2,3-Diamino-pyridinium 4-carb-oxy-butano-ate.

In the title mol-ecular salt, C(5)H(8)N(3) (+)·C(5)H(7)O(4) (-), the 2,3-diamino-pyridine mol-ecule is protonated at the pyridine N atom. The cation is essentially planar, with a maximum deviation of 0.015 (2) Å, and the anion adopts an extended conformation. In the crystal, the hydrogen glutarate (4-carb-oxy-butano-ate) anions are self-assembled through O-H⋯O hydrogen bonds, forming chains. The cations are connected to the anion chains via N-H⋯O hydrogen bonds, forming a three-dimensional network. The crystal structure also features aromatic π-π inter-actions between the pyridinium cations, with a centroid-centroid distance of 3.4464 (10) Å.

Related literature

For applications of 2-amino­pyridine derivatives, see: Bis et al. (2006 ▶); Gellert & Hsu (1988 ▶). For n class="Chemical">glutaric acid conformations, see: Saraswathi et al. (2001 ▶). 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 +·n class="Chemical">C5H7O4 −

M = 241.25

Monoclinic,

a = 7.7052 (1) Å

b = 21.4626 (4) Å

c = 7.8450 (1) Å

β = 119.473 (1)°

V = 1129.46 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 100 K

0.35 × 0.18 × 0.05 mm

Data collection

Bruker APEXII DUO CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.962, T max = 0.994

9826 measured reflections

3281 independent reflections

2475 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.123

S = 1.04

3281 reflections

191 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.43 e Å−3

Δρmin = −0.35 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAIn class="Chemical">NT; 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 datablock(s) global, I. DOI: 10.1107/S1600536811044473/hb6458sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811044473/hb6458Isup2.hkl

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

C5H8N3+·C5H7O4−	F(000) = 512
Mr = 241.25	Dx = 1.419 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3028 reflections
a = 7.7052 (1) Å	θ = 3.1–30.0°
b = 21.4626 (4) Å	µ = 0.11 mm−1
c = 7.8450 (1) Å	T = 100 K
β = 119.473 (1)°	Plate, brown
V = 1129.46 (3) Å3	0.35 × 0.18 × 0.05 mm
Z = 4

Bruker APEXII DUO CCD diffractometer	3281 independent reflections
Radiation source: fine-focus sealed tube	2475 reflections with I > 2σ(I)
graphite	Rint = 0.030
φ and ω scans	θmax = 30.1°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→9
Tmin = 0.962, Tmax = 0.994	k = −30→16
9826 measured reflections	l = −11→10

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) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0439P)2 + 0.6889P] where P = (Fo2 + 2Fc2)/3
3281 reflections	(Δ/σ)max = 0.001
191 parameters	Δρmax = 0.43 e Å−3
0 restraints	Δρmin = −0.35 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 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 > 2σ(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	0.1547 (2)	0.91493 (6)	1.0497 (2)	0.0199 (3)
H1N1	0.1763	0.8895	1.1428	0.024*
N2	0.4178 (2)	0.97294 (6)	1.27871 (19)	0.0227 (3)
H2N1	0.4358	0.9454	1.3657	0.027*
H2N2	0.4941	1.0051	1.3105	0.027*
N3	0.3437 (2)	1.06274 (6)	0.9866 (2)	0.0236 (3)
H3N1	0.3206	1.0897	0.8967	0.028*
H3N2	0.4382	1.0690	1.1044	0.028*
C1	0.2710 (2)	0.96571 (7)	1.0940 (2)	0.0174 (3)
C2	0.2301 (2)	1.00984 (7)	0.9422 (2)	0.0179 (3)
C3	0.0765 (3)	0.99662 (8)	0.7572 (2)	0.0218 (3)
C4	−0.0356 (3)	0.94140 (8)	0.7180 (2)	0.0243 (3)
C5	0.0045 (2)	0.90133 (8)	0.8661 (2)	0.0230 (3)
O1	0.37775 (18)	0.91001 (5)	0.58579 (17)	0.0259 (3)
O2	0.14921 (17)	0.85057 (5)	0.35117 (16)	0.0231 (3)
O3	0.89545 (17)	0.73680 (5)	0.77123 (18)	0.0250 (3)
H1O1	0.9696	0.7065	0.8003	0.037*
O4	0.68383 (19)	0.66708 (5)	0.78111 (19)	0.0286 (3)
C6	0.2633 (2)	0.86410 (7)	0.5313 (2)	0.0184 (3)
C7	0.2679 (2)	0.81908 (7)	0.6837 (2)	0.0180 (3)
C8	0.3856 (2)	0.76040 (7)	0.6920 (2)	0.0177 (3)
C9	0.5983 (2)	0.77618 (7)	0.7421 (2)	0.0181 (3)
C10	0.7278 (2)	0.72033 (7)	0.7669 (2)	0.0190 (3)
H3A	0.044 (3)	1.0263 (9)	0.654 (3)	0.031 (5)*
H4A	−0.143 (3)	0.9321 (9)	0.589 (3)	0.031 (5)*
H5A	−0.066 (3)	0.8624 (9)	0.854 (3)	0.026 (5)*
H7A	0.331 (3)	0.8398 (8)	0.812 (3)	0.019 (4)*
H7B	0.131 (3)	0.8081 (9)	0.649 (3)	0.025 (5)*
H8A	0.317 (3)	0.7388 (8)	0.562 (3)	0.019 (4)*
H8B	0.389 (3)	0.7319 (8)	0.792 (3)	0.018 (4)*
H9A	0.601 (3)	0.8033 (9)	0.642 (3)	0.025 (5)*
H9B	0.664 (3)	0.8000 (9)	0.867 (3)	0.028 (5)*

	U11	U22	U33	U12	U13	U23
N1	0.0211 (6)	0.0171 (6)	0.0228 (7)	−0.0007 (5)	0.0118 (5)	0.0011 (5)
N2	0.0241 (7)	0.0215 (6)	0.0182 (7)	−0.0050 (5)	0.0071 (6)	0.0039 (5)
N3	0.0300 (7)	0.0199 (6)	0.0181 (6)	−0.0049 (5)	0.0097 (6)	0.0028 (5)
C1	0.0182 (7)	0.0157 (7)	0.0196 (7)	0.0011 (5)	0.0102 (6)	0.0001 (5)
C2	0.0208 (7)	0.0160 (6)	0.0192 (7)	0.0014 (5)	0.0117 (6)	0.0006 (5)
C3	0.0251 (8)	0.0238 (8)	0.0168 (7)	0.0010 (6)	0.0105 (6)	0.0009 (6)
C4	0.0223 (8)	0.0294 (8)	0.0189 (8)	−0.0003 (6)	0.0085 (7)	−0.0058 (6)
C5	0.0218 (8)	0.0218 (8)	0.0272 (8)	−0.0022 (6)	0.0134 (7)	−0.0072 (6)
O1	0.0285 (6)	0.0209 (6)	0.0233 (6)	−0.0069 (5)	0.0091 (5)	0.0011 (4)
O2	0.0226 (6)	0.0232 (6)	0.0196 (6)	−0.0046 (4)	0.0073 (5)	0.0025 (4)
O3	0.0194 (6)	0.0228 (6)	0.0316 (7)	0.0047 (4)	0.0117 (5)	0.0022 (5)
O4	0.0326 (7)	0.0179 (6)	0.0386 (7)	0.0018 (5)	0.0200 (6)	−0.0013 (5)
C6	0.0172 (7)	0.0160 (7)	0.0214 (8)	0.0018 (5)	0.0090 (6)	0.0020 (5)
C7	0.0191 (7)	0.0174 (7)	0.0190 (7)	−0.0002 (6)	0.0105 (6)	0.0006 (5)
C8	0.0208 (7)	0.0154 (6)	0.0180 (7)	0.0004 (5)	0.0104 (6)	0.0016 (5)
C9	0.0192 (7)	0.0155 (7)	0.0189 (7)	0.0015 (5)	0.0088 (6)	0.0005 (5)
C10	0.0219 (7)	0.0187 (7)	0.0147 (7)	0.0020 (6)	0.0076 (6)	−0.0013 (5)

N1—C1	1.3435 (19)	O1—C6	1.2491 (18)
N1—C5	1.364 (2)	O2—C6	1.2774 (19)
N1—H1N1	0.8600	O3—C10	1.3235 (19)
N2—C1	1.338 (2)	O3—H1O1	0.8200
N2—H2N1	0.8600	O4—C10	1.2125 (19)
N2—H2N2	0.8600	C6—C7	1.524 (2)
N3—C2	1.3698 (19)	C7—C8	1.535 (2)
N3—H3N1	0.8600	C7—H7A	0.981 (18)
N3—H3N2	0.8600	C7—H7B	0.98 (2)
C1—C2	1.430 (2)	C8—C9	1.523 (2)
C2—C3	1.378 (2)	C8—H8A	0.999 (18)
C3—C4	1.408 (2)	C8—H8B	0.987 (18)
C3—H3A	0.96 (2)	C9—C10	1.510 (2)
C4—C5	1.353 (2)	C9—H9A	0.98 (2)
C4—H4A	0.96 (2)	C9—H9B	1.00 (2)
C5—H5A	0.97 (2)
C1—N1—C5	123.94 (14)	O1—C6—O2	122.93 (14)
C1—N1—H1N1	118.0	O1—C6—C7	119.46 (14)
C5—N1—H1N1	118.0	O2—C6—C7	117.48 (13)
C1—N2—H2N1	120.0	C6—C7—C8	109.78 (12)
C1—N2—H2N2	120.0	C6—C7—H7A	108.9 (11)
H2N1—N2—H2N2	120.0	C8—C7—H7A	110.1 (11)
C2—N3—H3N1	120.0	C6—C7—H7B	109.2 (11)
C2—N3—H3N2	120.0	C8—C7—H7B	110.4 (11)
H3N1—N3—H3N2	120.0	H7A—C7—H7B	108.4 (16)
N2—C1—N1	118.36 (13)	C9—C8—C7	111.52 (12)
N2—C1—C2	123.19 (14)	C9—C8—H8A	109.1 (10)
N1—C1—C2	118.44 (14)	C7—C8—H8A	109.5 (10)
N3—C2—C3	123.32 (14)	C9—C8—H8B	109.2 (10)
N3—C2—C1	119.05 (14)	C7—C8—H8B	109.0 (10)
C3—C2—C1	117.63 (14)	H8A—C8—H8B	108.5 (14)
C2—C3—C4	121.33 (15)	C10—C9—C8	114.57 (13)
C2—C3—H3A	118.8 (13)	C10—C9—H9A	107.5 (12)
C4—C3—H3A	119.9 (12)	C8—C9—H9A	111.5 (12)
C5—C4—C3	119.41 (15)	C10—C9—H9B	107.4 (11)
C5—C4—H4A	119.1 (12)	C8—C9—H9B	109.1 (12)
C3—C4—H4A	121.5 (12)	H9A—C9—H9B	106.4 (16)
C4—C5—N1	119.17 (15)	O4—C10—O3	124.24 (14)
C4—C5—H5A	125.4 (12)	O4—C10—C9	124.27 (15)
N1—C5—H5A	115.4 (11)	O3—C10—C9	111.48 (13)
C10—O3—H1O1	109.5
C5—N1—C1—N2	−177.92 (14)	C3—C4—C5—N1	−0.9 (2)
C5—N1—C1—C2	3.0 (2)	C1—N1—C5—C4	−1.6 (2)
N2—C1—C2—N3	−1.0 (2)	O1—C6—C7—C8	−101.51 (16)
N1—C1—C2—N3	178.07 (14)	O2—C6—C7—C8	74.36 (17)
N2—C1—C2—C3	179.09 (15)	C6—C7—C8—C9	58.61 (16)
N1—C1—C2—C3	−1.8 (2)	C7—C8—C9—C10	175.91 (13)
N3—C2—C3—C4	179.59 (15)	C8—C9—C10—O4	−12.6 (2)
C1—C2—C3—C4	−0.5 (2)	C8—C9—C10—O3	167.48 (13)
C2—C3—C4—C5	1.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O2i	0.86	1.94	2.7571 (18)	159
N2—H2N1···O1i	0.86	2.13	2.9077 (19)	151
N2—H2N2···O1ii	0.86	2.04	2.8766 (18)	164
N3—H3N1···O4iii	0.86	2.16	3.0054 (18)	168
N3—H3N2···O1ii	0.86	2.17	3.0194 (18)	167
O3—H1O1···O2iv	0.82	1.74	2.5546 (18)	171

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O2i	0.86	1.94	2.7571 (18)	159
N2—H2N1⋯O1i	0.86	2.13	2.9077 (19)	151
N2—H2N2⋯O1ii	0.86	2.04	2.8766 (18)	164
N3—H3N1⋯O4iii	0.86	2.16	3.0054 (18)	168
N3—H3N2⋯O1ii	0.86	2.17	3.0194 (18)	167
O3—H1O1⋯O2iv	0.82	1.74	2.5546 (18)	171

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