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In the title compound, 2C5H7N2+·C4H4O42−·C4H6O4, cyclic eight-membered hydrogen-bonded rings exist involving 2-amino­pyridinium and succinate ions. The succinic acid and succinate moieties lie on inversion centres. Succinic acid mol­ecules and succinate ions are linked into zigzag chains by O—H...O hydrogen bonds, with O...O distances of 2.6005 (16) Å.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102017808/fr1391sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102017808/fr1391Isup2.hkl
Contains datablock I

CCDC reference: 199445

Comment top

Hydrogen bonding plays a key role in molecular recognition (Goswami & Ghosh, 1997) and crystal engineering research (Goswami et al., 1998). The design of highly specific solid-state structures is of considerable significance in organic chemistry, due to their important applications in the development of new optical, magnetic and electronic systems (Lehn, 1990). Our investigation of the title compound, (I), shows that the 2-aminopyridinium ions are linked to the succinate ions by N1—H···O3 and N2—H2NA···O4 hydrogen bonds, resulting in the formation of cyclic eight-membered hydrogen-bonded rings. \sch

Each amino H atom in (I) is involved in a single hydrogen bond, one in the cyclic eight-membered hydrogen-bonded ring system and the other to another succinate ion (Fig. 1). The 2-aminopyridinium-succinate-succinic acid units are arranged so that a two-dimensional network of intermolecular N2—H2NB···O4 and O2—H6···O3 hydrogen bonds exists on each nearly perpendicular 2-aminopyridinium-succinate-succinic acid unit [dihedral angle 84.34 (8)°] (Fig. 2).

2-Aminopyridine, like other organic bases, is protonated in acidic solutions. The bonding of the H atom to the ring N atom of 2-aminopyridine, but not to the amino N atom, gives an ion for which an additional resonance structure can be written. As this monocation has more resonance energy (additional ionic resonance) than 2-aminopyridine itself, 2-aminopyridine is a strong base, like amidines (Acheson, 1967).

The present investigation clearly shows that the positive charge in (I) is on the amino group in the crystal, with hydrogen bonds. The C1—N2 bond length is 1.3272 (19) Å, and this is approximately equal to the CN double bond (Shanmuga Sundara Raj, Fun, Lu et al., 2000). This is also supported by the C1—N2—H2NA angle of 118.4 (11)° and by the fact that atoms C1, N2, H2NA and H2NB lie in the pyridine plane, with a maximum deviation of 0.04 (2) Å for atom H2NB. Similar C1—N2 bonds have also been observed in other 2-aminopyridine-containing molecules (Yang et al., 1995; Grobelny et al., 1995; Shanmuga Sundara Raj, Fun, Zhao et al., 2000).

Experimental top

The title compound was prepared by mixing 2-aminopyridine and succinic acid in a 1:1 molar ratio in water at 353 K, and crystals of (I) were obtained by slow evaporation of the solvent.

Refinement top

All H atom parameters were freely refined, with C—H distances in the range 0.92 (2)–0.982 (15) Å, and Uiso(H) in the range 0.039 (4)–0.075 (6) Å2.

Computing details top

Data collection: XSCANS (Siemens, 1991); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: WinGX (Farrugia, 1997).

Figures top
[Figure 1] Fig. 1. A view of the three moieties of (I), with 50% probability ellipsoids.
[Figure 2] Fig. 2. A packing diagram of the crystal structure of (I) along the b axis.
2-Aminopyridinium-succinate-succinic acid (2/1/1) top
Crystal data top
2C5H7N2+·C4H4O42·C4H6O4Dx = 1.436 Mg m3
Mr = 424.41Melting point = 433–436 K
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 10.228 (2) ÅCell parameters from 35 reflections
b = 5.184 (1) Åθ = 5–25°
c = 19.047 (4) ŵ = 0.11 mm1
β = 103.60 (3)°T = 153 K
V = 981.6 (4) Å3Rectangular, light yellow
Z = 20.3 × 0.2 × 0.2 mm
F(000) = 448
Data collection top
Siemens P4
diffractometer
Rint = 0.000
Radiation source: fine-focus sealed tubeθmax = 28.0°, θmin = 2.1°
Graphite monochromatorh = 1313
ω scansk = 06
2362 measured reflectionsl = 025
2362 independent reflections1 standard reflections every 120 min
1690 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037All H-atom parameters refined
wR(F2) = 0.104 w = 1/[σ2(Fo2) + (0.0496P)2 + 0.0805P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.001
2362 reflectionsΔρmax = 0.29 e Å3
185 parametersΔρmin = 0.19 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.015 (3)
Crystal data top
2C5H7N2+·C4H4O42·C4H6O4V = 981.6 (4) Å3
Mr = 424.41Z = 2
Monoclinic, P21/cMo Kα radiation
a = 10.228 (2) ŵ = 0.11 mm1
b = 5.184 (1) ÅT = 153 K
c = 19.047 (4) Å0.3 × 0.2 × 0.2 mm
β = 103.60 (3)°
Data collection top
Siemens P4
diffractometer
Rint = 0.000
2362 measured reflections1 standard reflections every 120 min
2362 independent reflections intensity decay: none
1690 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.104All H-atom parameters refined
S = 1.02Δρmax = 0.29 e Å3
2362 reflectionsΔρmin = 0.19 e Å3
185 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.30382 (13)0.4452 (3)0.76566 (7)0.0318 (3)
N10.25392 (12)0.6394 (2)0.71999 (6)0.0343 (3)
H1N0.2823 (17)0.661 (3)0.6753 (10)0.054 (5)*
O10.10349 (12)0.1882 (3)0.59636 (6)0.0568 (4)
C20.25934 (15)0.4253 (3)0.83038 (8)0.0365 (3)
H20.2968 (16)0.286 (3)0.8638 (9)0.043 (4)*
N20.39039 (14)0.2813 (3)0.74790 (8)0.0428 (3)
H2NA0.4196 (17)0.313 (3)0.7061 (10)0.049 (5)*
H2NB0.4221 (17)0.166 (4)0.7785 (10)0.049 (5)*
O20.21613 (12)0.1019 (2)0.51295 (6)0.0469 (3)
H60.255 (2)0.025 (4)0.5413 (11)0.073 (6)*
C30.16808 (15)0.5965 (3)0.84411 (8)0.0394 (4)
H30.1358 (15)0.584 (3)0.8886 (8)0.039 (4)*
O30.32876 (10)0.7216 (2)0.59400 (5)0.0411 (3)
C40.11800 (16)0.7937 (3)0.79499 (8)0.0410 (4)
H40.0564 (17)0.912 (3)0.8061 (9)0.049 (5)*
O40.49502 (10)0.4429 (2)0.62880 (5)0.0390 (3)
C50.16280 (15)0.8111 (3)0.73374 (8)0.0379 (4)
H50.1350 (15)0.941 (3)0.6971 (9)0.041 (4)*
C60.12474 (13)0.2267 (3)0.53772 (7)0.0327 (3)
C70.05024 (16)0.4226 (3)0.48564 (8)0.0371 (4)
H7A0.0095 (18)0.333 (4)0.4447 (10)0.055 (5)*
H7B0.1133 (19)0.528 (4)0.4726 (10)0.065 (6)*
C80.42447 (13)0.5836 (3)0.58213 (7)0.0293 (3)
C90.45189 (17)0.5993 (3)0.50755 (8)0.0376 (4)
H9A0.486 (2)0.773 (4)0.5036 (12)0.075 (6)*
H9B0.370 (2)0.600 (4)0.4732 (11)0.072 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0311 (7)0.0360 (8)0.0286 (7)0.0042 (6)0.0074 (5)0.0027 (6)
N10.0394 (6)0.0386 (7)0.0277 (6)0.0017 (5)0.0133 (5)0.0033 (5)
O10.0629 (8)0.0689 (9)0.0474 (7)0.0282 (7)0.0305 (6)0.0284 (6)
C20.0392 (8)0.0420 (9)0.0296 (7)0.0007 (7)0.0109 (6)0.0073 (7)
N20.0467 (8)0.0481 (8)0.0382 (7)0.0115 (7)0.0194 (6)0.0099 (7)
O20.0578 (7)0.0500 (7)0.0363 (6)0.0240 (6)0.0177 (5)0.0097 (5)
C30.0434 (8)0.0472 (9)0.0309 (7)0.0033 (7)0.0158 (6)0.0009 (7)
O30.0489 (6)0.0461 (6)0.0347 (5)0.0197 (5)0.0230 (5)0.0080 (5)
C40.0459 (9)0.0402 (9)0.0407 (8)0.0049 (7)0.0177 (7)0.0008 (7)
O40.0436 (6)0.0470 (6)0.0284 (5)0.0139 (5)0.0123 (4)0.0063 (5)
C50.0435 (8)0.0352 (8)0.0355 (8)0.0019 (7)0.0101 (6)0.0061 (7)
C60.0330 (7)0.0322 (7)0.0332 (7)0.0001 (6)0.0084 (6)0.0018 (6)
C70.0416 (8)0.0389 (9)0.0319 (8)0.0074 (7)0.0112 (6)0.0071 (7)
C80.0322 (7)0.0302 (7)0.0277 (6)0.0014 (6)0.0118 (5)0.0004 (6)
C90.0447 (9)0.0432 (9)0.0297 (7)0.0140 (7)0.0182 (6)0.0069 (7)
Geometric parameters (Å, º) top
C1—N21.3272 (19)O3—C81.2747 (16)
C1—N11.3500 (18)C4—C51.353 (2)
C1—C21.4145 (19)C4—H40.937 (18)
N1—C51.3578 (19)O4—C81.2413 (16)
N1—H1N0.969 (18)C5—H50.962 (17)
O1—C61.2038 (17)C6—C71.497 (2)
C2—C31.357 (2)C7—C7i1.504 (3)
C2—H20.978 (17)C7—H7A0.920 (18)
N2—H2NA0.929 (18)C7—H7B0.92 (2)
N2—H2NB0.84 (2)C8—C91.5135 (18)
O2—C61.3123 (17)C9—C9ii1.498 (3)
O2—H60.89 (2)C9—H9A0.98 (2)
C3—C41.399 (2)C9—H9B0.94 (2)
C3—H30.982 (15)
N2—C1—N1119.15 (13)C4—C5—H5124.7 (9)
N2—C1—C2123.11 (14)N1—C5—H5114.7 (9)
N1—C1—C2117.73 (13)O1—C6—O2123.44 (14)
C1—N1—C5122.50 (12)O1—C6—C7123.55 (13)
C1—N1—H1N120.4 (11)O2—C6—C7113.01 (12)
C5—N1—H1N117.1 (11)C6—C7—C7i113.93 (15)
C3—C2—C1119.81 (14)C6—C7—H7A106.0 (12)
C3—C2—H2122.6 (9)C7i—C7—H7A111.5 (11)
C1—C2—H2117.6 (9)C6—C7—H7B107.5 (12)
C1—N2—H2NA118.4 (11)C7i—C7—H7B111.3 (13)
C1—N2—H2NB116.6 (12)H7A—C7—H7B106.2 (16)
H2NA—N2—H2NB124.6 (16)O4—C8—O3122.95 (12)
C6—O2—H6113.7 (13)O4—C8—C9119.93 (12)
C2—C3—C4120.60 (14)O3—C8—C9117.11 (12)
C2—C3—H3120.6 (9)C9ii—C9—C8114.73 (16)
C4—C3—H3118.8 (9)C9ii—C9—H9A111.1 (13)
C5—C4—C3118.71 (15)C8—C9—H9A105.6 (13)
C5—C4—H4122.2 (11)C9ii—C9—H9B113.0 (13)
C3—C4—H4119.1 (11)C8—C9—H9B108.8 (12)
C4—C5—N1120.64 (15)H9A—C9—H9B102.7 (18)
N2—C1—N1—C5178.53 (14)C3—C4—C5—N10.4 (2)
C2—C1—N1—C50.8 (2)C1—N1—C5—C40.1 (2)
N2—C1—C2—C3178.40 (15)O1—C6—C7—C7i2.6 (3)
N1—C1—C2—C30.9 (2)O2—C6—C7—C7i177.09 (18)
C1—C2—C3—C40.4 (2)O4—C8—C9—C9ii11.1 (3)
C2—C3—C4—C50.3 (2)O3—C8—C9—C9ii169.72 (18)
Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O30.969 (18)1.751 (18)2.7185 (16)176.0 (17)
N2—H2NA···O40.929 (18)1.936 (19)2.8521 (18)168.2 (16)
N2—H2NB···O4iii0.84 (2)2.11 (2)2.9447 (19)167.7 (17)
O2—H6···O3iv0.89 (2)1.72 (2)2.6005 (16)178 (2)
Symmetry codes: (iii) x+1, y1/2, z+3/2; (iv) x, y1, z.

Experimental details

Crystal data
Chemical formula2C5H7N2+·C4H4O42·C4H6O4
Mr424.41
Crystal system, space groupMonoclinic, P21/c
Temperature (K)153
a, b, c (Å)10.228 (2), 5.184 (1), 19.047 (4)
β (°) 103.60 (3)
V3)981.6 (4)
Z2
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.3 × 0.2 × 0.2
Data collection
DiffractometerSiemens P4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
2362, 2362, 1690
Rint0.000
(sin θ/λ)max1)0.660
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.104, 1.02
No. of reflections2362
No. of parameters185
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.29, 0.19

Computer programs: XSCANS (Siemens, 1991), XSCANS, SHELXTL (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), WinGX (Farrugia, 1997).

Selected geometric parameters (Å, º) top
C1—N21.3272 (19)O2—C61.3123 (17)
C1—N11.3500 (18)O3—C81.2747 (16)
N1—C51.3578 (19)O4—C81.2413 (16)
O1—C61.2038 (17)
O1—C6—O2123.44 (14)O4—C8—O3122.95 (12)
N2—C1—N1—C5178.53 (14)O4—C8—C9—C9ii11.1 (3)
O1—C6—C7—C7i2.6 (3)O3—C8—C9—C9ii169.72 (18)
O2—C6—C7—C7i177.09 (18)
Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O30.969 (18)1.751 (18)2.7185 (16)176.0 (17)
N2—H2NA···O40.929 (18)1.936 (19)2.8521 (18)168.2 (16)
N2—H2NB···O4iii0.84 (2)2.11 (2)2.9447 (19)167.7 (17)
O2—H6···O3iv0.89 (2)1.72 (2)2.6005 (16)178 (2)
Symmetry codes: (iii) x+1, y1/2, z+3/2; (iv) x, y1, z.
 

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