2,3-Diamino-pyridinium benzoate benzoic acid solvate.

In the title compound, C(5)H(8)N(3) (+)·C(7)H(5)O(2) (-)·C(7)H(6)O(2), the carboxyl and carboxyl-ate groups are twisted away from their attached benzene rings by 10.75 (7) and 20.33 (6)°, respectively. In the crystal structure, the 2,3-diamino-pyridinium cations, benzoate anions and benzoic acid mol-ecules are linked into a two-dimensional network parallel to (001) by O-H⋯O, N-H⋯O and C-H⋯O hydrogen bonds and π-π inter-actions between the pyridinium rings [centroid-centroid distance = 3.4981 (7) Å].

Related literature

For substituted pyridines, see: Pozharski et al. (1997 ▶); Katritzky et al. (1996 ▶). For related structures, see: Fun & Balasubramani (2009 ▶); Balasubramani & Fun (2009a ▶,b ▶). For bond-length data, see: Allen et al. (1987 ▶). For details of 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 −·C7H6O2

M = 353.37

Monoclinic,

a = 12.5822 (2) Å

b = 11.0826 (1) Å

c = 12.5615 (2) Å

β = 96.345 (1)°

V = 1740.89 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 110 K

0.38 × 0.18 × 0.13 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.964, T max = 0.988

36881 measured reflections

5104 independent reflections

3848 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.111

S = 1.05

5104 reflections

259 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.32 e Å−3

Δρmin = −0.22 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810001443/ci5016sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810001443/ci5016Isup2.hkl

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

C5H8N3+·C7H5O2−·C7H6O2	F(000) = 744
Mr = 353.37	Dx = 1.348 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9414 reflections
a = 12.5822 (2) Å	θ = 2.5–30.0°
b = 11.0826 (1) Å	µ = 0.10 mm−1
c = 12.5615 (2) Å	T = 110 K
β = 96.345 (1)°	Block, orange
V = 1740.89 (4) Å3	0.38 × 0.18 × 0.13 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	5104 independent reflections
Radiation source: fine-focus sealed tube	3848 reflections with I > 2σ(I)
graphite	Rint = 0.037
φ and ω scans	θmax = 30.1°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −17→16
Tmin = 0.964, Tmax = 0.988	k = −15→15
36881 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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0464P)2 + 0.4367P] where P = (Fo2 + 2Fc2)/3
5104 reflections	(Δ/σ)max = 0.001
259 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.22 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems 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
O1A	0.85851 (7)	0.85383 (8)	0.03377 (7)	0.0290 (2)
O2A	0.95927 (7)	0.88574 (8)	−0.09759 (6)	0.02659 (19)
C1A	0.74939 (10)	1.07373 (11)	−0.01140 (9)	0.0281 (3)
H1AA	0.7494	1.0434	0.0576	0.034*
C2A	0.68601 (11)	1.17233 (12)	−0.04363 (11)	0.0335 (3)
H2AA	0.6455	1.2097	0.0045	0.040*
C3A	0.68306 (10)	1.21522 (12)	−0.14752 (11)	0.0336 (3)
H3AA	0.6393	1.2801	−0.1697	0.040*
C4A	0.74514 (11)	1.16156 (13)	−0.21788 (10)	0.0348 (3)
H4AA	0.7426	1.1899	−0.2878	0.042*
C5A	0.81149 (10)	1.06528 (11)	−0.18501 (9)	0.0274 (3)
H5AA	0.8549	1.0312	−0.2322	0.033*
C6A	0.81306 (9)	1.01987 (10)	−0.08187 (8)	0.0214 (2)
C7A	0.88181 (9)	0.91288 (10)	−0.04745 (8)	0.0222 (2)
N1	1.05200 (8)	0.68618 (9)	0.02224 (8)	0.0237 (2)
N2	0.98632 (9)	0.70123 (10)	0.18620 (9)	0.0278 (2)
N3	1.10673 (10)	0.49546 (11)	0.25569 (9)	0.0336 (3)
C8	1.04742 (9)	0.64369 (10)	0.12201 (9)	0.0221 (2)
C9	1.10929 (9)	0.53927 (10)	0.15432 (9)	0.0224 (2)
C10	1.16824 (9)	0.48674 (10)	0.08034 (9)	0.0244 (2)
H10A	1.2080	0.4177	0.0992	0.029*
C11	1.16949 (10)	0.53516 (11)	−0.02261 (9)	0.0268 (3)
H11A	1.2101	0.4992	−0.0714	0.032*
C12	1.11068 (10)	0.63515 (11)	−0.05016 (9)	0.0264 (3)
H12A	1.1106	0.6685	−0.1181	0.032*
O1B	0.69229 (8)	0.72978 (9)	0.06840 (7)	0.0321 (2)
O2B	0.75274 (7)	0.77725 (8)	0.23701 (7)	0.0310 (2)
C1B	0.54529 (11)	0.56665 (13)	0.13724 (12)	0.0364 (3)
H1BA	0.5578	0.5637	0.0657	0.044*
C2B	0.46748 (12)	0.49389 (14)	0.17377 (15)	0.0485 (4)
H2BA	0.4281	0.4417	0.1267	0.058*
C3B	0.44829 (13)	0.49857 (14)	0.27941 (15)	0.0501 (4)
H3BA	0.3953	0.4503	0.3033	0.060*
C4B	0.50734 (12)	0.57449 (14)	0.34983 (13)	0.0443 (4)
H4BA	0.4943	0.5771	0.4212	0.053*
C5B	0.58609 (11)	0.64699 (12)	0.31465 (10)	0.0315 (3)
H5BA	0.6264	0.6975	0.3625	0.038*
C6B	0.60470 (9)	0.64412 (10)	0.20783 (9)	0.0254 (2)
C7B	0.69011 (9)	0.72314 (10)	0.17338 (9)	0.0235 (2)
H1OB	0.7482 (18)	0.7795 (19)	0.0545 (17)	0.076 (6)*
H1N1	1.0151 (13)	0.7519 (15)	0.0012 (13)	0.038 (4)*
H1N2	0.9746 (13)	0.6707 (15)	0.2475 (14)	0.041 (4)*
H2N2	0.9452 (13)	0.7586 (15)	0.1570 (13)	0.045 (5)*
H1N3	1.0666 (13)	0.5270 (14)	0.3014 (13)	0.040 (4)*
H2N3	1.1455 (13)	0.4331 (15)	0.2731 (12)	0.038 (4)*

	U11	U22	U33	U12	U13	U23
O1A	0.0312 (5)	0.0296 (5)	0.0266 (4)	0.0009 (4)	0.0050 (3)	0.0098 (3)
O2A	0.0266 (4)	0.0268 (4)	0.0270 (4)	0.0029 (3)	0.0057 (3)	0.0008 (3)
C1A	0.0294 (6)	0.0309 (6)	0.0243 (5)	0.0016 (5)	0.0045 (5)	0.0020 (5)
C2A	0.0297 (7)	0.0330 (7)	0.0385 (7)	0.0051 (5)	0.0060 (5)	−0.0029 (5)
C3A	0.0282 (7)	0.0274 (6)	0.0445 (7)	0.0048 (5)	0.0010 (5)	0.0079 (5)
C4A	0.0352 (7)	0.0379 (7)	0.0312 (6)	0.0045 (6)	0.0031 (5)	0.0145 (5)
C5A	0.0282 (6)	0.0299 (6)	0.0246 (5)	0.0014 (5)	0.0055 (5)	0.0051 (4)
C6A	0.0208 (5)	0.0208 (5)	0.0222 (5)	−0.0029 (4)	0.0005 (4)	0.0019 (4)
C7A	0.0241 (6)	0.0219 (5)	0.0200 (5)	−0.0019 (4)	0.0000 (4)	0.0003 (4)
N1	0.0254 (5)	0.0207 (5)	0.0248 (5)	0.0020 (4)	0.0018 (4)	0.0014 (4)
N2	0.0301 (6)	0.0265 (5)	0.0280 (5)	0.0078 (4)	0.0082 (4)	0.0024 (4)
N3	0.0418 (7)	0.0340 (6)	0.0267 (5)	0.0160 (5)	0.0113 (5)	0.0093 (4)
C8	0.0212 (5)	0.0208 (5)	0.0241 (5)	−0.0012 (4)	0.0019 (4)	−0.0005 (4)
C9	0.0221 (6)	0.0214 (5)	0.0235 (5)	−0.0005 (4)	0.0018 (4)	0.0006 (4)
C10	0.0239 (6)	0.0212 (6)	0.0282 (6)	0.0029 (4)	0.0029 (4)	−0.0003 (4)
C11	0.0285 (6)	0.0280 (6)	0.0244 (5)	0.0016 (5)	0.0060 (5)	−0.0029 (4)
C12	0.0302 (6)	0.0279 (6)	0.0213 (5)	−0.0013 (5)	0.0041 (4)	0.0008 (4)
O1B	0.0342 (5)	0.0385 (5)	0.0237 (4)	−0.0063 (4)	0.0036 (4)	−0.0013 (4)
O2B	0.0313 (5)	0.0331 (5)	0.0284 (4)	−0.0075 (4)	0.0031 (4)	−0.0048 (4)
C1B	0.0311 (7)	0.0323 (7)	0.0451 (8)	−0.0034 (6)	0.0011 (6)	−0.0051 (6)
C2B	0.0355 (8)	0.0330 (8)	0.0760 (11)	−0.0094 (6)	0.0020 (8)	−0.0029 (7)
C3B	0.0364 (8)	0.0315 (8)	0.0845 (12)	−0.0028 (6)	0.0156 (8)	0.0184 (8)
C4B	0.0431 (9)	0.0413 (8)	0.0510 (9)	0.0068 (7)	0.0166 (7)	0.0208 (7)
C5B	0.0324 (7)	0.0297 (6)	0.0326 (6)	0.0034 (5)	0.0046 (5)	0.0074 (5)
C6B	0.0230 (6)	0.0207 (5)	0.0321 (6)	0.0033 (5)	0.0017 (5)	0.0017 (4)
C7B	0.0238 (6)	0.0214 (5)	0.0253 (5)	0.0031 (4)	0.0026 (4)	−0.0017 (4)

O1A—C7A	1.2733 (13)	C8—C9	1.4283 (16)
O2A—C7A	1.2541 (14)	C9—C10	1.3802 (16)
C1A—C2A	1.3866 (18)	C10—C11	1.4018 (16)
C1A—C6A	1.3922 (16)	C10—H10A	0.93
C1A—H1AA	0.93	C11—C12	1.3559 (17)
C2A—C3A	1.3855 (19)	C11—H11A	0.93
C2A—H2AA	0.93	C12—H12A	0.93
C3A—C4A	1.3775 (19)	O1B—C7B	1.3241 (14)
C3A—H3AA	0.93	O1B—H1OB	0.93 (2)
C4A—C5A	1.3891 (18)	O2B—C7B	1.2166 (14)
C4A—H4AA	0.93	C1B—C2B	1.385 (2)
C5A—C6A	1.3880 (15)	C1B—C6B	1.3913 (18)
C5A—H5AA	0.93	C1B—H1BA	0.93
C6A—C7A	1.5028 (16)	C2B—C3B	1.376 (2)
N1—C8	1.3461 (14)	C2B—H2BA	0.93
N1—C12	1.3566 (15)	C3B—C4B	1.377 (2)
N1—H1N1	0.888 (17)	C3B—H3BA	0.93
N2—C8	1.3358 (15)	C4B—C5B	1.3855 (19)
N2—H1N2	0.869 (17)	C4B—H4BA	0.93
N2—H2N2	0.875 (17)	C5B—C6B	1.3877 (17)
N3—C9	1.3665 (15)	C5B—H5BA	0.93
N3—H1N3	0.878 (17)	C6B—C7B	1.4873 (17)
N3—H2N3	0.860 (17)
C2A—C1A—C6A	120.34 (11)	N3—C9—C8	118.97 (11)
C2A—C1A—H1AA	119.8	C10—C9—C8	117.84 (10)
C6A—C1A—H1AA	119.8	C9—C10—C11	121.42 (11)
C3A—C2A—C1A	120.00 (12)	C9—C10—H10A	119.3
C3A—C2A—H2AA	120.0	C11—C10—H10A	119.3
C1A—C2A—H2AA	120.0	C12—C11—C10	119.13 (11)
C4A—C3A—C2A	119.88 (12)	C12—C11—H11A	120.4
C4A—C3A—H3AA	120.1	C10—C11—H11A	120.4
C2A—C3A—H3AA	120.1	C11—C12—N1	119.45 (11)
C3A—C4A—C5A	120.38 (12)	C11—C12—H12A	120.3
C3A—C4A—H4AA	119.8	N1—C12—H12A	120.3
C5A—C4A—H4AA	119.8	C7B—O1B—H1OB	108.7 (13)
C6A—C5A—C4A	120.13 (11)	C2B—C1B—C6B	119.86 (14)
C6A—C5A—H5AA	119.9	C2B—C1B—H1BA	120.1
C4A—C5A—H5AA	119.9	C6B—C1B—H1BA	120.1
C5A—C6A—C1A	119.22 (11)	C3B—C2B—C1B	120.22 (15)
C5A—C6A—C7A	120.19 (10)	C3B—C2B—H2BA	119.9
C1A—C6A—C7A	120.58 (10)	C1B—C2B—H2BA	119.9
O2A—C7A—O1A	122.65 (11)	C2B—C3B—C4B	120.18 (14)
O2A—C7A—C6A	119.96 (10)	C2B—C3B—H3BA	119.9
O1A—C7A—C6A	117.38 (10)	C4B—C3B—H3BA	119.9
C8—N1—C12	124.11 (11)	C3B—C4B—C5B	120.23 (15)
C8—N1—H1N1	119.3 (10)	C3B—C4B—H4BA	119.9
C12—N1—H1N1	116.6 (10)	C5B—C4B—H4BA	119.9
C8—N2—H1N2	121.0 (11)	C4B—C5B—C6B	119.88 (13)
C8—N2—H2N2	116.6 (11)	C4B—C5B—H5BA	120.1
H1N2—N2—H2N2	120.2 (15)	C6B—C5B—H5BA	120.1
C9—N3—H1N3	122.8 (10)	C5B—C6B—C1B	119.62 (12)
C9—N3—H2N3	116.8 (10)	C5B—C6B—C7B	118.18 (11)
H1N3—N3—H2N3	120.3 (14)	C1B—C6B—C7B	122.19 (11)
N2—C8—N1	118.79 (11)	O2B—C7B—O1B	122.94 (11)
N2—C8—C9	123.18 (10)	O2B—C7B—C6B	122.38 (11)
N1—C8—C9	118.03 (10)	O1B—C7B—C6B	114.68 (10)
N3—C9—C10	123.18 (11)
C6A—C1A—C2A—C3A	2.2 (2)	N3—C9—C10—C11	−179.41 (12)
C1A—C2A—C3A—C4A	−1.6 (2)	C8—C9—C10—C11	1.28 (17)
C2A—C3A—C4A—C5A	−0.6 (2)	C9—C10—C11—C12	−0.60 (18)
C3A—C4A—C5A—C6A	2.1 (2)	C10—C11—C12—N1	0.01 (18)
C4A—C5A—C6A—C1A	−1.49 (18)	C8—N1—C12—C11	−0.18 (18)
C4A—C5A—C6A—C7A	177.79 (11)	C6B—C1B—C2B—C3B	0.4 (2)
C2A—C1A—C6A—C5A	−0.64 (18)	C1B—C2B—C3B—C4B	−0.9 (2)
C2A—C1A—C6A—C7A	−179.92 (11)	C2B—C3B—C4B—C5B	0.3 (2)
C5A—C6A—C7A—O2A	20.53 (16)	C3B—C4B—C5B—C6B	0.7 (2)
C1A—C6A—C7A—O2A	−160.20 (11)	C4B—C5B—C6B—C1B	−1.17 (19)
C5A—C6A—C7A—O1A	−160.22 (11)	C4B—C5B—C6B—C7B	−179.87 (11)
C1A—C6A—C7A—O1A	19.05 (16)	C2B—C1B—C6B—C5B	0.6 (2)
C12—N1—C8—N2	−179.66 (11)	C2B—C1B—C6B—C7B	179.24 (12)
C12—N1—C8—C9	0.88 (17)	C5B—C6B—C7B—O2B	9.93 (17)
N2—C8—C9—N3	−0.17 (18)	C1B—C6B—C7B—O2B	−168.74 (12)
N1—C8—C9—N3	179.27 (11)	C5B—C6B—C7B—O1B	−170.02 (11)
N2—C8—C9—C10	179.17 (11)	C1B—C6B—C7B—O1B	11.31 (17)
N1—C8—C9—C10	−1.39 (16)

D—H···A	D—H	H···A	D···A	D—H···A
O1B—H1OB···O1A	0.93 (2)	1.66 (2)	2.5796 (13)	173 (2)
N1—H1N1···O1A	0.89 (2)	2.35 (2)	3.0786 (13)	140 (1)
N1—H1N1···O2A	0.89 (2)	2.01 (2)	2.8514 (13)	158 (2)
N2—H1N2···O2Ai	0.87 (2)	2.07 (2)	2.9370 (14)	173 (2)
N2—H2N2···O1A	0.87 (2)	2.08 (2)	2.9038 (14)	157 (2)
N3—H1N3···O2Ai	0.88 (2)	2.18 (2)	3.0543 (15)	175 (2)
N3—H2N3···O1Aii	0.86 (2)	2.59 (2)	3.0649 (14)	116 (1)
N3—H2N3···O2Bii	0.86 (2)	2.16 (2)	2.9912 (15)	162 (1)
C10—H10A···O2Bii	0.93	2.58	3.3375 (14)	138

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1B—H1OB⋯O1A	0.93 (2)	1.66 (2)	2.5796 (13)	173 (2)
N1—H1N1⋯O1A	0.89 (2)	2.35 (2)	3.0786 (13)	140 (1)
N1—H1N1⋯O2A	0.89 (2)	2.01 (2)	2.8514 (13)	158 (2)
N2—H1N2⋯O2Ai	0.87 (2)	2.07 (2)	2.9370 (14)	173 (2)
N2—H2N2⋯O1A	0.87 (2)	2.08 (2)	2.9038 (14)	157 (2)
N3—H1N3⋯O2Ai	0.88 (2)	2.18 (2)	3.0543 (15)	175 (2)
N3—H2N3⋯O1Aii	0.86 (2)	2.59 (2)	3.0649 (14)	116 (1)
N3—H2N3⋯O2Bii	0.86 (2)	2.16 (2)	2.9912 (15)	162 (1)
C10—H10A⋯O2Bii	0.93	2.58	3.3375 (14)	138

Symmetry codes: (i) ; (ii) .