2,3-Diamino-pyridinium 6-carb-oxy-pyridine-2-carboxyl-ate.

The asymmetric unit of the title proton-transfer compound, C(5)H(8)N(3) (+)·C(7)H(4)NO(4) (-), consists of one mono-deprotonated pyridine-2,6-dicarb-oxy-lic acid as anion and one protonated 2,3-diamino-pyridine as cation. The crystal packing shows extensive O-H⋯O, N-H⋯O and N-H⋯N hydrogen bonds. Thre are also several π-π inter-actions between the anions and also between the cations [centriod-centroid distances = 3.6634 (7), 3.7269 (7), 3.6705 (7) and 3.4164 (7) Å].

Related literature

For background to proton-transfer compounds, see: Aghabozorg et al. (2008b ▶). For related structures, see: Aghabozorg et al. (2008a ▶, 2011a ▶,b ▶); Sharif et al. (2010 ▶).

Experimental

Crystal data

C5H8N3 +·C7H4NO4 −

M = 276.26

Triclinic,

a = 6.9138 (1) Å

b = 8.3364 (2) Å

c = 11.2358 (2) Å

α = 81.448 (1)°

β = 73.831 (1)°

γ = 82.486 (1)°

V = 612.33 (2) Å3

Z = 2

Mo Kα radiation

μ = 0.12 mm−1

T = 296 K

0.24 × 0.20 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.706, T max = 0.746

34839 measured reflections

2654 independent reflections

2348 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.107

S = 1.07

2654 reflections

194 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.30 e Å−3

Δρmin = −0.17 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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811047647/bt5705sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811047647/bt5705Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811047647/bt5705Isup3.cml

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

C5H8N3+·C7H4NO4−	Z = 2
Mr = 276.26	F(000) = 288
Triclinic, P1	Dx = 1.498 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9138 (1) Å	Cell parameters from 9842 reflections
b = 8.3364 (2) Å	θ = 2.9–30.0°
c = 11.2358 (2) Å	µ = 0.12 mm−1
α = 81.448 (1)°	T = 296 K
β = 73.831 (1)°	Irregular, colorless
γ = 82.486 (1)°	0.24 × 0.20 × 0.12 mm
V = 612.33 (2) Å3

Bruker APEXII CCD diffractometer	2654 independent reflections
Radiation source: fine-focus sealed tube	2348 reflections with I > 2σ(I)
graphite	Rint = 0.025
φ and ω scans	θmax = 27.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −8→8
Tmin = 0.706, Tmax = 0.746	k = −10→10
34839 measured reflections	l = −14→14

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)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.107	w = 1/[σ2(Fo2) + (0.060P)2 + 0.1194P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max < 0.001
2654 reflections	Δρmax = 0.30 e Å−3
194 parameters	Δρmin = −0.17 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: 0.00070 (17)

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
O3	0.64901 (16)	0.46889 (11)	0.60916 (9)	0.0508 (3)
O2	0.91253 (17)	−0.01029 (10)	0.21751 (8)	0.0479 (3)
O1	0.91229 (15)	−0.25266 (10)	0.32864 (8)	0.0419 (2)
O4	0.83898 (16)	0.45238 (11)	0.41533 (8)	0.0480 (3)
C8	0.72493 (16)	0.42375 (14)	0.08478 (10)	0.0310 (2)
N4	0.85753 (15)	0.42597 (12)	−0.13478 (9)	0.0352 (2)
H	0.9115	0.3742	−0.1986	0.042*
N1	0.79718 (13)	0.13922 (10)	0.42873 (8)	0.0271 (2)
C9	0.81096 (17)	0.33895 (14)	−0.02186 (10)	0.0314 (2)
C10	0.8247 (2)	0.59072 (16)	−0.15453 (11)	0.0400 (3)
H10	0.8605	0.6451	−0.2349	0.048*
N3	0.84405 (18)	0.17690 (13)	−0.01308 (10)	0.0451 (3)
H3A	0.8947	0.1294	−0.0793	0.054*
H3B	0.8148	0.1199	0.0588	0.054*
C11	0.7393 (2)	0.67446 (15)	−0.05574 (12)	0.0417 (3)
H11	0.7130	0.7872	−0.0675	0.050*
C12	0.69064 (19)	0.58993 (15)	0.06456 (11)	0.0379 (3)
H12	0.6336	0.6481	0.1324	0.045*
C7	0.73268 (17)	0.39063 (13)	0.52423 (10)	0.0319 (3)
C6	0.72505 (16)	0.20977 (13)	0.53341 (10)	0.0276 (2)
C2	0.79375 (15)	−0.02216 (12)	0.43816 (9)	0.0262 (2)
C1	0.87808 (17)	−0.10003 (13)	0.31804 (10)	0.0299 (2)
C3	0.71865 (17)	−0.11635 (13)	0.55079 (10)	0.0307 (2)
H3	0.7201	−0.2286	0.5541	0.037*
C4	0.64189 (18)	−0.04065 (14)	0.65777 (11)	0.0350 (3)
H4	0.5889	−0.1007	0.7340	0.042*
C5	0.64532 (18)	0.12568 (14)	0.64934 (10)	0.0332 (3)
H5	0.5953	0.1802	0.7197	0.040*
N2	0.67215 (18)	0.33369 (15)	0.20004 (10)	0.0402 (3)
H2A	0.755 (3)	0.253 (2)	0.2184 (16)	0.057 (5)*
H2B	0.625 (3)	0.397 (2)	0.2583 (17)	0.057 (5)*
H1	0.840 (3)	0.560 (2)	0.4101 (17)	0.067 (5)*

	U11	U22	U33	U12	U13	U23
O3	0.0713 (7)	0.0303 (5)	0.0412 (5)	−0.0035 (4)	0.0066 (4)	−0.0163 (4)
O2	0.0818 (7)	0.0281 (4)	0.0250 (4)	0.0055 (4)	−0.0045 (4)	−0.0033 (3)
O1	0.0636 (6)	0.0200 (4)	0.0345 (5)	−0.0030 (4)	0.0009 (4)	−0.0068 (3)
O4	0.0736 (7)	0.0227 (4)	0.0374 (5)	−0.0120 (4)	0.0082 (4)	−0.0080 (3)
C8	0.0314 (5)	0.0338 (6)	0.0267 (5)	−0.0006 (4)	−0.0060 (4)	−0.0059 (4)
N4	0.0408 (5)	0.0369 (5)	0.0247 (5)	0.0027 (4)	−0.0051 (4)	−0.0064 (4)
N1	0.0332 (5)	0.0206 (4)	0.0257 (4)	−0.0017 (3)	−0.0049 (3)	−0.0040 (3)
C9	0.0327 (5)	0.0319 (6)	0.0285 (5)	0.0003 (4)	−0.0071 (4)	−0.0054 (4)
C10	0.0457 (7)	0.0385 (6)	0.0311 (6)	0.0024 (5)	−0.0092 (5)	0.0028 (5)
N3	0.0653 (7)	0.0318 (5)	0.0317 (5)	0.0031 (5)	−0.0038 (5)	−0.0069 (4)
C11	0.0500 (7)	0.0299 (6)	0.0420 (7)	0.0053 (5)	−0.0121 (5)	−0.0025 (5)
C12	0.0430 (6)	0.0356 (6)	0.0331 (6)	0.0044 (5)	−0.0069 (5)	−0.0110 (5)
C7	0.0378 (6)	0.0252 (5)	0.0312 (5)	−0.0023 (4)	−0.0046 (4)	−0.0076 (4)
C6	0.0303 (5)	0.0233 (5)	0.0283 (5)	−0.0015 (4)	−0.0050 (4)	−0.0058 (4)
C2	0.0303 (5)	0.0211 (5)	0.0267 (5)	−0.0005 (4)	−0.0072 (4)	−0.0035 (4)
C1	0.0384 (6)	0.0220 (5)	0.0280 (5)	−0.0016 (4)	−0.0064 (4)	−0.0046 (4)
C3	0.0384 (6)	0.0209 (5)	0.0309 (5)	−0.0033 (4)	−0.0073 (4)	−0.0008 (4)
C4	0.0421 (6)	0.0314 (6)	0.0269 (5)	−0.0057 (5)	−0.0030 (4)	0.0011 (4)
C5	0.0395 (6)	0.0313 (6)	0.0257 (5)	−0.0022 (4)	−0.0017 (4)	−0.0077 (4)
N2	0.0489 (6)	0.0394 (6)	0.0263 (5)	0.0006 (5)	−0.0022 (4)	−0.0043 (4)

O3—C7	1.2041 (14)	N3—H3A	0.8600
O2—C1	1.2401 (14)	N3—H3B	0.8600
O1—C1	1.2574 (13)	C11—C12	1.4008 (18)
O4—C7	1.3088 (14)	C11—H11	0.9300
O4—H1	0.89 (2)	C12—H12	0.9300
C8—C12	1.3702 (17)	C7—C6	1.5028 (15)
C8—N2	1.3760 (15)	C6—C5	1.3862 (15)
C8—C9	1.4262 (15)	C2—C3	1.3903 (14)
N4—C9	1.3414 (14)	C2—C1	1.5185 (14)
N4—C10	1.3575 (16)	C3—C4	1.3811 (16)
N4—H	0.8600	C3—H3	0.9300
N1—C6	1.3343 (14)	C4—C5	1.3786 (16)
N1—C2	1.3365 (13)	C4—H4	0.9300
C9—N3	1.3338 (15)	C5—H5	0.9300
C10—C11	1.3512 (18)	N2—H2A	0.868 (19)
C10—H10	0.9300	N2—H2B	0.87 (2)
C7—O4—H1	112.4 (12)	O3—C7—C6	122.78 (10)
C12—C8—N2	124.24 (10)	O4—C7—C6	112.99 (9)
C12—C8—C9	117.42 (10)	N1—C6—C5	123.76 (10)
N2—C8—C9	118.25 (10)	N1—C6—C7	117.67 (9)
C9—N4—C10	124.00 (10)	C5—C6—C7	118.57 (10)
C9—N4—H	118.0	N1—C2—C3	122.83 (9)
C10—N4—H	118.0	N1—C2—C1	116.38 (9)
C6—N1—C2	117.28 (9)	C3—C2—C1	120.79 (9)
N3—C9—N4	119.21 (10)	O2—C1—O1	124.63 (10)
N3—C9—C8	122.31 (10)	O2—C1—C2	118.57 (9)
N4—C9—C8	118.47 (10)	O1—C1—C2	116.78 (9)
C11—C10—N4	119.02 (11)	C4—C3—C2	118.99 (10)
C11—C10—H10	120.5	C4—C3—H3	120.5
N4—C10—H10	120.5	C2—C3—H3	120.5
C9—N3—H3A	120.0	C5—C4—C3	118.73 (10)
C9—N3—H3B	120.0	C5—C4—H4	120.6
H3A—N3—H3B	120.0	C3—C4—H4	120.6
C10—C11—C12	119.37 (11)	C4—C5—C6	118.40 (10)
C10—C11—H11	120.3	C4—C5—H5	120.8
C12—C11—H11	120.3	C6—C5—H5	120.8
C8—C12—C11	121.69 (11)	C8—N2—H2A	118.7 (12)
C8—C12—H12	119.2	C8—N2—H2B	110.6 (12)
C11—C12—H12	119.2	H2A—N2—H2B	113.8 (16)
O3—C7—O4	124.23 (10)
C10—N4—C9—N3	178.04 (12)	O3—C7—C6—C5	−10.12 (18)
C10—N4—C9—C8	−1.15 (17)	O4—C7—C6—C5	169.81 (11)
C12—C8—C9—N3	−177.65 (11)	C6—N1—C2—C3	0.21 (16)
N2—C8—C9—N3	−0.97 (17)	C6—N1—C2—C1	−179.54 (9)
C12—C8—C9—N4	1.52 (16)	N1—C2—C1—O2	−11.91 (15)
N2—C8—C9—N4	178.20 (10)	C3—C2—C1—O2	168.34 (11)
C9—N4—C10—C11	−0.31 (19)	N1—C2—C1—O1	166.52 (10)
N4—C10—C11—C12	1.3 (2)	C3—C2—C1—O1	−13.22 (16)
N2—C8—C12—C11	−176.99 (12)	N1—C2—C3—C4	0.76 (17)
C9—C8—C12—C11	−0.54 (18)	C1—C2—C3—C4	−179.51 (10)
C10—C11—C12—C8	−0.9 (2)	C2—C3—C4—C5	−0.98 (17)
C2—N1—C6—C5	−0.96 (16)	C3—C4—C5—C6	0.29 (18)
C2—N1—C6—C7	178.62 (9)	N1—C6—C5—C4	0.71 (18)
O3—C7—C6—N1	170.28 (12)	C7—C6—C5—C4	−178.86 (10)
O4—C7—C6—N1	−9.79 (15)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H···O1i	0.86	1.94	2.7872 (12)	167.
N2—H2B···O3ii	0.87 (2)	2.329 (19)	3.1108 (14)	150.0 (15)
N3—H3A···O2i	0.86	2.03	2.8674 (14)	163.
N3—H3B···O2	0.86	2.17	2.9427 (14)	149.
O4—H1···O1iii	0.89 (2)	1.75 (2)	2.5673 (12)	151.9 (18)
N2—H2A···O2	0.868 (19)	2.32 (2)	3.1290 (15)	156.0 (16)
N2—H2A···N1	0.868 (19)	2.491 (18)	3.0999 (14)	127.8 (15)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H⋯O1i	0.86	1.94	2.7872 (12)	167
N2—H2B⋯O3ii	0.87 (2)	2.329 (19)	3.1108 (14)	150.0 (15)
N3—H3A⋯O2i	0.86	2.03	2.8674 (14)	163
N3—H3B⋯O2	0.86	2.17	2.9427 (14)	149
O4—H1⋯O1iii	0.89 (2)	1.75 (2)	2.5673 (12)	151.9 (18)
N2—H2A⋯O2	0.868 (19)	2.32 (2)	3.1290 (15)	156.0 (16)
N2—H2A⋯N1	0.868 (19)	2.491 (18)	3.0999 (14)	127.8 (15)

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