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

In the title compound, C(6)H(9)N(2) (+)·C(7)H(4)NO(4) (-), the nitro group of the 4-nitro-benzoate anion is twisted by 6.2 (2)° from the attached ring. In the crystal structure, the cations and anions are linked via strong N-H⋯O and weak C-H⋯O hydrogen bonds, forming a three-dimensional network.

Related literature

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997 ▶); Katritzky et al. (1996 ▶); Hemamalini & Fun (2010 ▶). For details of n class="Chemical">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 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C6H9N2 +·n class="Chemical">C7H4NO4 −

M = 275.26

Monoclinic,

a = 13.684 (12) Å

b = 4.025 (4) Å

c = 12.706 (11) Å

β = 114.94 (2)°

V = 634.5 (10) Å3

Z = 2

Mo Kα radiation

μ = 0.11 mm−1

T = 100 K

0.36 × 0.18 × 0.08 mm

Data collection

Bruker APEX DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.961, T max = 0.991

7053 measured reflections

1854 independent reflections

1283 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.116

S = 1.06

1854 reflections

222 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.19 e Å−3

Δρmin = −0.20 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/S1600536810005301/sj2727sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810005301/sj2727Isup2.hkl

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

C6H9N2+·C7H4NO4−	F(000) = 288
Mr = 275.26	Dx = 1.441 Mg m−3
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2yc	Cell parameters from 1854 reflections
a = 13.684 (12) Å	θ = 3.2–28.2°
b = 4.025 (4) Å	µ = 0.11 mm−1
c = 12.706 (11) Å	T = 100 K
β = 114.94 (2)°	Block, colourless
V = 634.5 (10) Å3	0.36 × 0.18 × 0.08 mm
Z = 2

Bruker APEX DUO CCD area-detector diffractometer	1854 independent reflections
Radiation source: fine-focus sealed tube	1283 reflections with I > 2σ(I)
graphite	Rint = 0.042
φ and ω scans	θmax = 30.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −18→19
Tmin = 0.961, Tmax = 0.991	k = −5→5
7053 measured reflections	l = −17→17

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0604P)2] where P = (Fo2 + 2Fc2)/3
1854 reflections	(Δ/σ)max < 0.001
222 parameters	Δρmax = 0.19 e Å−3
2 restraints	Δρmin = −0.20 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
N1	0.83203 (19)	0.0861 (6)	0.16111 (18)	0.0407 (6)
N2	0.7398 (2)	0.0221 (8)	−0.0369 (2)	0.0498 (7)
C1	0.8230 (2)	0.1476 (7)	0.0532 (2)	0.0399 (7)
C2	0.9053 (3)	0.3372 (8)	0.0431 (3)	0.0489 (8)
C3	0.9897 (3)	0.4449 (9)	0.1392 (3)	0.0508 (8)
C4	0.9979 (3)	0.3777 (7)	0.2514 (3)	0.0459 (7)
C5	0.9169 (2)	0.1971 (8)	0.2569 (3)	0.0429 (7)
C6	1.0921 (3)	0.4935 (10)	0.3582 (3)	0.0653 (9)
H6A	1.0781	0.4540	0.4251	0.098*
H6B	1.1030	0.7269	0.3519	0.098*
H6C	1.1555	0.3739	0.3662	0.098*
O1	0.1957 (2)	−0.0891 (11)	0.1134 (2)	0.0995 (12)
O2	0.2751 (3)	−0.0198 (10)	0.2954 (3)	0.0953 (11)
O3	0.61995 (19)	0.6210 (7)	0.04604 (18)	0.0613 (7)
O4	0.70099 (15)	0.7415 (6)	0.23282 (17)	0.0504 (5)
N3	0.2718 (2)	0.0063 (7)	0.1991 (2)	0.0548 (7)
C7	0.5306 (2)	0.4378 (8)	0.2704 (2)	0.0401 (6)
C8	0.4456 (2)	0.2895 (8)	0.2828 (2)	0.0428 (6)
C9	0.3641 (2)	0.1565 (7)	0.1870 (2)	0.0400 (6)
C10	0.3648 (3)	0.1575 (8)	0.0790 (3)	0.0470 (7)
C11	0.4522 (2)	0.3019 (8)	0.0683 (2)	0.0443 (7)
C12	0.5345 (2)	0.4473 (7)	0.1622 (2)	0.0339 (5)
C13	0.6260 (2)	0.6165 (7)	0.1462 (2)	0.0401 (7)
H2A	0.896 (2)	0.396 (9)	−0.035 (3)	0.048 (8)*
H3A	1.042 (3)	0.577 (9)	0.131 (3)	0.059 (10)*
H5A	0.915 (3)	0.145 (9)	0.328 (3)	0.055 (9)*
H7A	0.585 (2)	0.545 (7)	0.333 (2)	0.034 (7)*
H9A	0.442 (3)	0.273 (8)	0.355 (4)	0.061 (10)*
H10A	0.308 (3)	0.083 (10)	0.017 (3)	0.065 (11)*
H11A	0.459 (3)	0.323 (10)	−0.006 (4)	0.070 (11)*
H1N1	0.775 (4)	−0.035 (9)	0.171 (3)	0.059 (10)*
H1N2	0.728 (3)	0.097 (9)	−0.107 (3)	0.052 (9)*
H2N2	0.691 (3)	−0.087 (9)	−0.019 (3)	0.055 (10)*

	U11	U22	U33	U12	U13	U23
N1	0.0419 (14)	0.0442 (13)	0.0410 (12)	0.0003 (11)	0.0224 (11)	0.0046 (11)
N2	0.0518 (16)	0.0608 (17)	0.0392 (13)	0.0021 (13)	0.0217 (12)	0.0057 (12)
C1	0.0431 (16)	0.0395 (16)	0.0406 (14)	0.0106 (12)	0.0211 (13)	0.0076 (12)
C2	0.061 (2)	0.0446 (17)	0.0533 (17)	0.0047 (14)	0.0356 (16)	0.0118 (14)
C3	0.0485 (19)	0.0460 (18)	0.064 (2)	−0.0025 (15)	0.0299 (16)	0.0072 (15)
C4	0.0455 (17)	0.0389 (15)	0.0514 (16)	0.0041 (13)	0.0186 (14)	0.0031 (14)
C5	0.0444 (16)	0.0457 (16)	0.0393 (15)	0.0034 (13)	0.0183 (13)	0.0043 (13)
C6	0.052 (2)	0.064 (2)	0.066 (2)	−0.0083 (17)	0.0123 (16)	0.0025 (17)
O1	0.069 (2)	0.162 (3)	0.0674 (18)	−0.061 (2)	0.0293 (16)	−0.0244 (19)
O2	0.090 (2)	0.152 (3)	0.0620 (17)	−0.046 (2)	0.0490 (17)	−0.0059 (18)
O3	0.0633 (15)	0.0915 (18)	0.0378 (11)	−0.0184 (13)	0.0299 (11)	−0.0033 (12)
O4	0.0455 (12)	0.0696 (14)	0.0406 (11)	−0.0138 (11)	0.0224 (9)	−0.0070 (10)
N3	0.0509 (16)	0.0659 (18)	0.0539 (16)	−0.0126 (14)	0.0283 (13)	−0.0038 (14)
C7	0.0454 (16)	0.0462 (16)	0.0284 (12)	−0.0042 (13)	0.0151 (12)	−0.0026 (11)
C8	0.0498 (17)	0.0510 (18)	0.0330 (13)	−0.0057 (14)	0.0227 (12)	−0.0005 (12)
C9	0.0410 (16)	0.0405 (16)	0.0424 (15)	0.0001 (11)	0.0216 (13)	0.0031 (12)
C10	0.0476 (18)	0.0576 (19)	0.0325 (14)	−0.0095 (15)	0.0135 (13)	−0.0051 (13)
C11	0.0524 (18)	0.0542 (19)	0.0305 (13)	−0.0037 (14)	0.0216 (13)	−0.0002 (12)
C12	0.0377 (14)	0.0360 (14)	0.0297 (11)	0.0035 (10)	0.0160 (10)	0.0013 (10)
C13	0.0445 (17)	0.0470 (16)	0.0330 (14)	−0.0004 (13)	0.0203 (12)	0.0017 (11)

N1—C1	1.347 (3)	O1—N3	1.208 (4)
N1—C5	1.355 (4)	O2—N3	1.210 (4)
N1—H1N1	0.97 (4)	O3—C13	1.241 (3)
N2—C1	1.328 (4)	O4—C13	1.251 (3)
N2—H1N2	0.89 (4)	N3—C9	1.466 (4)
N2—H2N2	0.90 (4)	C7—C8	1.374 (4)
C1—C2	1.410 (4)	C7—C12	1.399 (4)
C2—C3	1.350 (5)	C7—H7A	0.94 (3)
C2—H2A	0.97 (3)	C8—C9	1.366 (4)
C3—C4	1.408 (5)	C8—H9A	0.94 (4)
C3—H3A	0.94 (4)	C9—C10	1.375 (4)
C4—C5	1.352 (5)	C10—C11	1.387 (5)
C4—C6	1.499 (5)	C10—H10A	0.89 (4)
C5—H5A	0.93 (4)	C11—C12	1.379 (4)
C6—H6A	0.9600	C11—H11A	0.98 (4)
C6—H6B	0.9600	C12—C13	1.512 (4)
C6—H6C	0.9600
C1—N1—C5	122.0 (3)	H6B—C6—H6C	109.5
C1—N1—H1N1	119 (2)	O1—N3—O2	122.2 (3)
C5—N1—H1N1	119 (2)	O1—N3—C9	119.3 (3)
C1—N2—H1N2	117 (2)	O2—N3—C9	118.4 (3)
C1—N2—H2N2	115 (2)	C8—C7—C12	120.6 (3)
H1N2—N2—H2N2	125 (3)	C8—C7—H7A	121.1 (18)
N2—C1—N1	119.0 (3)	C12—C7—H7A	118.2 (18)
N2—C1—C2	123.7 (3)	C9—C8—C7	118.7 (3)
N1—C1—C2	117.2 (3)	C9—C8—H9A	118 (2)
C3—C2—C1	120.2 (3)	C7—C8—H9A	123 (2)
C3—C2—H2A	122.6 (19)	C8—C9—C10	122.8 (3)
C1—C2—H2A	117.1 (19)	C8—C9—N3	118.9 (2)
C2—C3—C4	121.7 (3)	C10—C9—N3	118.3 (3)
C2—C3—H3A	119 (2)	C9—C10—C11	117.9 (3)
C4—C3—H3A	119 (2)	C9—C10—H10A	120 (2)
C5—C4—C3	116.0 (3)	C11—C10—H10A	122 (2)
C5—C4—C6	122.1 (3)	C12—C11—C10	121.1 (3)
C3—C4—C6	121.8 (3)	C12—C11—H11A	115 (2)
C4—C5—N1	122.8 (3)	C10—C11—H11A	124 (2)
C4—C5—H5A	122 (2)	C11—C12—C7	118.9 (3)
N1—C5—H5A	116 (2)	C11—C12—C13	119.7 (2)
C4—C6—H6A	109.5	C7—C12—C13	121.4 (2)
C4—C6—H6B	109.5	O3—C13—O4	124.8 (3)
H6A—C6—H6B	109.5	O3—C13—C12	116.3 (2)
C4—C6—H6C	109.5	O4—C13—C12	118.8 (2)
H6A—C6—H6C	109.5
C5—N1—C1—N2	177.7 (3)	O2—N3—C9—C8	−6.1 (5)
C5—N1—C1—C2	−0.7 (4)	O1—N3—C9—C10	−5.5 (5)
N2—C1—C2—C3	−177.3 (3)	O2—N3—C9—C10	173.9 (3)
N1—C1—C2—C3	1.1 (4)	C8—C9—C10—C11	−0.3 (5)
C1—C2—C3—C4	−1.0 (5)	N3—C9—C10—C11	179.6 (3)
C2—C3—C4—C5	0.6 (5)	C9—C10—C11—C12	−1.6 (5)
C2—C3—C4—C6	179.3 (3)	C10—C11—C12—C7	2.1 (4)
C3—C4—C5—N1	−0.2 (5)	C10—C11—C12—C13	−177.2 (3)
C6—C4—C5—N1	−178.9 (3)	C8—C7—C12—C11	−0.8 (4)
C1—N1—C5—C4	0.3 (4)	C8—C7—C12—C13	178.5 (3)
C12—C7—C8—C9	−1.1 (4)	C11—C12—C13—O3	1.7 (4)
C7—C8—C9—C10	1.6 (5)	C7—C12—C13—O3	−177.6 (3)
C7—C8—C9—N3	−178.3 (3)	C11—C12—C13—O4	−178.7 (3)
O1—N3—C9—C8	174.4 (4)	C7—C12—C13—O4	2.1 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O3i	0.97 (5)	2.47 (4)	3.238 (5)	136 (3)
N1—H1N1···O4i	0.97 (5)	1.77 (5)	2.711 (4)	163 (3)
N2—H1N2···O4ii	0.89 (4)	2.02 (4)	2.905 (4)	179 (5)
N2—H2N2···O3i	0.91 (4)	1.92 (4)	2.804 (5)	165 (4)
C3—H3A···O1iii	0.93 (4)	2.58 (4)	3.514 (6)	176 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O3i	0.97 (5)	2.47 (4)	3.238 (5)	136 (3)
N1—H1N1⋯O4i	0.97 (5)	1.77 (5)	2.711 (4)	163 (3)
N2—H1N2⋯O4ii	0.89 (4)	2.02 (4)	2.905 (4)	179 (5)
N2—H2N2⋯O3i	0.91 (4)	1.92 (4)	2.804 (5)	165 (4)
C3—H3A⋯O1iii	0.93 (4)	2.58 (4)	3.514 (6)	176 (3)

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