2-Amino-4-methylpyridinium 2-hy-droxy-3,5-dinitro-benzoate.

In the anion of the title mol-ecular salt, C(6)H(9)N(2) (+)·C(7)H(3)N(2)O(7) (-), the two nitro groups are twisted from the attached benzene ring with dihedral angles of 27.36 (10) and 4.86 (11)°. The anion is stabilized by an intra-molecular O-H⋯O hydrogen bond, which generates an S(6) ring motif. In the crystal, the cations and anions are linked by N-H⋯O and C-H⋯O inter-actions and are further consolidated by C-H⋯π inter-actions, to generate a three-dimensional network. A short O⋯N contact of 2.876 (2) Å also occurs.

Related literature

For substituted pyridines, see: Pozharski et al. (1997 ▶); Katritzky et al. (1996 ▶). For details of hydrogen bonding, see: Scheiner (1997 ▶); Jeffrey & Saenger (1991 ▶); Jeffrey (1997 ▶). For 2-amino-substituted pyridines, see: Navarro Ranninger et al. (1985 ▶); Luque et al. (1997 ▶); Qin et al. (1999 ▶); Ren et al. (2002 ▶); Rivas et al. (2003 ▶); Jin et al. (2001 ▶); Albrecht et al. (2003 ▶). For Lewis bases with 3,5-dinitrosalicylic acid, see: Hindawey et al. (1980 ▶); Issa et al. (1981 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For related structures, see: Quah et al. (2008a ▶,b ▶, 2010 ▶). For reference bond lengths, see: Allen et al. (1987 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C6H9N2 +·C7H3N2O7 −

M = 336.27

Monoclinic,

a = 6.0111 (15) Å

b = 9.652 (3) Å

c = 24.436 (6) Å

β = 100.546 (7)°

V = 1393.8 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.13 mm−1

T = 100 K

0.48 × 0.08 × 0.06 mm

Data collection

Bruker SMART APEXII DUO CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.939, T max = 0.992

12178 measured reflections

3229 independent reflections

2283 reflections with I > 2σ(I)

R int = 0.057

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.153

S = 1.03

3229 reflections

222 parameters

H-atom parameters constrained

Δρmax = 0.31 e Å−3

Δρmin = −0.44 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 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810025912/hb5538sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810025912/hb5538Isup2.hkl

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

C6H9N2+·C7H3N2O7−	F(000) = 696
Mr = 336.27	Dx = 1.602 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2122 reflections
a = 6.0111 (15) Å	θ = 2.7–26.4°
b = 9.652 (3) Å	µ = 0.13 mm−1
c = 24.436 (6) Å	T = 100 K
β = 100.546 (7)°	Needle, yellow
V = 1393.8 (7) Å3	0.48 × 0.08 × 0.06 mm
Z = 4

Bruker SMART APEXII DUO CCD diffractometer	3229 independent reflections
Radiation source: fine-focus sealed tube	2283 reflections with I > 2σ(I)
graphite	Rint = 0.057
φ and ω scans	θmax = 27.6°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −7→7
Tmin = 0.939, Tmax = 0.992	k = −12→12
12178 measured reflections	l = −31→26

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.153	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0909P)2] where P = (Fo2 + 2Fc2)/3
3229 reflections	(Δ/σ)max = 0.001
222 parameters	Δρmax = 0.31 e Å−3
0 restraints	Δρmin = −0.44 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems 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	0.2405 (3)	0.80105 (17)	0.83755 (7)	0.0179 (4)
H1N1	0.1325	0.7348	0.8455	0.034 (7)*
N2	0.5190 (3)	0.75204 (18)	0.91264 (7)	0.0220 (4)
H1N2	0.4146	0.6810	0.9219	0.052 (9)*
H2N2	0.6655	0.7664	0.9340	0.063 (10)*
C1	0.4517 (3)	0.8236 (2)	0.86605 (8)	0.0170 (4)
C2	0.5856 (3)	0.9234 (2)	0.84489 (9)	0.0187 (4)
H2A	0.7321	0.9408	0.8636	0.022*
C3	0.5022 (3)	0.9946 (2)	0.79722 (9)	0.0187 (4)
C4	0.2784 (3)	0.9680 (2)	0.76912 (9)	0.0199 (4)
H4A	0.2179	1.0163	0.7369	0.024*
C5	0.1541 (3)	0.8708 (2)	0.79013 (9)	0.0192 (4)
H5A	0.0076	0.8518	0.7718	0.023*
C6	0.6432 (4)	1.1006 (2)	0.77401 (9)	0.0231 (5)
H6A	0.7790	1.1181	0.8006	0.035*
H6B	0.5587	1.1850	0.7666	0.035*
H6C	0.6820	1.0662	0.7401	0.035*
O1	1.1381 (2)	0.34244 (14)	0.99102 (6)	0.0198 (3)
H1O1	1.2304	0.4181	0.9798	0.119 (16)*
O2	0.9779 (2)	0.16274 (14)	1.05842 (6)	0.0218 (4)
O3	0.7607 (2)	0.00824 (15)	1.01170 (7)	0.0242 (4)
O4	0.1674 (2)	0.17877 (16)	0.86962 (7)	0.0264 (4)
O5	0.2470 (3)	0.33999 (17)	0.81463 (7)	0.0321 (4)
O6	0.9513 (2)	0.60237 (15)	0.85954 (6)	0.0219 (3)
O7	1.2134 (2)	0.53070 (14)	0.93122 (6)	0.0206 (3)
N3	0.8463 (3)	0.12385 (17)	1.01644 (7)	0.0176 (4)
N4	0.2953 (3)	0.26704 (18)	0.85650 (7)	0.0212 (4)
C7	0.9355 (3)	0.32562 (19)	0.96014 (9)	0.0159 (4)
C8	0.7863 (3)	0.2196 (2)	0.97011 (8)	0.0169 (4)
C9	0.5784 (3)	0.1992 (2)	0.93658 (9)	0.0172 (4)
H9A	0.4837	0.1279	0.9438	0.021*
C10	0.5143 (3)	0.2876 (2)	0.89190 (8)	0.0176 (4)
C11	0.6536 (3)	0.3935 (2)	0.88017 (9)	0.0179 (4)
H11A	0.6066	0.4515	0.8499	0.022*
C12	0.8626 (3)	0.4127 (2)	0.91368 (8)	0.0164 (4)
C13	1.0164 (3)	0.5246 (2)	0.89969 (9)	0.0175 (4)

	U11	U22	U33	U12	U13	U23
N1	0.0180 (8)	0.0159 (8)	0.0193 (9)	−0.0010 (6)	0.0019 (7)	−0.0004 (7)
N2	0.0196 (8)	0.0221 (9)	0.0226 (10)	−0.0029 (7)	−0.0002 (7)	0.0060 (7)
C1	0.0167 (9)	0.0148 (9)	0.0197 (11)	0.0023 (7)	0.0034 (8)	−0.0016 (8)
C2	0.0175 (9)	0.0153 (9)	0.0229 (11)	0.0004 (7)	0.0029 (8)	0.0005 (8)
C3	0.0221 (10)	0.0133 (9)	0.0218 (11)	0.0011 (8)	0.0066 (8)	−0.0027 (8)
C4	0.0242 (10)	0.0159 (10)	0.0195 (11)	0.0034 (8)	0.0039 (8)	0.0006 (8)
C5	0.0181 (9)	0.0189 (10)	0.0195 (11)	0.0037 (8)	0.0008 (8)	−0.0012 (8)
C6	0.0278 (11)	0.0168 (10)	0.0256 (12)	0.0000 (8)	0.0069 (9)	0.0029 (9)
O1	0.0170 (7)	0.0188 (7)	0.0215 (8)	−0.0024 (6)	−0.0014 (6)	0.0008 (6)
O2	0.0205 (7)	0.0234 (8)	0.0200 (8)	−0.0013 (6)	−0.0001 (6)	−0.0001 (6)
O3	0.0203 (7)	0.0164 (7)	0.0353 (9)	−0.0040 (6)	0.0033 (6)	0.0049 (7)
O4	0.0200 (7)	0.0276 (8)	0.0309 (9)	−0.0066 (6)	0.0028 (6)	−0.0028 (7)
O5	0.0303 (9)	0.0338 (9)	0.0272 (9)	−0.0016 (7)	−0.0084 (7)	0.0069 (7)
O6	0.0245 (8)	0.0183 (7)	0.0216 (8)	−0.0039 (6)	0.0006 (6)	0.0028 (6)
O7	0.0182 (7)	0.0181 (7)	0.0244 (8)	−0.0021 (5)	0.0009 (6)	0.0025 (6)
N3	0.0152 (8)	0.0162 (8)	0.0218 (9)	−0.0002 (6)	0.0042 (7)	0.0022 (7)
N4	0.0187 (8)	0.0203 (9)	0.0238 (10)	0.0003 (7)	0.0016 (7)	−0.0026 (8)
C7	0.0144 (9)	0.0144 (9)	0.0186 (10)	0.0010 (7)	0.0021 (8)	−0.0025 (8)
C8	0.0186 (9)	0.0139 (9)	0.0177 (10)	0.0021 (7)	0.0020 (8)	−0.0006 (8)
C9	0.0169 (9)	0.0142 (9)	0.0207 (11)	−0.0004 (7)	0.0037 (8)	−0.0017 (8)
C10	0.0161 (9)	0.0162 (9)	0.0191 (11)	0.0008 (7)	−0.0007 (8)	−0.0028 (8)
C11	0.0198 (9)	0.0159 (9)	0.0181 (10)	0.0043 (8)	0.0035 (8)	0.0000 (8)
C12	0.0164 (9)	0.0132 (9)	0.0199 (11)	0.0005 (7)	0.0038 (8)	−0.0018 (8)
C13	0.0189 (9)	0.0144 (9)	0.0193 (11)	−0.0002 (7)	0.0040 (8)	−0.0001 (8)

N1—C1	1.349 (2)	O1—H1O1	0.9856
N1—C5	1.359 (3)	O2—N3	1.234 (2)
N1—H1N1	0.9560	O3—N3	1.226 (2)
N2—C1	1.330 (3)	O4—N4	1.229 (2)
N2—H1N2	0.9833	O5—N4	1.232 (2)
N2—H2N2	0.9478	O6—C13	1.241 (2)
C1—C2	1.413 (3)	O7—C13	1.291 (2)
C2—C3	1.366 (3)	N3—C8	1.455 (3)
C2—H2A	0.9300	N4—C10	1.450 (2)
C3—C4	1.417 (3)	C7—C8	1.411 (3)
C3—C6	1.504 (3)	C7—C12	1.416 (3)
C4—C5	1.358 (3)	C8—C9	1.377 (3)
C4—H4A	0.9300	C9—C10	1.383 (3)
C5—H5A	0.9300	C9—H9A	0.9300
C6—H6A	0.9600	C10—C11	1.385 (3)
C6—H6B	0.9600	C11—C12	1.381 (3)
C6—H6C	0.9600	C11—H11A	0.9300
O1—C7	1.320 (2)	C12—C13	1.501 (3)
C1—N1—C5	122.49 (18)	O3—N3—O2	123.37 (17)
C1—N1—H1N1	127.8	O3—N3—C8	117.70 (16)
C5—N1—H1N1	109.6	O2—N3—C8	118.93 (16)
C1—N2—H1N2	116.8	O4—N4—O5	123.33 (18)
C1—N2—H2N2	120.1	O4—N4—C10	118.81 (17)
H1N2—N2—H2N2	122.9	O5—N4—C10	117.86 (17)
N2—C1—N1	117.93 (18)	O1—C7—C8	122.67 (18)
N2—C1—C2	124.26 (18)	O1—C7—C12	120.20 (18)
N1—C1—C2	117.80 (18)	C8—C7—C12	117.10 (17)
C3—C2—C1	120.67 (19)	C9—C8—C7	122.50 (19)
C3—C2—H2A	119.7	C9—C8—N3	116.15 (17)
C1—C2—H2A	119.7	C7—C8—N3	121.34 (17)
C2—C3—C4	119.33 (19)	C8—C9—C10	118.22 (19)
C2—C3—C6	121.29 (19)	C8—C9—H9A	120.9
C4—C3—C6	119.38 (18)	C10—C9—H9A	120.9
C5—C4—C3	118.77 (19)	C9—C10—C11	121.79 (18)
C5—C4—H4A	120.6	C9—C10—N4	118.56 (18)
C3—C4—H4A	120.6	C11—C10—N4	119.65 (18)
C4—C5—N1	120.93 (18)	C12—C11—C10	119.70 (19)
C4—C5—H5A	119.5	C12—C11—H11A	120.2
N1—C5—H5A	119.5	C10—C11—H11A	120.2
C3—C6—H6A	109.5	C11—C12—C7	120.68 (18)
C3—C6—H6B	109.5	C11—C12—C13	119.52 (18)
H6A—C6—H6B	109.5	C7—C12—C13	119.77 (17)
C3—C6—H6C	109.5	O6—C13—O7	124.53 (18)
H6A—C6—H6C	109.5	O6—C13—C12	119.82 (18)
H6B—C6—H6C	109.5	O7—C13—C12	115.65 (17)
C7—O1—H1O1	116.1
C5—N1—C1—N2	178.61 (18)	N3—C8—C9—C10	−179.85 (17)
C5—N1—C1—C2	−0.4 (3)	C8—C9—C10—C11	0.6 (3)
N2—C1—C2—C3	−178.7 (2)	C8—C9—C10—N4	−179.81 (17)
N1—C1—C2—C3	0.2 (3)	O4—N4—C10—C9	5.3 (3)
C1—C2—C3—C4	0.3 (3)	O5—N4—C10—C9	−174.93 (18)
C1—C2—C3—C6	−179.65 (19)	O4—N4—C10—C11	−175.09 (18)
C2—C3—C4—C5	−0.8 (3)	O5—N4—C10—C11	4.7 (3)
C6—C3—C4—C5	179.17 (19)	C9—C10—C11—C12	0.0 (3)
C3—C4—C5—N1	0.7 (3)	N4—C10—C11—C12	−179.65 (18)
C1—N1—C5—C4	−0.1 (3)	C10—C11—C12—C7	−0.4 (3)
O1—C7—C8—C9	−177.55 (19)	C10—C11—C12—C13	177.93 (18)
C12—C7—C8—C9	0.3 (3)	O1—C7—C12—C11	178.16 (18)
O1—C7—C8—N3	1.6 (3)	C8—C7—C12—C11	0.3 (3)
C12—C7—C8—N3	179.39 (17)	O1—C7—C12—C13	−0.2 (3)
O3—N3—C8—C9	26.5 (3)	C8—C7—C12—C13	−178.04 (17)
O2—N3—C8—C9	−152.80 (18)	C11—C12—C13—O6	2.8 (3)
O3—N3—C8—C7	−152.64 (18)	C7—C12—C13—O6	−178.83 (19)
O2—N3—C8—C7	28.0 (3)	C11—C12—C13—O7	−176.29 (18)
C7—C8—C9—C10	−0.7 (3)	C7—C12—C13—O7	2.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O6i	0.96	1.75	2.707 (2)	175
N2—H1N2···O7i	0.98	1.93	2.907 (2)	173
N2—H2N2···O1ii	0.95	2.25	2.974 (2)	133
N2—H2N2···O2ii	0.95	2.23	3.089 (2)	151
O1—H1O1···O7	0.99	1.60	2.426 (2)	138
C2—H2A···O2ii	0.93	2.54	3.300 (3)	139
C4—H4A···O6iii	0.93	2.53	3.447 (3)	169
C5—H5A···O5iv	0.93	2.37	3.193 (3)	147
C9—H9A···O3v	0.93	2.38	3.272 (3)	161
C6—H6B···Cg1iii	0.96	2.99	3.623 (2)	12

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O6i	0.96	1.75	2.707 (2)	175
N2—H1N2⋯O7i	0.98	1.93	2.907 (2)	173
N2—H2N2⋯O1ii	0.95	2.25	2.974 (2)	133
N2—H2N2⋯O2ii	0.95	2.23	3.089 (2)	151
O1—H1O1⋯O7	0.99	1.60	2.426 (2)	138
C2—H2A⋯O2ii	0.93	2.54	3.300 (3)	139
C4—H4A⋯O6iii	0.93	2.53	3.447 (3)	169
C5—H5A⋯O5iv	0.93	2.37	3.193 (3)	147
C9—H9A⋯O3v	0.93	2.38	3.272 (3)	161
C6—H6B⋯Cg1iii	0.96	2.99	3.623 (2)	12

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