (5)
C6	0.0409 (6)	0.0363 (6)	0.0334 (6)	0.0026 (5)	0.0118 (5)	0.0053 (4)
C7	0.0410 (6)	0.0395 (6)	0.0335 (6)	0.0019 (5)	0.0095 (5)	−0.0001 (5)
C8	0.0572 (8)	0.0520 (7)	0.0299 (6)	0.0070 (6)	0.0089 (5)	−0.0020 (5)
C9	0.0504 (7)	0.0528 (7)	0.0368 (6)	0.0087 (6)	0.0053 (5)	0.0017 (5)
C10	0.0460 (7)	0.0396 (6)	0.0435 (7)	0.0020 (5)	0.0139 (6)	0.0008 (5)
C11	0.0503 (7)	0.0417 (6)	0.0352 (6)	0.0010 (5)	0.0130 (5)	−0.0047 (5)
C12	0.0460 (7)	0.0416 (6)	0.0321 (6)	0.0010 (5)	0.0115 (5)	0.0005 (5)
C13	0.0599 (9)	0.0541 (8)	0.0621 (9)	0.0150 (7)	0.0131 (7)	−0.0064 (7)
N1	0.0510 (7)	0.0649 (8)	0.0446 (7)	−0.0082 (6)	0.0016 (5)	−0.0002 (6)
N3	0.0479 (6)	0.0452 (6)	0.0318 (5)	0.0083 (5)	0.0114 (4)	−0.0001 (4)
N4	0.0627 (8)	0.0625 (8)	0.0355 (6)	0.0192 (6)	0.0026 (5)	−0.0050 (5)
O1	0.1008 (11)	0.1144 (12)	0.0473 (7)	0.0141 (9)	−0.0148 (7)	0.0027 (7)
O2	0.1014 (10)	0.0528 (7)	0.0671 (8)	−0.0131 (6)	0.0094 (7)	−0.0113 (6)
O3	0.0669 (7)	0.0634 (6)	0.0391 (5)	0.0162 (5)	0.0237 (5)	0.0062 (4)
O4	0.0522 (6)	0.0648 (6)	0.0372 (5)	0.0209 (5)	0.0111 (4)	0.0079 (4)

C1—C2	1.382 (2)	C9—C10	1.4137 (19)
C1—C6	1.3880 (17)	C9—H9	0.9300
C1—N1	1.4682 (18)	C10—C11	1.3688 (18)
C2—C3	1.379 (3)	C10—C13	1.4985 (19)
C2—H2	0.9300	C11—C12	1.4101 (18)
C3—C4	1.372 (2)	C11—H11	0.9300
C3—H3	0.9300	C12—N4	1.3295 (17)
C4—C5	1.385 (2)	C12—N3	1.3505 (16)
C4—H4	0.9300	C13—H13A	0.9600
C5—C6	1.3872 (18)	C13—H13B	0.9600
C5—H5	0.9300	C13—H13C	0.9600
C6—C7	1.5122 (17)	N1—O2	1.2165 (18)
C7—O3	1.2372 (15)	N1—O1	1.2203 (17)
C7—O4	1.2585 (15)	N3—H3A	0.933 (18)
C8—C9	1.3510 (19)	N4—H4B	0.871 (19)
C8—N3	1.3526 (17)	N4—H4A	0.923 (19)
C8—H8	0.9300
C2—C1—C6	122.54 (13)	C10—C9—H9	120.3
C2—C1—N1	117.55 (13)	C11—C10—C9	118.75 (12)
C6—C1—N1	119.83 (12)	C11—C10—C13	121.87 (12)
C3—C2—C1	118.83 (14)	C9—C10—C13	119.37 (12)
C3—C2—H2	120.6	C10—C11—C12	120.57 (12)
C1—C2—H2	120.6	C10—C11—H11	119.7
C4—C3—C2	120.27 (14)	C12—C11—H11	119.7
C4—C3—H3	119.9	N4—C12—N3	118.01 (12)
C2—C3—H3	119.9	N4—C12—C11	123.81 (12)
C3—C4—C5	120.01 (15)	N3—C12—C11	118.18 (11)
C3—C4—H4	120.0	C10—C13—H13A	109.5
C5—C4—H4	120.0	C10—C13—H13B	109.5
C4—C5—C6	121.40 (13)	H13A—C13—H13B	109.5
C4—C5—H5	119.3	C10—C13—H13C	109.5
C6—C5—H5	119.3	H13A—C13—H13C	109.5
C5—C6—C1	116.90 (11)	H13B—C13—H13C	109.5
C5—C6—C7	119.41 (11)	O2—N1—O1	124.08 (15)
C1—C6—C7	123.29 (11)	O2—N1—C1	118.07 (12)
O3—C7—O4	125.59 (12)	O1—N1—C1	117.84 (14)
O3—C7—C6	117.46 (11)	C12—N3—C8	122.02 (11)
O4—C7—C6	116.88 (10)	C12—N3—H3A	120.8 (11)
C9—C8—N3	121.08 (12)	C8—N3—H3A	117.1 (11)
C9—C8—H8	119.5	C12—N4—H4B	119.2 (11)
N3—C8—H8	119.5	C12—N4—H4A	118.3 (11)
C8—C9—C10	119.39 (12)	H4B—N4—H4A	122.2 (16)
C8—C9—H9	120.3
C6—C1—C2—C3	−1.2 (2)	N3—C8—C9—C10	−0.6 (2)
N1—C1—C2—C3	175.64 (14)	C8—C9—C10—C11	0.4 (2)
C1—C2—C3—C4	−0.8 (2)	C8—C9—C10—C13	−178.59 (14)
C2—C3—C4—C5	1.4 (3)	C9—C10—C11—C12	−0.1 (2)
C3—C4—C5—C6	0.0 (2)	C13—C10—C11—C12	178.84 (13)
C4—C5—C6—C1	−1.9 (2)	C10—C11—C12—N4	−179.53 (14)
C4—C5—C6—C7	171.12 (13)	C10—C11—C12—N3	0.1 (2)
C2—C1—C6—C5	2.48 (19)	C2—C1—N1—O2	−137.16 (16)
N1—C1—C6—C5	−174.27 (12)	C6—C1—N1—O2	39.75 (19)
C2—C1—C6—C7	−170.21 (12)	C2—C1—N1—O1	41.9 (2)
N1—C1—C6—C7	13.05 (18)	C6—C1—N1—O1	−141.19 (15)
C5—C6—C7—O3	−134.09 (13)	N4—C12—N3—C8	179.29 (13)
C1—C6—C7—O3	38.42 (18)	C11—C12—N3—C8	−0.33 (19)
C5—C6—C7—O4	43.01 (17)	C9—C8—N3—C12	0.6 (2)
C1—C6—C7—O4	−144.48 (13)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O4i	0.933 (18)	1.752 (19)	2.6746 (16)	169.5 (17)
N4—H4A···O3i	0.923 (19)	1.972 (19)	2.8734 (18)	164.9 (17)
N4—H4B···O4ii	0.871 (19)	2.033 (19)	2.8937 (16)	169.7 (18)
C11—H11···O3iii	0.93	2.58	3.3624 (16)	142

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O4i	0.933 (18)	1.752 (19)	2.6746 (16)	169.5 (17)
N4—H4A⋯O3i	0.923 (19)	1.972 (19)	2.8734 (18)	164.9 (17)
N4—H4B⋯O4ii	0.871 (19)	2.033 (19)	2.8937 (16)	169.7 (18)
C11—H11⋯O3iii	0.93	2.58	3.3624 (16)	142

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