2,3-Diamino-pyridinium 3-amino-benzoate.

In the title salt, C(5)H(8)N(3) (+)·C(7)H(6)NO(2) (-), the pyridine N atom of the 2,3-diamino-pyridine mol-ecule is protonated. The proton-ated N atom and one of the two N atoms of the 2-amino groups are hydrogen bonded to the 3-amino-benzoate anion through a pair of N-H⋯O hydrogen bonds, forming an R(2) (2)(8) ring motif. The carboxyl-ate mean plane of the 3-amino-benzoate anion is twisted by 8.81 (7)° from the attached ring. The crystal structure is further stabilized by π-π inter-actions [centroid-centroid distance 3.6827 (7) Å].

Related literature

For substituted pyridines, see: Pozharski et al. (1997 ▶); Katritzky et al. (1996 ▶). For n class="Chemical">hydrogen bonding in pyridine and its substituted derivatives, see: Jeffrey & Saenger (1991 ▶); Jeffrey (1997 ▶); Scheiner (1997 ▶). For related structures, see: Fun & Balasubramani (2009 ▶); Balasubramani & Fun (2009a ▶,b ▶). For bond-length data, see: Allen et al. (1987 ▶). 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 +·n class="Chemical">C7H6NO2 −

M = 246.27

Monoclinic,

a = 9.9119 (2) Å

b = 10.1751 (2) Å

c = 12.4060 (2) Å

β = 106.811 (1)°

V = 1197.73 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 100 K

0.46 × 0.14 × 0.06 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.957, T max = 0.994

19514 measured reflections

4434 independent reflections

2965 reflections with I > 2σ(I)

R int = 0.046

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.142

S = 1.06

4434 reflections

219 parameters

All H-atom parameters refined

Δρmax = 0.33 e Å−3

Δρmin = −0.23 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/S1600536809024362/bt2977sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809024362/bt2977Isup2.hkl

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

C5H8N3+·C7H6NO2−	F(000) = 520
Mr = 246.27	Dx = 1.366 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3436 reflections
a = 9.9119 (2) Å	θ = 2.9–32.6°
b = 10.1751 (2) Å	µ = 0.10 mm−1
c = 12.4060 (2) Å	T = 100 K
β = 106.811 (1)°	Plate, brown
V = 1197.73 (4) Å3	0.46 × 0.14 × 0.06 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	4434 independent reflections
Radiation source: fine-focus sealed tube	2965 reflections with I > 2σ(I)
graphite	Rint = 0.046
φ and ω scans	θmax = 32.8°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −14→15
Tmin = 0.957, Tmax = 0.994	k = −12→15
19514 measured reflections	l = −18→18

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.142	All H-atom parameters refined
S = 1.06	w = 1/[σ2(Fo2) + (0.0681P)2 + 0.0752P] where P = (Fo2 + 2Fc2)/3
4434 reflections	(Δ/σ)max < 0.001
219 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.23 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 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
N1	0.45804 (11)	0.32315 (11)	0.46427 (8)	0.0219 (2)
N2	0.56864 (12)	0.28026 (12)	0.32806 (9)	0.0252 (2)
N3	0.36894 (13)	0.43692 (12)	0.17546 (9)	0.0275 (2)
C8	0.46690 (12)	0.34222 (12)	0.35929 (10)	0.0199 (2)
C9	0.36669 (13)	0.42721 (12)	0.28567 (10)	0.0223 (2)
C10	0.26897 (14)	0.48893 (14)	0.32782 (11)	0.0276 (3)
C11	0.26420 (14)	0.46612 (14)	0.43889 (12)	0.0286 (3)
C12	0.35938 (13)	0.38245 (13)	0.50509 (11)	0.0252 (3)
H10	0.1974 (16)	0.5508 (16)	0.2749 (13)	0.032 (4)*
H11	0.1881 (16)	0.5151 (16)	0.4685 (13)	0.033 (4)*
H12	0.3671 (16)	0.3657 (15)	0.5851 (13)	0.028 (4)*
H1N1	0.5279 (18)	0.2611 (17)	0.5122 (14)	0.040 (5)*
H1N2	0.6338 (18)	0.2303 (17)	0.3822 (15)	0.040 (5)*
H2N2	0.5864 (19)	0.2985 (18)	0.2620 (16)	0.045 (5)*
H1N3	0.453 (2)	0.4228 (19)	0.1593 (16)	0.056 (6)*
H2N3	0.311 (2)	0.504 (2)	0.1305 (16)	0.053 (5)*
C4	0.96875 (12)	−0.19646 (13)	0.66376 (10)	0.0226 (2)
C5	0.89408 (12)	−0.08847 (12)	0.60585 (10)	0.0206 (2)
H1	0.7131 (18)	−0.0025 (17)	0.7829 (14)	0.042 (5)*
H2	0.8458 (18)	−0.1824 (17)	0.8828 (15)	0.039 (4)*
H3	1.0060 (16)	−0.3052 (16)	0.8108 (13)	0.032 (4)*
H5	0.9082 (15)	−0.0651 (14)	0.5321 (12)	0.023 (4)*
C6	0.80059 (12)	−0.01887 (12)	0.64902 (9)	0.0191 (2)
C7	0.72259 (12)	0.09741 (12)	0.58352 (9)	0.0198 (2)
O1	0.75796 (9)	0.13487 (9)	0.49856 (7)	0.0232 (2)
O2	0.62586 (10)	0.15115 (9)	0.61617 (7)	0.0259 (2)
N4	1.05563 (14)	−0.26916 (14)	0.61717 (11)	0.0347 (3)
C1	0.78080 (13)	−0.05510 (13)	0.75193 (10)	0.0231 (2)
C2	0.85824 (14)	−0.16013 (13)	0.81132 (11)	0.0261 (3)
C3	0.94998 (13)	−0.23049 (13)	0.76778 (11)	0.0249 (3)
H1N4	1.097 (2)	−0.224 (2)	0.5680 (17)	0.057 (6)*
H2N4	1.109 (2)	−0.329 (2)	0.6604 (17)	0.053 (5)*

	U11	U22	U33	U12	U13	U23
N1	0.0232 (5)	0.0234 (5)	0.0198 (5)	0.0005 (4)	0.0075 (4)	0.0013 (4)
N2	0.0283 (5)	0.0289 (6)	0.0206 (5)	0.0065 (4)	0.0105 (4)	0.0062 (4)
N3	0.0298 (6)	0.0314 (6)	0.0196 (5)	0.0039 (5)	0.0045 (4)	0.0048 (4)
C8	0.0208 (5)	0.0193 (5)	0.0196 (5)	−0.0018 (4)	0.0059 (4)	0.0005 (4)
C9	0.0225 (5)	0.0220 (6)	0.0204 (5)	−0.0007 (5)	0.0031 (4)	0.0010 (4)
C10	0.0238 (6)	0.0285 (7)	0.0283 (6)	0.0038 (5)	0.0041 (5)	0.0003 (5)
C11	0.0252 (6)	0.0307 (7)	0.0310 (7)	0.0016 (5)	0.0097 (5)	−0.0041 (5)
C12	0.0262 (6)	0.0280 (7)	0.0234 (6)	−0.0009 (5)	0.0104 (5)	−0.0029 (5)
C4	0.0201 (5)	0.0230 (6)	0.0257 (6)	−0.0015 (5)	0.0083 (4)	0.0014 (5)
C5	0.0209 (5)	0.0223 (6)	0.0187 (5)	−0.0014 (4)	0.0057 (4)	0.0012 (4)
C6	0.0200 (5)	0.0196 (5)	0.0171 (5)	−0.0019 (4)	0.0043 (4)	−0.0002 (4)
C7	0.0231 (5)	0.0207 (6)	0.0151 (5)	−0.0020 (4)	0.0046 (4)	−0.0015 (4)
O1	0.0251 (4)	0.0266 (5)	0.0183 (4)	0.0010 (4)	0.0072 (3)	0.0034 (3)
O2	0.0318 (5)	0.0272 (5)	0.0213 (4)	0.0078 (4)	0.0116 (4)	0.0033 (3)
N4	0.0351 (6)	0.0352 (7)	0.0405 (7)	0.0139 (5)	0.0216 (5)	0.0126 (6)
C1	0.0257 (6)	0.0234 (6)	0.0217 (6)	0.0010 (5)	0.0096 (5)	0.0016 (5)
C2	0.0302 (6)	0.0279 (7)	0.0223 (6)	0.0012 (5)	0.0107 (5)	0.0061 (5)
C3	0.0235 (6)	0.0243 (6)	0.0273 (6)	0.0016 (5)	0.0078 (5)	0.0067 (5)

N1—C8	1.3445 (15)	C4—N4	1.3822 (17)
N1—C12	1.3650 (16)	C4—C3	1.3995 (17)
N1—H1N1	0.997 (18)	C4—C5	1.4013 (17)
N2—C8	1.3382 (16)	C5—C6	1.3907 (16)
N2—H1N2	0.936 (18)	C5—H5	0.994 (14)
N2—H2N2	0.906 (19)	C6—C1	1.3961 (16)
N3—C9	1.3775 (16)	C6—C7	1.5147 (17)
N3—H1N3	0.92 (2)	C7—O1	1.2621 (14)
N3—H2N3	0.96 (2)	C7—O2	1.2677 (14)
C8—C9	1.4296 (16)	N4—H1N4	0.95 (2)
C9—C10	1.3781 (18)	N4—H2N4	0.88 (2)
C10—C11	1.4115 (19)	C1—C2	1.3954 (18)
C10—H10	1.030 (16)	C1—H1	1.017 (17)
C11—C12	1.3569 (19)	C2—C3	1.3839 (18)
C11—H11	1.054 (16)	C2—H2	0.957 (17)
C12—H12	0.988 (15)	C3—H3	1.000 (16)
C8—N1—C12	123.37 (11)	N4—C4—C3	121.21 (12)
C8—N1—H1N1	116.1 (10)	N4—C4—C5	120.39 (11)
C12—N1—H1N1	120.5 (10)	C3—C4—C5	118.38 (11)
C8—N2—H1N2	118.0 (10)	C6—C5—C4	120.92 (11)
C8—N2—H2N2	121.7 (12)	C6—C5—H5	121.3 (8)
H1N2—N2—H2N2	119.1 (15)	C4—C5—H5	117.7 (8)
C9—N3—H1N3	118.6 (12)	C5—C6—C1	120.21 (11)
C9—N3—H2N3	116.7 (11)	C5—C6—C7	118.99 (10)
H1N3—N3—H2N3	114.2 (16)	C1—C6—C7	120.79 (11)
N2—C8—N1	118.57 (11)	O1—C7—O2	123.71 (11)
N2—C8—C9	122.86 (11)	O1—C7—C6	117.51 (10)
N1—C8—C9	118.57 (11)	O2—C7—C6	118.77 (10)
N3—C9—C10	123.98 (12)	C4—N4—H1N4	116.5 (12)
N3—C9—C8	118.02 (11)	C4—N4—H2N4	117.0 (12)
C10—C9—C8	117.90 (11)	H1N4—N4—H2N4	115.6 (17)
C9—C10—C11	121.41 (12)	C2—C1—C6	118.93 (12)
C9—C10—H10	117.8 (8)	C2—C1—H1	121.7 (10)
C11—C10—H10	120.8 (8)	C6—C1—H1	119.3 (10)
C12—C11—C10	118.71 (12)	C3—C2—C1	120.88 (12)
C12—C11—H11	121.8 (9)	C3—C2—H2	121.0 (10)
C10—C11—H11	119.4 (9)	C1—C2—H2	118.1 (10)
C11—C12—N1	120.00 (12)	C2—C3—C4	120.64 (12)
C11—C12—H12	123.7 (9)	C2—C3—H3	120.7 (9)
N1—C12—H12	116.1 (9)	C4—C3—H3	118.6 (9)
C12—N1—C8—N2	179.31 (11)	C4—C5—C6—C1	0.65 (18)
C12—N1—C8—C9	−1.04 (17)	C4—C5—C6—C7	179.83 (11)
N2—C8—C9—N3	5.26 (18)	C5—C6—C7—O1	−7.75 (16)
N1—C8—C9—N3	−174.37 (11)	C1—C6—C7—O1	171.43 (11)
N2—C8—C9—C10	−178.13 (12)	C5—C6—C7—O2	171.97 (11)
N1—C8—C9—C10	2.23 (17)	C1—C6—C7—O2	−8.85 (17)
N3—C9—C10—C11	174.31 (12)	C5—C6—C1—C2	1.28 (18)
C8—C9—C10—C11	−2.08 (19)	C7—C6—C1—C2	−177.89 (11)
C9—C10—C11—C12	0.7 (2)	C6—C1—C2—C3	−2.1 (2)
C10—C11—C12—N1	0.6 (2)	C1—C2—C3—C4	1.0 (2)
C8—N1—C12—C11	−0.41 (19)	N4—C4—C3—C2	−177.33 (13)
N4—C4—C5—C6	176.53 (12)	C5—C4—C3—C2	0.93 (19)
C3—C4—C5—C6	−1.75 (18)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N2···O2i	0.91 (2)	2.02 (2)	2.9293 (14)	177.1 (17)
N3—H1N3···O2i	0.92 (2)	2.08 (2)	2.9854 (16)	167.3 (18)
N3—H2N3···O1ii	0.96 (2)	2.04 (2)	2.9544 (14)	158.1 (16)
N4—H1N4···O1iii	0.95 (2)	2.06 (2)	2.9794 (15)	162.3 (18)
N1—H1N1···O2	0.99 (2)	1.77 (2)	2.7510 (13)	167.1 (15)
N2—H1N2···O1	0.94 (2)	1.87 (2)	2.8086 (14)	175.7 (16)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N2⋯O2i	0.91 (2)	2.02 (2)	2.9293 (14)	177.1 (17)
N3—H1N3⋯O2i	0.92 (2)	2.08 (2)	2.9854 (16)	167.3 (18)
N3—H2N3⋯O1ii	0.96 (2)	2.04 (2)	2.9544 (14)	158.1 (16)
N4—H1N4⋯O1iii	0.95 (2)	2.06 (2)	2.9794 (15)	162.3 (18)
N1—H1N1⋯O2	0.99 (2)	1.77 (2)	2.7510 (13)	167.1 (15)
N2—H1N2⋯O1	0.94 (2)	1.87 (2)	2.8086 (14)	175.7 (16)

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