2,3-Diamino-pyridinium 4-nitro-benzoate.

In the title salt, C(5)H(8)N(3) (+)·C(7)H(4)NO(4) (-), the pyridine N atom of the 2,3-diamino-pyridine mol-ecule is protonated. The protonated N atom and one of the two 2-amino groups are hydrogen bonded to the 4-nitro-benzoate anion through a pair of N-H⋯O hydrogen bonds, forming an R(2) (2)(8) ring motif. The carboxyl-ate mean plane of the 4-nitro-benzoate anion is twisted by 3.77 (5)° from the attached ring and the nitro group is similarly twisted by 2.28 (10)°. In the crystal, the mol-ecules are linked by N-H⋯O and C-H⋯O inter-actions into sheets parallel to (100).

Related literature

For substituted pyridines, see: Pozharski et al. (1997 ▶); Katritzky et al. (1996 ▶); Jeffrey & Saenger (1991 ▶); Jeffrey (1997 ▶); Scheiner (1997 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C5H8N3 +·C7H4NO4 −

M = 276.26

Monoclinic,

a = 8.0827 (2) Å

b = 6.7365 (1) Å

c = 11.4489 (3) Å

β = 101.967 (1)°

V = 609.83 (2) Å3

Z = 2

Mo Kα radiation

μ = 0.12 mm−1

T = 100 K

0.25 × 0.17 × 0.10 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.972, T max = 0.988

11659 measured reflections

2808 independent reflections

2155 reflections with I > 2σ(I)

R int = 0.045

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.116

S = 1.04

2808 reflections

229 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.43 e Å−3

Δρmin = −0.30 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAIn class="Chemical">NT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTLsoftware used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680902100X/tk2462sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680902100X/tk2462Isup2.hkl

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

C5H8N3+·C7H4NO4−	F(000) = 288
Mr = 276.26	Dx = 1.504 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 2526 reflections
a = 8.0827 (2) Å	θ = 2.8–31.7°
b = 6.7365 (1) Å	µ = 0.12 mm−1
c = 11.4489 (3) Å	T = 100 K
β = 101.967 (1)°	Block, brown
V = 609.83 (2) Å3	0.25 × 0.17 × 0.10 mm
Z = 2

Bruker SMART APEXII CCD area-detector diffractometer	2808 independent reflections
Radiation source: fine-focus sealed tube	2155 reflections with I > 2σ(I)
graphite	Rint = 0.045
φ and ω scans	θmax = 34.9°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −12→12
Tmin = 0.972, Tmax = 0.988	k = −10→10
11659 measured reflections	l = −17→18

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0571P)2 + 0.026P] where P = (Fo2 + 2Fc2)/3
2808 reflections	(Δ/σ)max < 0.001
229 parameters	Δρmax = 0.43 e Å−3
1 restraint	Δρmin = −0.30 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 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 > 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
O1	−0.0506 (2)	−0.7085 (2)	0.85306 (17)	0.0306 (4)
O2	−0.04637 (19)	−0.7831 (2)	0.66897 (16)	0.0269 (4)
O3	0.35100 (19)	0.1109 (2)	0.60686 (14)	0.0223 (3)
O4	0.35695 (19)	0.1713 (2)	0.79972 (14)	0.0210 (3)
N4	−0.0141 (2)	−0.6717 (3)	0.75606 (18)	0.0213 (4)
C1	0.1816 (2)	−0.1740 (3)	0.82546 (19)	0.0178 (4)
C2	0.1021 (2)	−0.3532 (3)	0.8391 (2)	0.0183 (4)
C3	0.0723 (2)	−0.4824 (3)	0.7432 (2)	0.0178 (4)
C4	0.1172 (2)	−0.4421 (3)	0.6355 (2)	0.0196 (4)
C5	0.1973 (2)	−0.2624 (3)	0.6234 (2)	0.0180 (4)
C6	0.2309 (2)	−0.1287 (3)	0.71862 (19)	0.0162 (4)
C7	0.3201 (2)	0.0666 (3)	0.70675 (18)	0.0169 (4)
N1	0.5459 (2)	0.4983 (2)	0.80784 (16)	0.0179 (3)
N2	0.5600 (2)	0.4619 (3)	0.60992 (18)	0.0213 (4)
N3	0.7324 (2)	0.8308 (3)	0.62077 (18)	0.0212 (4)
C8	0.5959 (2)	0.5681 (3)	0.71027 (19)	0.0166 (4)
C9	0.6873 (2)	0.7522 (3)	0.72040 (19)	0.0168 (4)
C10	0.7217 (2)	0.8451 (3)	0.8301 (2)	0.0197 (4)
C11	0.6717 (2)	0.7629 (3)	0.9295 (2)	0.0213 (4)
C12	0.5820 (2)	0.5895 (3)	0.91644 (19)	0.0199 (4)
H1A	0.201 (3)	−0.084 (4)	0.887 (2)	0.020 (6)*
H2A	0.068 (3)	−0.384 (4)	0.914 (2)	0.020 (6)*
H4A	0.089 (3)	−0.535 (5)	0.569 (2)	0.033 (7)*
H5A	0.232 (3)	−0.233 (4)	0.547 (2)	0.021 (6)*
H10A	0.782 (3)	0.972 (5)	0.834 (2)	0.029 (7)*
H11A	0.711 (3)	0.821 (4)	1.010 (2)	0.027 (7)*
H12A	0.540 (3)	0.527 (4)	0.978 (2)	0.021 (6)*
H1N1	0.478 (3)	0.375 (5)	0.793 (3)	0.038 (8)*
H1N2	0.497 (4)	0.353 (5)	0.608 (3)	0.038 (8)*
H2N2	0.579 (3)	0.496 (4)	0.542 (2)	0.017 (6)*
H1N3	0.735 (3)	0.759 (5)	0.560 (2)	0.025 (7)*
H2N3	0.806 (4)	0.917 (5)	0.635 (3)	0.037 (8)*

	U11	U22	U33	U12	U13	U23
O1	0.0374 (9)	0.0213 (8)	0.0368 (10)	−0.0086 (6)	0.0162 (8)	0.0038 (7)
O2	0.0274 (7)	0.0170 (7)	0.0348 (10)	−0.0058 (6)	0.0027 (7)	−0.0027 (7)
O3	0.0293 (7)	0.0175 (6)	0.0226 (8)	−0.0035 (5)	0.0109 (6)	0.0002 (6)
O4	0.0281 (7)	0.0164 (6)	0.0199 (8)	−0.0056 (5)	0.0083 (6)	−0.0023 (6)
N4	0.0165 (7)	0.0146 (7)	0.0320 (10)	−0.0015 (6)	0.0030 (7)	0.0026 (8)
C1	0.0213 (8)	0.0139 (8)	0.0187 (10)	−0.0012 (7)	0.0053 (7)	−0.0008 (8)
C2	0.0185 (8)	0.0155 (8)	0.0215 (10)	−0.0007 (6)	0.0054 (7)	0.0030 (8)
C3	0.0166 (8)	0.0116 (7)	0.0255 (11)	−0.0015 (6)	0.0053 (7)	0.0010 (7)
C4	0.0216 (8)	0.0132 (8)	0.0249 (11)	−0.0008 (6)	0.0067 (8)	−0.0015 (8)
C5	0.0205 (8)	0.0146 (8)	0.0196 (10)	−0.0010 (7)	0.0056 (7)	−0.0018 (8)
C6	0.0176 (8)	0.0111 (8)	0.0201 (10)	0.0012 (6)	0.0043 (7)	0.0032 (7)
C7	0.0180 (8)	0.0128 (8)	0.0208 (10)	0.0003 (6)	0.0058 (7)	0.0008 (8)
N1	0.0188 (7)	0.0161 (7)	0.0191 (9)	−0.0021 (6)	0.0048 (6)	0.0004 (7)
N2	0.0300 (9)	0.0176 (8)	0.0182 (9)	−0.0056 (6)	0.0094 (7)	−0.0014 (7)
N3	0.0273 (8)	0.0178 (7)	0.0201 (9)	−0.0061 (7)	0.0089 (7)	−0.0003 (8)
C8	0.0158 (7)	0.0136 (8)	0.0208 (10)	−0.0012 (6)	0.0046 (7)	0.0007 (8)
C9	0.0157 (7)	0.0161 (8)	0.0189 (9)	0.0003 (6)	0.0042 (6)	0.0023 (8)
C10	0.0199 (8)	0.0168 (8)	0.0228 (11)	−0.0021 (7)	0.0055 (7)	−0.0018 (8)
C11	0.0210 (8)	0.0225 (9)	0.0206 (11)	−0.0001 (7)	0.0051 (7)	−0.0028 (8)
C12	0.0201 (8)	0.0223 (9)	0.0176 (10)	−0.0010 (7)	0.0045 (7)	0.0004 (8)

O1—N4	1.232 (2)	N1—C8	1.349 (3)
O2—N4	1.232 (2)	N1—C12	1.363 (3)
O3—C7	1.256 (2)	N1—H1N1	0.99 (3)
O4—C7	1.260 (2)	N2—C8	1.333 (3)
N4—C3	1.476 (2)	N2—H1N2	0.89 (3)
C1—C2	1.391 (3)	N2—H2N2	0.85 (3)
C1—C6	1.397 (3)	N3—C9	1.373 (3)
C1—H1A	0.92 (3)	N3—H1N3	0.85 (3)
C2—C3	1.383 (3)	N3—H2N3	0.82 (3)
C2—H2A	0.98 (3)	C8—C9	1.435 (3)
C3—C4	1.382 (3)	C9—C10	1.379 (3)
C4—C5	1.394 (3)	C10—C11	1.399 (3)
C4—H4A	0.98 (3)	C10—H10A	0.98 (3)
C5—C6	1.396 (3)	C11—C12	1.367 (3)
C5—H5A	0.99 (3)	C11—H11A	0.99 (3)
C6—C7	1.520 (3)	C12—H12A	0.94 (3)
O2—N4—O1	123.84 (17)	C8—N1—C12	123.62 (17)
O2—N4—C3	118.06 (18)	C8—N1—H1N1	113.8 (17)
O1—N4—C3	118.10 (18)	C12—N1—H1N1	122.6 (17)
C2—C1—C6	120.69 (19)	C8—N2—H1N2	119.0 (19)
C2—C1—H1A	119.4 (17)	C8—N2—H2N2	126.1 (17)
C6—C1—H1A	119.9 (17)	H1N2—N2—H2N2	114 (2)
C3—C2—C1	117.7 (2)	C9—N3—H1N3	121 (2)
C3—C2—H2A	122.2 (16)	C9—N3—H2N3	114 (2)
C1—C2—H2A	120.1 (16)	H1N3—N3—H2N3	115 (3)
C4—C3—C2	123.38 (18)	N2—C8—N1	118.49 (17)
C4—C3—N4	118.44 (18)	N2—C8—C9	123.34 (19)
C2—C3—N4	118.18 (18)	N1—C8—C9	118.16 (18)
C3—C4—C5	118.21 (19)	N3—C9—C10	122.90 (18)
C3—C4—H4A	120.7 (17)	N3—C9—C8	119.10 (19)
C5—C4—H4A	121.1 (17)	C10—C9—C8	117.97 (18)
C4—C5—C6	120.13 (19)	C9—C10—C11	121.58 (18)
C4—C5—H5A	118.6 (16)	C9—C10—H10A	116.5 (16)
C6—C5—H5A	121.2 (16)	C11—C10—H10A	121.9 (16)
C5—C6—C1	119.87 (17)	C12—C11—C10	119.1 (2)
C5—C6—C7	120.51 (17)	C12—C11—H11A	120.1 (16)
C1—C6—C7	119.62 (17)	C10—C11—H11A	120.5 (16)
O3—C7—O4	125.37 (18)	N1—C12—C11	119.6 (2)
O3—C7—C6	118.35 (18)	N1—C12—H12A	115.8 (16)
O4—C7—C6	116.28 (17)	C11—C12—H12A	124.6 (16)
C6—C1—C2—C3	−0.8 (3)	C1—C6—C7—O3	−174.40 (17)
C1—C2—C3—C4	−0.1 (3)	C5—C6—C7—O4	−174.72 (17)
C1—C2—C3—N4	−179.16 (16)	C1—C6—C7—O4	5.6 (2)
O2—N4—C3—C4	−1.9 (3)	C12—N1—C8—N2	177.00 (18)
O1—N4—C3—C4	178.55 (18)	C12—N1—C8—C9	−2.2 (3)
O2—N4—C3—C2	177.21 (18)	N2—C8—C9—N3	3.9 (3)
O1—N4—C3—C2	−2.3 (3)	N1—C8—C9—N3	−176.90 (17)
C2—C3—C4—C5	0.4 (3)	N2—C8—C9—C10	−177.88 (18)
N4—C3—C4—C5	179.44 (17)	N1—C8—C9—C10	1.3 (2)
C3—C4—C5—C6	0.2 (3)	N3—C9—C10—C11	178.94 (19)
C4—C5—C6—C1	−1.0 (3)	C8—C9—C10—C11	0.8 (3)
C4—C5—C6—C7	179.32 (16)	C9—C10—C11—C12	−2.1 (3)
C2—C1—C6—C5	1.3 (3)	C8—N1—C12—C11	0.9 (3)
C2—C1—C6—C7	−179.02 (17)	C10—C11—C12—N1	1.3 (3)
C5—C6—C7—O3	5.3 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O4	0.99 (3)	1.70 (3)	2.671 (2)	167 (3)
N2—H1N2···O3	0.89 (3)	2.01 (3)	2.901 (2)	178 (5)
N2—H2N2···O3i	0.86 (2)	2.06 (2)	2.903 (2)	171 (2)
N3—H1N3···O3i	0.85 (3)	2.14 (3)	2.951 (3)	159 (2)
N3—H2N3···O2ii	0.82 (3)	2.34 (3)	3.140 (2)	165 (3)
C10—H10A···O1ii	0.98 (3)	2.53 (3)	3.507 (2)	176.9 (16)
C11—H11A···O4iii	0.99 (2)	2.56 (2)	3.216 (3)	123.5 (19)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O4	0.99 (3)	1.70 (3)	2.671 (2)	167 (3)
N2—H1N2⋯O3	0.89 (3)	2.01 (3)	2.901 (2)	178 (5)
N2—H2N2⋯O3i	0.86 (2)	2.06 (2)	2.903 (2)	171 (2)
N3—H1N3⋯O3i	0.85 (3)	2.14 (3)	2.951 (3)	159 (2)
N3—H2N3⋯O2ii	0.82 (3)	2.34 (3)	3.140 (2)	165 (3)
C10—H10A⋯O1ii	0.98 (3)	2.53 (3)	3.507 (2)	177 (2)
C11—H11A⋯O4iii	0.99 (2)	2.56 (2)	3.216 (3)	124 (2)

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