2,6-Diamino-pyridinium 2-carb-oxy-benzoate.

In the crystal of the title mol-ecular salt, C(5)H(8)N(3) (+)·C(8)H(5)O(4) (-), the diamino-pyridine cation and the phthalate anion are linked by a pair of N-H⋯O hydrogen bonds. Within the phthalate anion, an almost symmetrical O-H⋯O hydrogen bond is observed. The ion pairs are linked by further N-H⋯O hydrogen bonds, generating a two-dimensional network lying parallel to (10).

Related literature

For background to 2,6-diamino­pyridines, see: Abu Zuhri & Cox (1989 ▶); Inuzuka & Fujimoto (1990 ▶); El-Mossalamy (2001 ▶). For background and the biological activity of phthalic acid, see: Brike et al. (2002 ▶); Yamamoto et al. (1990 ▶). For related structures: see: Büyükgüngör & Odabąsoğlu (2006 ▶); Al-Dajani et al. (2009 ▶); Raissi Shabari et al. (2010 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C5H8N3 +·C8H5O4 −

M = 275.26

Monoclinic,

a = 32.332 (11) Å

b = 3.7246 (14) Å

c = 24.184 (8) Å

β = 123.036 (6)°

V = 2441.5 (15) Å3

Z = 8

Mo Kα radiation

μ = 0.11 mm−1

T = 100 K

0.47 × 0.10 × 0.03 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.948, T max = 0.996

5492 measured reflections

2757 independent reflections

1869 reflections with I > 2σ(I)

R int = 0.041

Refinement

R[F 2 > 2σ(F 2)] = 0.053

wR(F 2) = 0.197

S = 1.06

2757 reflections

181 parameters

H-atom parameters constrained

Δρmax = 0.41 e Å−3

Δρmin = −0.40 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/S1600536810032903/hb5557sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810032903/hb5557Isup2.hkl

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

C5H8N3+·C8H5O4−	F(000) = 1152
Mr = 275.26	Dx = 1.498 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 975 reflections
a = 32.332 (11) Å	θ = 3.8–28.1°
b = 3.7246 (14) Å	µ = 0.11 mm−1
c = 24.184 (8) Å	T = 100 K
β = 123.036 (6)°	Plate, brown
V = 2441.5 (15) Å3	0.47 × 0.10 × 0.03 mm
Z = 8

Bruker APEXII DUO CCD area-detector diffractometer	2757 independent reflections
Radiation source: fine-focus sealed tube	1869 reflections with I > 2σ(I)
graphite	Rint = 0.041
φ and ω scans	θmax = 27.5°, θmin = 3.4°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −36→42
Tmin = 0.948, Tmax = 0.996	k = −4→4
5492 measured reflections	l = −31→27

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.197	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.1138P)2] where P = (Fo2 + 2Fc2)/3
2757 reflections	(Δ/σ)max < 0.001
181 parameters	Δρmax = 0.41 e Å−3
0 restraints	Δρmin = −0.40 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 esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.09892 (7)	0.9810 (6)	0.16036 (9)	0.0153 (5)
H1A	0.1109	0.8974	0.1388	0.018*
N2	0.02334 (7)	0.8089 (7)	0.07262 (10)	0.0195 (5)
H2A	0.0381	0.7329	0.0542	0.023*
H2B	−0.0082	0.7882	0.0526	0.023*
N3	0.17839 (7)	1.1355 (7)	0.24299 (10)	0.0210 (5)
H3A	0.1883	1.0487	0.2192	0.025*
H3B	0.1993	1.2268	0.2810	0.025*
C1	0.04920 (8)	0.9585 (7)	0.13210 (11)	0.0158 (5)
C2	0.02953 (9)	1.0896 (8)	0.16702 (11)	0.0179 (6)
H2C	−0.0042	1.0754	0.1494	0.021*
C3	0.06092 (9)	1.2402 (8)	0.22794 (12)	0.0191 (6)
H3C	0.0478	1.3309	0.2510	0.023*
C4	0.11140 (9)	1.2624 (8)	0.25640 (11)	0.0169 (5)
H4A	0.1319	1.3636	0.2980	0.020*
C5	0.13083 (8)	1.1287 (7)	0.22106 (11)	0.0153 (5)
O1	0.26121 (6)	−0.0595 (6)	0.12827 (8)	0.0228 (5)
O2	0.21888 (6)	0.2628 (6)	0.15685 (7)	0.0191 (4)
H1O2	0.1816	0.4181	0.1225	0.029*
O3	0.14264 (6)	0.6094 (5)	0.10279 (8)	0.0193 (5)
O4	0.06986 (6)	0.5317 (6)	0.01065 (9)	0.0272 (5)
C6	0.18695 (8)	0.1875 (7)	0.03925 (11)	0.0148 (5)
C7	0.20221 (9)	0.0642 (8)	−0.00144 (12)	0.0170 (5)
H7A	0.2336	−0.0336	0.0179	0.020*
C8	0.17220 (9)	0.0825 (8)	−0.06960 (12)	0.0193 (6)
H8A	0.1836	0.0045	−0.0955	0.023*
C9	0.12537 (9)	0.2173 (8)	−0.09827 (11)	0.0195 (6)
H9A	0.1045	0.2259	−0.1440	0.023*
C10	0.10903 (9)	0.3408 (7)	−0.05943 (11)	0.0159 (5)
H10A	0.0772	0.4316	−0.0797	0.019*
C11	0.13903 (8)	0.3330 (7)	0.00959 (11)	0.0145 (5)
C12	0.11507 (8)	0.4977 (7)	0.04302 (11)	0.0161 (5)
C13	0.22537 (8)	0.1262 (7)	0.11219 (11)	0.0154 (5)

	U11	U22	U33	U12	U13	U23
N1	0.0160 (10)	0.0203 (12)	0.0105 (9)	0.0010 (9)	0.0079 (8)	−0.0016 (9)
N2	0.0140 (9)	0.0278 (13)	0.0146 (9)	−0.0007 (10)	0.0066 (8)	−0.0046 (10)
N3	0.0140 (9)	0.0340 (15)	0.0135 (9)	−0.0008 (10)	0.0064 (8)	−0.0042 (10)
C1	0.0162 (11)	0.0156 (13)	0.0147 (10)	0.0007 (10)	0.0079 (9)	0.0025 (10)
C2	0.0162 (11)	0.0185 (14)	0.0181 (11)	0.0005 (11)	0.0089 (10)	0.0018 (11)
C3	0.0236 (12)	0.0207 (14)	0.0175 (11)	0.0051 (12)	0.0141 (10)	0.0020 (11)
C4	0.0196 (11)	0.0175 (13)	0.0136 (11)	−0.0001 (11)	0.0091 (10)	−0.0004 (11)
C5	0.0170 (11)	0.0148 (13)	0.0111 (10)	−0.0031 (10)	0.0057 (9)	−0.0006 (10)
O1	0.0190 (9)	0.0286 (11)	0.0184 (8)	0.0056 (9)	0.0085 (7)	0.0023 (9)
O2	0.0170 (8)	0.0274 (11)	0.0127 (8)	0.0010 (8)	0.0078 (7)	−0.0007 (8)
O3	0.0155 (8)	0.0272 (11)	0.0151 (8)	0.0011 (8)	0.0084 (7)	−0.0045 (8)
O4	0.0152 (9)	0.0409 (13)	0.0235 (9)	−0.0007 (9)	0.0092 (7)	−0.0105 (10)
C6	0.0147 (10)	0.0162 (13)	0.0134 (10)	−0.0004 (10)	0.0076 (9)	0.0005 (10)
C7	0.0161 (11)	0.0185 (13)	0.0184 (11)	−0.0018 (11)	0.0107 (9)	−0.0010 (11)
C8	0.0261 (13)	0.0192 (14)	0.0191 (11)	−0.0028 (12)	0.0166 (10)	−0.0008 (11)
C9	0.0209 (12)	0.0205 (14)	0.0126 (10)	−0.0037 (11)	0.0062 (9)	−0.0003 (11)
C10	0.0141 (10)	0.0156 (13)	0.0162 (11)	−0.0024 (10)	0.0072 (9)	−0.0013 (10)
C11	0.0153 (10)	0.0127 (12)	0.0162 (11)	−0.0016 (10)	0.0090 (9)	−0.0017 (10)
C12	0.0159 (11)	0.0176 (14)	0.0161 (11)	−0.0023 (11)	0.0095 (9)	−0.0015 (11)
C13	0.0141 (10)	0.0166 (13)	0.0161 (11)	−0.0004 (10)	0.0086 (9)	0.0020 (10)

N1—C1	1.364 (3)	O2—C13	1.310 (3)
N1—C5	1.368 (3)	O2—H1O2	1.1764
N1—H1A	0.8600	O3—C12	1.285 (3)
N2—C1	1.329 (3)	O3—H1O2	1.2919
N2—H2A	0.8600	O4—C12	1.232 (3)
N2—H2B	0.8600	C6—C7	1.397 (3)
N3—C5	1.326 (3)	C6—C11	1.413 (3)
N3—H3A	0.8600	C6—C13	1.522 (3)
N3—H3B	0.8600	C7—C8	1.385 (3)
C1—C2	1.393 (3)	C7—H7A	0.9300
C2—C3	1.373 (3)	C8—C9	1.372 (3)
C2—H2C	0.9300	C8—H8A	0.9300
C3—C4	1.386 (3)	C9—C10	1.383 (3)
C3—H3C	0.9300	C9—H9A	0.9300
C4—C5	1.399 (3)	C10—C11	1.401 (3)
C4—H4A	0.9300	C10—H10A	0.9300
O1—C13	1.217 (3)	C11—C12	1.521 (3)
C1—N1—C5	123.8 (2)	C12—O3—H1O2	100.1
C1—N1—H1A	118.1	C7—C6—C11	118.6 (2)
C5—N1—H1A	118.1	C7—C6—C13	112.8 (2)
C1—N2—H2A	120.0	C11—C6—C13	128.5 (2)
C1—N2—H2B	120.0	C8—C7—C6	122.3 (2)
H2A—N2—H2B	120.0	C8—C7—H7A	118.8
C5—N3—H3A	120.0	C6—C7—H7A	118.8
C5—N3—H3B	120.0	C9—C8—C7	118.9 (2)
H3A—N3—H3B	120.0	C9—C8—H8A	120.5
N2—C1—N1	116.2 (2)	C7—C8—H8A	120.5
N2—C1—C2	125.2 (2)	C8—C9—C10	120.2 (2)
N1—C1—C2	118.5 (2)	C8—C9—H9A	119.9
C3—C2—C1	118.6 (2)	C10—C9—H9A	119.9
C3—C2—H2C	120.7	C9—C10—C11	122.0 (2)
C1—C2—H2C	120.7	C9—C10—H10A	119.0
C2—C3—C4	122.6 (2)	C11—C10—H10A	119.0
C2—C3—H3C	118.7	C10—C11—C6	117.9 (2)
C4—C3—H3C	118.7	C10—C11—C12	113.7 (2)
C3—C4—C5	118.3 (2)	C6—C11—C12	128.3 (2)
C3—C4—H4A	120.8	O4—C12—O3	122.4 (2)
C5—C4—H4A	120.8	O4—C12—C11	118.4 (2)
N3—C5—N1	118.0 (2)	O3—C12—C11	119.1 (2)
N3—C5—C4	123.9 (2)	O1—C13—O2	120.6 (2)
N1—C5—C4	118.1 (2)	O1—C13—C6	119.3 (2)
C13—O2—H1O2	99.9	O2—C13—C6	120.0 (2)
C5—N1—C1—N2	179.6 (2)	C9—C10—C11—C6	−1.2 (4)
C5—N1—C1—C2	−0.7 (4)	C9—C10—C11—C12	177.1 (2)
N2—C1—C2—C3	−179.5 (3)	C7—C6—C11—C10	0.9 (4)
N1—C1—C2—C3	0.9 (4)	C13—C6—C11—C10	−175.8 (2)
C1—C2—C3—C4	−0.9 (4)	C7—C6—C11—C12	−177.1 (3)
C2—C3—C4—C5	0.7 (4)	C13—C6—C11—C12	6.2 (4)
C1—N1—C5—N3	−179.8 (2)	C10—C11—C12—O4	19.0 (4)
C1—N1—C5—C4	0.5 (4)	C6—C11—C12—O4	−162.9 (3)
C3—C4—C5—N3	179.8 (3)	C10—C11—C12—O3	−158.2 (2)
C3—C4—C5—N1	−0.4 (4)	C6—C11—C12—O3	19.9 (4)
C11—C6—C7—C8	0.5 (4)	C7—C6—C13—O1	−9.9 (3)
C13—C6—C7—C8	177.8 (3)	C11—C6—C13—O1	167.0 (3)
C6—C7—C8—C9	−1.8 (4)	C7—C6—C13—O2	172.4 (2)
C7—C8—C9—C10	1.6 (4)	C11—C6—C13—O2	−10.8 (4)
C8—C9—C10—C11	−0.1 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1O2···O3	1.18	1.29	2.437 (3)	162
N1—H1A···O3	0.86	1.98	2.828 (3)	167
N2—H2A···O4	0.86	1.98	2.834 (3)	177
N2—H2B···O4i	0.86	2.10	2.851 (3)	145
N3—H3A···O2ii	0.86	2.35	3.042 (3)	138
N3—H3B···O1iii	0.86	2.01	2.858 (3)	171

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H1O2⋯O3	1.18	1.29	2.437 (3)	162
N1—H1A⋯O3	0.86	1.98	2.828 (3)	167
N2—H2A⋯O4	0.86	1.98	2.834 (3)	177
N2—H2B⋯O4i	0.86	2.10	2.851 (3)	145
N3—H3A⋯O2ii	0.86	2.35	3.042 (3)	138
N3—H3B⋯O1iii	0.86	2.01	2.858 (3)	171

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