2-Amino-5-methyl-pyridinium 2-hydr-oxy-3,5-dinitro-benzoate.

In the title mol-ecular salt, C(6)H(9)N(2) (+)·C(7)H(3)N(2)O(7) (-), the 2-amino-5-methyl-pyridinium cation is essentially planar, with a maximum deviation of 0.023 (1) Å. There is an intra-molecular O-H⋯O hydrogen bond in the 3,5-dinitro-salicylate anion, which generates an S(6) ring motif. In the crystal, the protonated N atom and the 2-amino group 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. Weak inter-molecular C-H⋯O inter-actions help to further stabilize the crystal structure.

Related literature

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997 ▶); Katritzky et al. (1996 ▶); Nahringbauer & Kvick (1977 ▶). For 3,5-dinitro­salicylic acid, see: Hindawey et al. (1980 ▶); Issa et al. (1981 ▶). 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 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C6H9N2 +·C7H3N2O7 −

M = 336.27

Triclinic,

a = 5.8673 (7) Å

b = 8.0991 (9) Å

c = 15.2437 (17) Å

α = 86.844 (3)°

β = 84.252 (3)°

γ = 81.209 (3)°

V = 711.69 (14) Å3

Z = 2

Mo Kα radiation

μ = 0.13 mm−1

T = 100 K

0.29 × 0.14 × 0.08 mm

Data collection

Bruker APEX DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.963, T max = 0.990

12709 measured reflections

4947 independent reflections

3922 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.150

S = 1.08

4947 reflections

219 parameters

H-atom parameters constrained

Δρmax = 0.51 e Å−3

Δρmin = −0.46 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/S1600536810014480/hb5405sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810014480/hb5405Isup2.hkl

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

C6H9N2+·C7H3N2O7−	Z = 2
Mr = 336.27	F(000) = 348
Triclinic, P1	Dx = 1.569 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.8673 (7) Å	Cell parameters from 5139 reflections
b = 8.0991 (9) Å	θ = 2.7–32.4°
c = 15.2437 (17) Å	µ = 0.13 mm−1
α = 86.844 (3)°	T = 100 K
β = 84.252 (3)°	Block, yellow
γ = 81.209 (3)°	0.29 × 0.14 × 0.08 mm
V = 711.69 (14) Å3

Bruker APEX DUO CCD area-detector diffractometer	4947 independent reflections
Radiation source: fine-focus sealed tube	3922 reflections with I > 2σ(I)
graphite	Rint = 0.023
φ and ω scans	θmax = 32.5°, θmin = 1.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −8→8
Tmin = 0.963, Tmax = 0.990	k = −12→11
12709 measured reflections	l = −22→23

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) = 0.150	H-atom parameters constrained
S = 1.08	w = 1/[σ2(Fo2) + (0.0741P)2 + 0.3055P] where P = (Fo2 + 2Fc2)/3
4947 reflections	(Δ/σ)max < 0.001
219 parameters	Δρmax = 0.51 e Å−3
0 restraints	Δρmin = −0.46 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	0.50349 (18)	0.28625 (13)	0.24313 (7)	0.0151 (2)
H1	0.4877	0.2768	0.1882	0.018*
N2	0.82364 (19)	0.41676 (14)	0.19955 (7)	0.0176 (2)
H2A	0.8060	0.4015	0.1454	0.021*
H2B	0.9352	0.4662	0.2121	0.021*
C1	0.6777 (2)	0.36374 (15)	0.26413 (8)	0.0146 (2)
C2	0.3509 (2)	0.22205 (16)	0.30452 (8)	0.0162 (2)
H2	0.2353	0.1692	0.2859	0.019*
C3	0.3654 (2)	0.23421 (16)	0.39271 (8)	0.0177 (2)
C4	0.5424 (2)	0.31915 (17)	0.41660 (8)	0.0196 (2)
H4	0.5553	0.3318	0.4761	0.023*
C5	0.6949 (2)	0.38321 (16)	0.35500 (8)	0.0180 (2)
H5	0.8088	0.4391	0.3726	0.022*
C6	0.2014 (2)	0.1628 (2)	0.46135 (9)	0.0252 (3)
H6A	0.0930	0.1115	0.4329	0.038*
H6B	0.1192	0.2508	0.4971	0.038*
H6C	0.2873	0.0806	0.4980	0.038*
O1	0.17251 (16)	0.61810 (13)	0.14298 (6)	0.01924 (19)
H1A	0.1638	0.6119	0.0899	0.029*
O2	0.10528 (18)	0.60967 (13)	0.31694 (7)	0.0243 (2)
O3	0.28454 (18)	0.76459 (15)	0.38862 (6)	0.0270 (2)
O4	0.93341 (17)	0.99542 (13)	0.26211 (7)	0.0237 (2)
O5	1.00019 (18)	1.02494 (14)	0.11971 (8)	0.0274 (2)
O6	0.55546 (18)	0.76372 (13)	−0.07527 (6)	0.0222 (2)
O7	0.26539 (17)	0.63243 (12)	−0.01529 (6)	0.01923 (19)
N3	0.25086 (18)	0.70325 (14)	0.31952 (7)	0.0166 (2)
N4	0.89119 (18)	0.97295 (13)	0.18590 (8)	0.0181 (2)
C7	0.3389 (2)	0.70035 (15)	0.15497 (8)	0.0136 (2)
C8	0.3891 (2)	0.74498 (15)	0.23904 (8)	0.0141 (2)
C9	0.5696 (2)	0.83248 (15)	0.24908 (8)	0.0152 (2)
H9	0.6004	0.8588	0.3049	0.018*
C10	0.7029 (2)	0.87992 (15)	0.17497 (8)	0.0148 (2)
C11	0.6613 (2)	0.84379 (15)	0.09005 (8)	0.0154 (2)
H11	0.7517	0.8788	0.0409	0.018*
C12	0.4831 (2)	0.75506 (14)	0.08054 (7)	0.0136 (2)
C13	0.4365 (2)	0.71642 (15)	−0.01015 (8)	0.0160 (2)

	U11	U22	U33	U12	U13	U23
N1	0.0161 (4)	0.0167 (5)	0.0128 (4)	−0.0032 (4)	−0.0022 (3)	−0.0010 (3)
N2	0.0184 (5)	0.0215 (5)	0.0143 (4)	−0.0086 (4)	−0.0004 (3)	−0.0001 (4)
C1	0.0161 (5)	0.0138 (5)	0.0138 (5)	−0.0018 (4)	−0.0014 (4)	−0.0003 (4)
C2	0.0144 (5)	0.0164 (5)	0.0180 (5)	−0.0032 (4)	−0.0014 (4)	−0.0009 (4)
C3	0.0183 (5)	0.0184 (5)	0.0156 (5)	−0.0022 (4)	0.0005 (4)	0.0009 (4)
C4	0.0238 (6)	0.0234 (6)	0.0123 (5)	−0.0048 (5)	−0.0033 (4)	−0.0007 (4)
C5	0.0200 (5)	0.0205 (6)	0.0149 (5)	−0.0058 (5)	−0.0039 (4)	−0.0005 (4)
C6	0.0225 (6)	0.0321 (7)	0.0206 (6)	−0.0078 (5)	0.0030 (5)	0.0045 (5)
O1	0.0192 (4)	0.0257 (5)	0.0154 (4)	−0.0105 (4)	−0.0028 (3)	−0.0014 (3)
O2	0.0271 (5)	0.0276 (5)	0.0202 (5)	−0.0141 (4)	0.0037 (4)	−0.0011 (4)
O3	0.0285 (5)	0.0422 (6)	0.0122 (4)	−0.0098 (5)	−0.0019 (4)	−0.0062 (4)
O4	0.0210 (4)	0.0230 (5)	0.0296 (5)	−0.0032 (4)	−0.0110 (4)	−0.0068 (4)
O5	0.0235 (5)	0.0269 (5)	0.0337 (6)	−0.0121 (4)	−0.0010 (4)	0.0021 (4)
O6	0.0286 (5)	0.0266 (5)	0.0127 (4)	−0.0099 (4)	0.0000 (3)	−0.0007 (3)
O7	0.0215 (4)	0.0242 (5)	0.0142 (4)	−0.0094 (4)	−0.0031 (3)	−0.0008 (3)
N3	0.0163 (4)	0.0197 (5)	0.0134 (4)	−0.0017 (4)	−0.0011 (3)	−0.0005 (4)
N4	0.0144 (4)	0.0149 (5)	0.0261 (5)	−0.0027 (4)	−0.0048 (4)	−0.0025 (4)
C7	0.0133 (5)	0.0139 (5)	0.0135 (5)	−0.0018 (4)	−0.0015 (4)	−0.0009 (4)
C8	0.0137 (5)	0.0158 (5)	0.0128 (5)	−0.0021 (4)	−0.0006 (4)	−0.0009 (4)
C9	0.0145 (5)	0.0151 (5)	0.0162 (5)	−0.0007 (4)	−0.0038 (4)	−0.0030 (4)
C10	0.0125 (5)	0.0132 (5)	0.0195 (5)	−0.0031 (4)	−0.0028 (4)	−0.0017 (4)
C11	0.0148 (5)	0.0140 (5)	0.0171 (5)	−0.0019 (4)	−0.0007 (4)	−0.0010 (4)
C12	0.0147 (5)	0.0144 (5)	0.0119 (5)	−0.0029 (4)	−0.0014 (4)	−0.0008 (4)
C13	0.0187 (5)	0.0162 (5)	0.0136 (5)	−0.0028 (4)	−0.0028 (4)	−0.0014 (4)

N1—C1	1.3509 (15)	O1—H1A	0.8200
N1—C2	1.3668 (15)	O2—N3	1.2302 (14)
N1—H1	0.8600	O3—N3	1.2348 (14)
N2—C1	1.3355 (15)	O4—N4	1.2404 (15)
N2—H2A	0.8600	O5—N4	1.2291 (15)
N2—H2B	0.8600	O6—C13	1.2331 (15)
C1—C5	1.4181 (16)	O7—C13	1.3067 (15)
C2—C3	1.3652 (17)	N3—C8	1.4546 (15)
C2—H2	0.9300	N4—C10	1.4563 (15)
C3—C4	1.4164 (18)	C7—C8	1.4208 (16)
C3—C6	1.5019 (18)	C7—C12	1.4372 (16)
C4—C5	1.3681 (18)	C8—C9	1.3861 (16)
C4—H4	0.9300	C9—C10	1.3794 (17)
C5—H5	0.9300	C9—H9	0.9300
C6—H6A	0.9600	C10—C11	1.3956 (17)
C6—H6B	0.9600	C11—C12	1.3793 (16)
C6—H6C	0.9600	C11—H11	0.9300
O1—C7	1.2957 (14)	C12—C13	1.4943 (16)
C1—N1—C2	123.48 (10)	O2—N3—O3	122.24 (11)
C1—N1—H1	118.2	O2—N3—C8	119.70 (10)
C2—N1—H1	118.3	O3—N3—C8	118.06 (11)
C1—N2—H2A	120.0	O5—N4—O4	123.31 (11)
C1—N2—H2B	120.0	O5—N4—C10	118.76 (11)
H2A—N2—H2B	120.0	O4—N4—C10	117.93 (11)
N2—C1—N1	119.16 (11)	O1—C7—C8	123.94 (11)
N2—C1—C5	123.65 (11)	O1—C7—C12	120.07 (10)
N1—C1—C5	117.18 (11)	C8—C7—C12	115.98 (10)
C3—C2—N1	121.14 (11)	C9—C8—C7	122.15 (11)
C3—C2—H2	119.4	C9—C8—N3	116.22 (10)
N1—C2—H2	119.4	C7—C8—N3	121.63 (10)
C2—C3—C4	116.59 (11)	C10—C9—C8	118.97 (11)
C2—C3—C6	122.06 (12)	C10—C9—H9	120.5
C4—C3—C6	121.34 (12)	C8—C9—H9	120.5
C5—C4—C3	122.13 (11)	C9—C10—C11	122.23 (11)
C5—C4—H4	118.9	C9—C10—N4	118.70 (11)
C3—C4—H4	118.9	C11—C10—N4	119.06 (11)
C4—C5—C1	119.43 (11)	C12—C11—C10	118.54 (11)
C4—C5—H5	120.3	C12—C11—H11	120.7
C1—C5—H5	120.3	C10—C11—H11	120.7
C3—C6—H6A	109.5	C11—C12—C7	122.12 (10)
C3—C6—H6B	109.5	C11—C12—C13	118.93 (10)
H6A—C6—H6B	109.5	C7—C12—C13	118.95 (10)
C3—C6—H6C	109.5	O6—C13—O7	123.31 (11)
H6A—C6—H6C	109.5	O6—C13—C12	120.35 (11)
H6B—C6—H6C	109.5	O7—C13—C12	116.34 (10)
C7—O1—H1A	109.5
C2—N1—C1—N2	177.44 (11)	N3—C8—C9—C10	−178.15 (10)
C2—N1—C1—C5	−2.27 (17)	C8—C9—C10—C11	0.44 (18)
C1—N1—C2—C3	0.56 (19)	C8—C9—C10—N4	179.53 (11)
N1—C2—C3—C4	1.24 (18)	O5—N4—C10—C9	−175.21 (11)
N1—C2—C3—C6	−179.26 (12)	O4—N4—C10—C9	4.88 (17)
C2—C3—C4—C5	−1.29 (19)	O5—N4—C10—C11	3.91 (17)
C6—C3—C4—C5	179.21 (13)	O4—N4—C10—C11	−176.00 (11)
C3—C4—C5—C1	−0.4 (2)	C9—C10—C11—C12	−1.15 (18)
N2—C1—C5—C4	−177.56 (12)	N4—C10—C11—C12	179.76 (11)
N1—C1—C5—C4	2.14 (18)	C10—C11—C12—C7	0.51 (18)
O1—C7—C8—C9	179.70 (12)	C10—C11—C12—C13	179.74 (11)
C12—C7—C8—C9	−1.52 (17)	O1—C7—C12—C11	179.60 (11)
O1—C7—C8—N3	−1.24 (19)	C8—C7—C12—C11	0.77 (17)
C12—C7—C8—N3	177.54 (10)	O1—C7—C12—C13	0.37 (17)
O2—N3—C8—C9	−171.71 (11)	C8—C7—C12—C13	−178.46 (10)
O3—N3—C8—C9	8.51 (17)	C11—C12—C13—O6	−0.21 (18)
O2—N3—C8—C7	9.17 (18)	C7—C12—C13—O6	179.05 (11)
O3—N3—C8—C7	−170.60 (11)	C11—C12—C13—O7	−179.85 (11)
C7—C8—C9—C10	0.96 (18)	C7—C12—C13—O7	−0.59 (16)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O7	0.82	1.66	2.4200 (13)	152
N1—H1···O6i	0.86	1.82	2.6768 (14)	174
N2—H2A···O7i	0.86	2.11	2.9668 (15)	176
N2—H2B···O1ii	0.86	2.16	2.8468 (15)	137
N2—H2B···O2ii	0.86	2.40	3.1723 (16)	149
C2—H2···O4iii	0.93	2.49	3.4073 (16)	169
C4—H4···O3iv	0.93	2.39	3.2371 (16)	151
C5—H5···O2ii	0.93	2.44	3.2328 (17)	143

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O7	0.82	1.66	2.4200 (13)	152
N1—H1⋯O6i	0.86	1.82	2.6768 (14)	174
N2—H2A⋯O7i	0.86	2.11	2.9668 (15)	176
N2—H2B⋯O1ii	0.86	2.16	2.8468 (15)	137
N2—H2B⋯O2ii	0.86	2.40	3.1723 (16)	149
C2—H2⋯O4iii	0.93	2.49	3.4073 (16)	169
C4—H4⋯O3iv	0.93	2.39	3.2371 (16)	151
C5—H5⋯O2ii	0.93	2.44	3.2328 (17)	143

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