2,3-Diamino-pyridinium benzoate.

In the title compound, C(5)H(8)N(3) (+)·C(7)H(5)O(2) (-), the pyridine N atom is protonated. The carboxyl-ate group of the benzoate anion is twisted away from the attached ring by 10.91 (9)°. In the crystal structure, N-H⋯O hydrogen bonds between 2,3-diamino-pyridinium cations and benzoate anions, and π-π inter-actions between the pyridinium rings [centroid-centroid distance = 3.6467 (9) Å] form a two-dimensional network parallel to (001). In the network, N-H⋯O hydrogen bonds form R(2) (2)(8) and R(2) (1)(7) ring motifs.

Related literature

For general background to pyridine derivatives, see: Pozharski et al. (1997 ▶); Katritzky et al. (1996 ▶). For bond-length data, see: Allen et al. (1987 ▶). For details of n class="Chemical">hydrogen bonding, see: 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 +·C7H5O2 −

M = 231.25

Orthorhombic,

a = 10.1498 (3) Å

b = 11.0656 (3) Å

c = 20.7368 (7) Å

V = 2329.03 (12) Å3

Z = 8

Mo Kα radiation

μ = 0.09 mm−1

T = 100 K

0.43 × 0.40 × 0.03 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.935, T max = 0.998

27109 measured reflections

3443 independent reflections

2559 reflections with I > 2σ(I)

R int = 0.070

Refinement

R[F 2 > 2σ(F 2)] = 0.065

wR(F 2) = 0.124

S = 1.09

3443 reflections

206 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.26 e Å−3

Δρmin = −0.22 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/S1600536809021011/ci2821sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809021011/ci2821Isup2.hkl

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

C5H8N3+·C7H5O2−	F(000) = 976
Mr = 231.25	Dx = 1.319 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3782 reflections
a = 10.1498 (3) Å	θ = 2.8–27.9°
b = 11.0656 (3) Å	µ = 0.09 mm−1
c = 20.7368 (7) Å	T = 100 K
V = 2329.03 (12) Å3	Plate, brown
Z = 8	0.43 × 0.40 × 0.03 mm

Bruker SMART APEXII CCD area-detector diffractometer	3443 independent reflections
Radiation source: fine-focus sealed tube	2559 reflections with I > 2σ(I)
graphite	Rint = 0.070
φ and ω scans	θmax = 30.1°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −14→14
Tmin = 0.935, Tmax = 0.998	k = −15→15
27109 measured reflections	l = −26→29

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.0394P)2 + 1.0527P] where P = (Fo2 + 2Fc2)/3
3443 reflections	(Δ/σ)max = 0.001
206 parameters	Δρmax = 0.26 e Å−3
0 restraints	Δρmin = −0.22 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 e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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	0.41320 (11)	0.39789 (9)	0.63510 (5)	0.0253 (3)
O2	0.39681 (11)	0.57595 (9)	0.58541 (5)	0.0257 (3)
C6	0.54129 (15)	0.55976 (13)	0.67572 (8)	0.0217 (3)
C1	0.57778 (16)	0.49395 (15)	0.73019 (8)	0.0271 (4)
C2	0.66687 (18)	0.54115 (17)	0.77390 (10)	0.0347 (4)
C3	0.72160 (19)	0.65474 (16)	0.76378 (10)	0.0365 (4)
C4	0.68658 (19)	0.72004 (16)	0.70966 (10)	0.0375 (5)
C5	0.59687 (17)	0.67368 (14)	0.66578 (9)	0.0296 (4)
C7	0.44423 (15)	0.50698 (13)	0.62917 (7)	0.0211 (3)
C9	0.06661 (15)	0.32936 (13)	0.46855 (8)	0.0220 (3)
C8	0.15562 (15)	0.37759 (13)	0.51515 (8)	0.0211 (3)
N1	0.22115 (13)	0.47997 (11)	0.50049 (7)	0.0230 (3)
N2	0.17608 (14)	0.32713 (12)	0.57320 (7)	0.0239 (3)
N3	−0.00614 (14)	0.22766 (12)	0.48334 (8)	0.0273 (3)
C12	0.20715 (17)	0.53936 (14)	0.44310 (9)	0.0270 (4)
C11	0.12491 (17)	0.49519 (15)	0.39762 (9)	0.0288 (4)
C10	0.05443 (17)	0.38821 (14)	0.41056 (9)	0.0268 (4)
H12A	0.262 (2)	0.6122 (17)	0.4384 (9)	0.039 (5)*
H11A	0.1152 (17)	0.5333 (16)	0.3555 (9)	0.028 (5)*
H10A	−0.0033 (18)	0.3556 (15)	0.3778 (9)	0.027 (5)*
H1A	0.5401 (19)	0.4138 (17)	0.7363 (9)	0.037 (5)*
H2A	0.690 (2)	0.4955 (18)	0.8134 (10)	0.045 (6)*
H3A	0.785 (2)	0.6890 (17)	0.7969 (10)	0.043 (6)*
H4A	0.726 (2)	0.7970 (19)	0.7013 (10)	0.051 (6)*
H5A	0.5737 (18)	0.7200 (17)	0.6276 (9)	0.032 (5)*
H1N1	0.283 (2)	0.5096 (18)	0.5312 (9)	0.039 (5)*
H1N2	0.248 (2)	0.3487 (16)	0.5959 (9)	0.033 (5)*
H2N2	0.146 (2)	0.253 (2)	0.5800 (10)	0.047 (6)*
H1N3	0.021 (2)	0.1812 (18)	0.5170 (10)	0.042 (6)*
H2N3	−0.043 (2)	0.1882 (17)	0.4469 (10)	0.041 (6)*

	U11	U22	U33	U12	U13	U23
O1	0.0278 (6)	0.0181 (5)	0.0298 (6)	−0.0009 (4)	−0.0021 (5)	0.0002 (4)
O2	0.0280 (6)	0.0205 (5)	0.0285 (6)	−0.0020 (4)	−0.0058 (5)	0.0020 (4)
C6	0.0181 (7)	0.0209 (7)	0.0261 (8)	0.0037 (5)	0.0001 (6)	−0.0025 (6)
C1	0.0252 (8)	0.0271 (8)	0.0291 (9)	0.0039 (6)	−0.0009 (7)	0.0015 (7)
C2	0.0335 (10)	0.0398 (10)	0.0308 (10)	0.0067 (8)	−0.0089 (8)	0.0007 (8)
C3	0.0339 (10)	0.0346 (9)	0.0410 (11)	0.0058 (7)	−0.0150 (8)	−0.0104 (8)
C4	0.0361 (10)	0.0245 (8)	0.0520 (12)	−0.0009 (7)	−0.0165 (9)	−0.0026 (8)
C5	0.0298 (9)	0.0227 (7)	0.0364 (10)	0.0003 (6)	−0.0111 (8)	0.0019 (7)
C7	0.0197 (7)	0.0210 (7)	0.0226 (8)	0.0019 (5)	0.0027 (6)	−0.0013 (6)
C9	0.0194 (7)	0.0182 (7)	0.0285 (9)	0.0017 (5)	−0.0004 (6)	−0.0027 (6)
C8	0.0192 (7)	0.0175 (6)	0.0265 (8)	0.0028 (5)	0.0011 (6)	−0.0016 (6)
N1	0.0223 (7)	0.0186 (6)	0.0281 (7)	−0.0011 (5)	−0.0013 (6)	−0.0012 (5)
N2	0.0237 (7)	0.0213 (6)	0.0269 (8)	−0.0029 (5)	−0.0020 (6)	0.0014 (5)
N3	0.0288 (7)	0.0217 (6)	0.0314 (8)	−0.0048 (5)	−0.0055 (7)	0.0010 (6)
C12	0.0286 (9)	0.0204 (7)	0.0320 (9)	−0.0014 (6)	0.0008 (7)	0.0038 (6)
C11	0.0319 (9)	0.0260 (8)	0.0285 (9)	0.0006 (7)	−0.0019 (7)	0.0054 (7)
C10	0.0252 (8)	0.0269 (8)	0.0283 (9)	0.0000 (6)	−0.0043 (7)	−0.0014 (7)

O1—C7	1.2537 (17)	C9—N3	1.3805 (19)
O2—C7	1.2796 (18)	C9—C8	1.427 (2)
C6—C1	1.394 (2)	C8—N2	1.343 (2)
C6—C5	1.396 (2)	C8—N1	1.3484 (19)
C6—C7	1.498 (2)	N1—C12	1.367 (2)
C1—C2	1.383 (2)	N1—H1N1	0.96 (2)
C1—H1A	0.974 (19)	N2—H1N2	0.90 (2)
C2—C3	1.390 (3)	N2—H2N2	0.88 (2)
C2—H2A	0.99 (2)	N3—H1N3	0.91 (2)
C3—C4	1.381 (3)	N3—H2N3	0.95 (2)
C3—H3A	1.02 (2)	C12—C11	1.351 (2)
C4—C5	1.386 (2)	C12—H12A	0.99 (2)
C4—H4A	0.96 (2)	C11—C10	1.409 (2)
C5—H5A	0.972 (19)	C11—H11A	0.975 (18)
C9—C10	1.373 (2)	C10—H10A	0.966 (18)
C1—C6—C5	118.94 (15)	N3—C9—C8	119.55 (15)
C1—C6—C7	119.56 (14)	N2—C8—N1	118.36 (14)
C5—C6—C7	121.50 (14)	N2—C8—C9	123.34 (14)
C2—C1—C6	120.50 (16)	N1—C8—C9	118.29 (14)
C2—C1—H1A	121.0 (12)	C8—N1—C12	123.30 (14)
C6—C1—H1A	118.5 (12)	C8—N1—H1N1	117.7 (12)
C1—C2—C3	120.25 (17)	C12—N1—H1N1	119.0 (12)
C1—C2—H2A	120.4 (12)	C8—N2—H1N2	118.9 (12)
C3—C2—H2A	119.3 (12)	C8—N2—H2N2	118.3 (14)
C4—C3—C2	119.53 (17)	H1N2—N2—H2N2	116.3 (18)
C4—C3—H3A	121.2 (11)	C9—N3—H1N3	117.9 (13)
C2—C3—H3A	119.3 (11)	C9—N3—H2N3	114.0 (12)
C3—C4—C5	120.59 (17)	H1N3—N3—H2N3	118.1 (17)
C3—C4—H4A	120.4 (13)	C11—C12—N1	119.87 (15)
C5—C4—H4A	119.0 (13)	C11—C12—H12A	125.2 (11)
C4—C5—C6	120.18 (17)	N1—C12—H12A	114.9 (11)
C4—C5—H5A	119.9 (11)	C12—C11—C10	118.99 (16)
C6—C5—H5A	119.9 (11)	C12—C11—H11A	122.1 (11)
O1—C7—O2	123.33 (14)	C10—C11—H11A	118.9 (11)
O1—C7—C6	118.52 (14)	C9—C10—C11	121.30 (16)
O2—C7—C6	118.15 (13)	C9—C10—H10A	119.5 (10)
C10—C9—N3	122.21 (15)	C11—C10—H10A	119.2 (10)
C10—C9—C8	118.22 (14)
C5—C6—C1—C2	0.5 (2)	C10—C9—C8—N2	−179.52 (15)
C7—C6—C1—C2	−179.77 (15)	N3—C9—C8—N2	1.9 (2)
C6—C1—C2—C3	−0.3 (3)	C10—C9—C8—N1	1.4 (2)
C1—C2—C3—C4	−0.1 (3)	N3—C9—C8—N1	−177.16 (13)
C2—C3—C4—C5	0.5 (3)	N2—C8—N1—C12	−179.52 (14)
C3—C4—C5—C6	−0.3 (3)	C9—C8—N1—C12	−0.4 (2)
C1—C6—C5—C4	−0.1 (3)	C8—N1—C12—C11	−0.4 (2)
C7—C6—C5—C4	−179.90 (16)	N1—C12—C11—C10	0.2 (2)
C1—C6—C7—O1	−10.6 (2)	N3—C9—C10—C11	176.89 (15)
C5—C6—C7—O1	169.17 (15)	C8—C9—C10—C11	−1.7 (2)
C1—C6—C7—O2	169.17 (14)	C12—C11—C10—C9	0.8 (3)
C5—C6—C7—O2	−11.1 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O2	0.96 (2)	1.77 (2)	2.7218 (18)	176 (2)
N2—H1N2···O1	0.90 (2)	1.94 (2)	2.8377 (18)	173 (2)
N2—H2N2···O2i	0.88 (2)	2.01 (2)	2.8873 (17)	170 (2)
N3—H1N3···O2i	0.91 (2)	2.02 (2)	2.9206 (19)	173 (2)
N3—H2N3···O1ii	0.95 (2)	2.00 (2)	2.9382 (19)	170 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O2	0.96 (2)	1.77 (2)	2.7218 (18)	176 (2)
N2—H1N2⋯O1	0.90 (2)	1.94 (2)	2.8377 (18)	173 (2)
N2—H2N2⋯O2i	0.88 (2)	2.01 (2)	2.8873 (17)	170 (2)
N3—H1N3⋯O2i	0.91 (2)	2.02 (2)	2.9206 (19)	173 (2)
N3—H2N3⋯O1ii	0.95 (2)	2.00 (2)	2.9382 (19)	170 (2)

Symmetry codes: (i) ; (ii) .