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

In the title compound, C(5)H(8)N(3) (+)·C(7)H(5)O(3) (-), the pyridine N atom is protonated. In the 4-hydroxy-benzoate anion, the carboxyl-ate group is twisted slightly out of the benzene ring plane by an angle of 3.77 (5)°. The protonated N atom and one of the two amino groups are hydrogen-bonded to the 4-hydroxy-benzoate anion through a pair of N-H⋯O hydrogen bonds, forming an R(2) (2)(8) ring motif. The crystal structure is further stabilized by O-H⋯O and C-H⋯O hydrogen bonds and π-π inter-actions involving the pyridinium rings [centroid-centroid distance of 3.6277 (5) Å], leading to the formation of a three-dimensional network.

Related literature

For general background to substituted pyridines, see: Pozharski et al. (1997 ▶); Katritzky et al. (1996 ▶). 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

C5H8N3 +·C7H5O3 −

M = 247.25

Monoclinic,

a = 10.2915 (2) Å

b = 11.4946 (2) Å

c = 11.0921 (2) Å

β = 112.644 (1)°

V = 1211.01 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 100 K

0.51 × 0.39 × 0.14 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.950, T max = 0.986

25821 measured reflections

5296 independent reflections

4257 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.138

S = 1.04

5296 reflections

215 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.65 e Å−3

Δρmin = −0.19 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); 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/S1600536809020832/ci2813sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809020832/ci2813Isup2.hkl

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

C5H8N3+·C7H5O3−	F(000) = 520
Mr = 247.25	Dx = 1.356 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9979 reflections
a = 10.2915 (2) Å	θ = 2.7–37.8°
b = 11.4946 (2) Å	µ = 0.10 mm−1
c = 11.0921 (2) Å	T = 100 K
β = 112.644 (1)°	Plate, brown
V = 1211.01 (4) Å3	0.51 × 0.39 × 0.14 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	5296 independent reflections
Radiation source: fine-focus sealed tube	4257 reflections with I > 2σ(I)
graphite	Rint = 0.034
φ and ω scans	θmax = 35.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −16→16
Tmin = 0.950, Tmax = 0.986	k = −16→18
25821 measured reflections	l = −17→17

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.138	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0817P)2 + 0.1673P] where P = (Fo2 + 2Fc2)/3
5296 reflections	(Δ/σ)max = 0.001
215 parameters	Δρmax = 0.65 e Å−3
0 restraints	Δρmin = −0.18 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	0.45467 (8)	0.16900 (6)	0.43336 (6)	0.02563 (15)
O2	0.84786 (7)	0.61461 (5)	0.52034 (5)	0.02074 (13)
O3	0.73136 (6)	0.62156 (5)	0.30541 (5)	0.01784 (12)
N1	1.01845 (8)	0.79427 (6)	0.49674 (6)	0.01857 (14)
N2	0.87767 (8)	0.81703 (7)	0.27844 (7)	0.02195 (15)
N3	1.05767 (9)	0.99458 (8)	0.25977 (7)	0.02666 (17)
C1	0.57827 (9)	0.42070 (7)	0.30431 (7)	0.01757 (14)
C2	0.50323 (9)	0.32084 (7)	0.30618 (7)	0.01879 (15)
C3	0.52248 (9)	0.26810 (7)	0.42538 (7)	0.01899 (15)
C4	0.61617 (11)	0.31656 (8)	0.54174 (8)	0.02518 (18)
C5	0.69083 (10)	0.41624 (8)	0.53881 (7)	0.02324 (17)
C6	0.67313 (8)	0.46970 (7)	0.41995 (7)	0.01604 (14)
C7	0.75521 (8)	0.57533 (6)	0.41592 (7)	0.01540 (14)
C8	0.99181 (9)	0.84838 (7)	0.38181 (7)	0.01678 (14)
C9	1.08674 (9)	0.93716 (7)	0.37590 (7)	0.01803 (15)
C10	1.20049 (9)	0.96332 (8)	0.48910 (8)	0.02092 (16)
C11	1.22331 (9)	0.90438 (8)	0.60700 (8)	0.02314 (17)
C12	1.13117 (10)	0.82008 (8)	0.60867 (8)	0.02224 (17)
H1	0.5647 (15)	0.4565 (11)	0.2226 (13)	0.031 (3)*
H2	0.4376 (14)	0.2854 (12)	0.2229 (13)	0.029 (3)*
H4	0.6280 (18)	0.2759 (15)	0.6232 (17)	0.051 (4)*
H5	0.7615 (17)	0.4479 (13)	0.6225 (15)	0.039 (4)*
H10	1.2669 (14)	1.0227 (12)	0.4848 (12)	0.028 (3)*
H11	1.3091 (16)	0.9246 (13)	0.6883 (14)	0.039 (4)*
H12	1.1341 (17)	0.7745 (14)	0.6809 (15)	0.043 (4)*
H1N1	0.9588 (15)	0.7391 (12)	0.4987 (13)	0.031 (3)*
H1N2	0.8601 (17)	0.8454 (12)	0.2011 (15)	0.033 (3)*
H2N2	0.8275 (15)	0.7565 (12)	0.2854 (13)	0.027 (3)*
H1N3	0.9924 (17)	0.9660 (13)	0.1840 (15)	0.040 (4)*
H2N3	1.1284 (16)	1.0365 (12)	0.2548 (14)	0.034 (3)*
H1O1	0.3995 (19)	0.1445 (15)	0.3531 (18)	0.051 (5)*

	U11	U22	U33	U12	U13	U23
O1	0.0299 (3)	0.0248 (3)	0.0172 (3)	−0.0123 (2)	0.0034 (2)	0.0013 (2)
O2	0.0238 (3)	0.0217 (3)	0.0141 (2)	−0.0059 (2)	0.0044 (2)	−0.00153 (19)
O3	0.0188 (3)	0.0178 (3)	0.0149 (2)	0.0002 (2)	0.00434 (19)	0.00308 (19)
N1	0.0200 (3)	0.0194 (3)	0.0148 (3)	−0.0020 (2)	0.0051 (2)	0.0018 (2)
N2	0.0232 (3)	0.0234 (3)	0.0154 (3)	−0.0072 (3)	0.0031 (2)	0.0021 (2)
N3	0.0284 (4)	0.0324 (4)	0.0171 (3)	−0.0118 (3)	0.0065 (3)	0.0037 (3)
C1	0.0190 (3)	0.0187 (3)	0.0131 (3)	−0.0014 (3)	0.0041 (2)	0.0005 (2)
C2	0.0198 (4)	0.0205 (3)	0.0131 (3)	−0.0037 (3)	0.0031 (2)	−0.0007 (2)
C3	0.0202 (4)	0.0199 (3)	0.0150 (3)	−0.0046 (3)	0.0047 (3)	−0.0001 (2)
C4	0.0316 (5)	0.0273 (4)	0.0130 (3)	−0.0114 (3)	0.0046 (3)	0.0008 (3)
C5	0.0286 (4)	0.0251 (4)	0.0131 (3)	−0.0099 (3)	0.0049 (3)	−0.0015 (3)
C6	0.0173 (3)	0.0167 (3)	0.0131 (3)	−0.0016 (2)	0.0048 (2)	−0.0007 (2)
C7	0.0167 (3)	0.0152 (3)	0.0140 (3)	0.0013 (2)	0.0055 (2)	−0.0002 (2)
C8	0.0177 (3)	0.0174 (3)	0.0143 (3)	−0.0003 (3)	0.0052 (2)	0.0001 (2)
C9	0.0183 (3)	0.0204 (3)	0.0155 (3)	−0.0023 (3)	0.0066 (2)	0.0000 (2)
C10	0.0192 (4)	0.0249 (4)	0.0178 (3)	−0.0044 (3)	0.0062 (3)	−0.0010 (3)
C11	0.0200 (4)	0.0294 (4)	0.0166 (3)	−0.0029 (3)	0.0032 (3)	−0.0007 (3)
C12	0.0230 (4)	0.0262 (4)	0.0145 (3)	−0.0014 (3)	0.0038 (3)	0.0023 (3)

O1—C3	1.3565 (10)	C2—C3	1.3976 (11)
O1—H1O1	0.897 (18)	C2—H2	0.997 (13)
O2—C7	1.2666 (9)	C3—C4	1.3956 (11)
O3—C7	1.2702 (9)	C4—C5	1.3869 (12)
N1—C8	1.3484 (10)	C4—H4	0.982 (17)
N1—C12	1.3661 (11)	C5—C6	1.4014 (11)
N1—H1N1	0.888 (15)	C5—H5	1.001 (15)
N2—C8	1.3369 (10)	C6—C7	1.4896 (11)
N2—H1N2	0.869 (15)	C8—C9	1.4316 (11)
N2—H2N2	0.887 (14)	C9—C10	1.3805 (11)
N3—C9	1.3739 (10)	C10—C11	1.4100 (12)
N3—H1N3	0.911 (16)	C10—H10	0.981 (14)
N3—H2N3	0.892 (15)	C11—C12	1.3608 (13)
C1—C2	1.3881 (11)	C11—H11	1.017 (15)
C1—C6	1.3969 (10)	C12—H12	0.948 (15)
C1—H1	0.955 (13)
C3—O1—H1O1	110.1 (11)	C4—C5—H5	119.3 (8)
C8—N1—C12	123.47 (7)	C6—C5—H5	119.9 (9)
C8—N1—H1N1	117.5 (9)	C1—C6—C5	118.61 (7)
C12—N1—H1N1	119.1 (9)	C1—C6—C7	120.33 (6)
C8—N2—H1N2	121.7 (10)	C5—C6—C7	121.05 (7)
C8—N2—H2N2	119.1 (9)	O2—C7—O3	122.08 (7)
H1N2—N2—H2N2	118.2 (13)	O2—C7—C6	119.94 (6)
C9—N3—H1N3	120.6 (10)	O3—C7—C6	117.96 (6)
C9—N3—H2N3	115.4 (9)	N2—C8—N1	118.57 (7)
H1N3—N3—H2N3	117.8 (13)	N2—C8—C9	122.86 (7)
C2—C1—C6	121.05 (7)	N1—C8—C9	118.57 (7)
C2—C1—H1	119.4 (8)	N3—C9—C10	123.40 (8)
C6—C1—H1	119.5 (8)	N3—C9—C8	118.64 (7)
C1—C2—C3	119.72 (7)	C10—C9—C8	117.92 (7)
C1—C2—H2	120.4 (8)	C9—C10—C11	121.27 (8)
C3—C2—H2	119.9 (8)	C9—C10—H10	118.1 (8)
O1—C3—C4	117.67 (7)	C11—C10—H10	120.6 (8)
O1—C3—C2	122.47 (7)	C12—C11—C10	119.12 (8)
C4—C3—C2	119.85 (7)	C12—C11—H11	121.5 (8)
C5—C4—C3	119.99 (7)	C10—C11—H11	119.4 (8)
C5—C4—H4	122.8 (10)	C11—C12—N1	119.65 (7)
C3—C4—H4	117.2 (10)	C11—C12—H12	127.5 (10)
C4—C5—C6	120.78 (7)	N1—C12—H12	112.8 (10)
C6—C1—C2—C3	−0.01 (13)	C5—C6—C7—O3	−178.02 (8)
C1—C2—C3—O1	−178.47 (8)	C12—N1—C8—N2	−179.40 (8)
C1—C2—C3—C4	0.46 (14)	C12—N1—C8—C9	0.41 (12)
O1—C3—C4—C5	178.40 (9)	N2—C8—C9—N3	1.55 (13)
C2—C3—C4—C5	−0.57 (15)	N1—C8—C9—N3	−178.25 (8)
C3—C4—C5—C6	0.24 (15)	N2—C8—C9—C10	179.31 (8)
C2—C1—C6—C5	−0.32 (13)	N1—C8—C9—C10	−0.49 (12)
C2—C1—C6—C7	178.59 (7)	N3—C9—C10—C11	177.91 (9)
C4—C5—C6—C1	0.21 (14)	C8—C9—C10—C11	0.26 (13)
C4—C5—C6—C7	−178.70 (9)	C9—C10—C11—C12	0.06 (14)
C1—C6—C7—O2	−175.21 (8)	C10—C11—C12—N1	−0.16 (14)
C5—C6—C7—O2	3.67 (12)	C8—N1—C12—C11	−0.08 (13)
C1—C6—C7—O3	3.09 (11)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O2	0.89 (2)	1.903 (15)	2.7874 (9)	173 (1)
N2—H2N2···O3	0.89 (1)	1.898 (14)	2.7843 (9)	176 (1)
N2—H1N2···O2i	0.87 (1)	2.014 (15)	2.8689 (9)	168 (1)
N3—H1N3···O2i	0.91 (2)	2.071 (16)	2.9790 (10)	174 (1)
N3—H2N3···O3ii	0.89 (2)	2.057 (15)	2.9285 (10)	166 (1)
O1—H1O1···O3iii	0.90 (2)	1.775 (19)	2.6595 (8)	168 (2)
C2—H2···O3iii	1.00 (1)	2.500 (14)	3.2104 (10)	128 (1)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O2	0.89 (2)	1.903 (15)	2.7874 (9)	173 (1)
N2—H2N2⋯O3	0.89 (1)	1.898 (14)	2.7843 (9)	176 (1)
N2—H1N2⋯O2i	0.87 (1)	2.014 (15)	2.8689 (9)	168 (1)
N3—H1N3⋯O2i	0.91 (2)	2.071 (16)	2.9790 (10)	174 (1)
N3—H2N3⋯O3ii	0.89 (2)	2.057 (15)	2.9285 (10)	166 (1)
O1—H1O1⋯O3iii	0.90 (2)	1.775 (19)	2.6595 (8)	168 (2)
C2—H2⋯O3iii	1.00 (1)	2.500 (14)	3.2104 (10)	128 (1)

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