Bis(2,6-diamino­pyridinium)–adipate–adipic acid–water (2/1/1/2)

Nevzat Karadayı

doi:10.1107/S1600536807055602

. 2007 Dec 18;64(Pt 1):o300. doi: 10.1107/S1600536807055602

Bis(2,6-diaminopyridinium)–adipate–adipic acid–water (2/1/1/2)

Nevzat Karadayı ^a,^*

PMCID: PMC2915349 PMID: 21200865

Abstract

The crystal structure of the title compound, 2C₅H₈N₃ ⁺·C₆H₈O₄ ²⁻·C₆H₁₀O₄·2H₂O, consists of aminopyridinium cations, adipate dianions, adipic acid molecules and disordered solvent water molecules [occupancies 0.50 (4) and 0.50 (4)]. Both the adipate and adipic acid are located across inversion centres. Eight-membered hydrogen-bonded rings exist involving aminopyridinium and adipate ions. Adipic acid molecules and adipate anions are linked into zigzag supramolecular chains by O—H⋯O hydrogen bonds.

Related literature

For general background, see: Lah et al. (2001 ▶); Yang et al. (1995 ▶); Goswami & Ghosh (1997 ▶); Lehn (1990 ▶). For related structures, see: Büyükgüngör & Odabaşoğlu (2002 ▶, 2006 ▶); Odabaşoğlu & Büyükgüngör (2006 ▶); Shanmuga Sundara Raj et al., (2000 ▶). For synthesis, see: Odabaşoğlu & Büyükgüngör (2006 ▶).

Experimental

Crystal data

2C₅H₈N₃ ⁺·C₆H₈O₄ ²⁻·C₆H₁₀O₄·2H₂O
M _r = 546.58
Triclinic,
a = 5.0645 (7) Å
b = 7.6261 (11) Å
c = 17.702 (3) Å
α = 87.861 (11)°
β = 85.169 (11)°
γ = 73.323 (11)°
V = 652.55 (18) Å³
Z = 1
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 296 (2) K
0.60 × 0.48 × 0.08 mm

Data collection

Stoe IPDS 2 diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T _min = 0.949, T _max = 0.993
7575 measured reflections
2996 independent reflections
2261 reflections with I > 2σ(I)
R _int = 0.043

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.118
S = 1.05
2996 reflections
192 parameters
17 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and PLATON (Spek, 2003 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807055602/xu2332sup1.cif

e-64-0o300-sup1.cif^{(17KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807055602/xu2332Isup2.hkl

e-64-0o300-Isup2.hkl^{(144KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.86	2.03	2.8917 (14)	175
N2—H2A⋯O4ⁱ	0.86	2.15	2.8589 (16)	139
N2—H2B⋯O5	0.86	2.25	3.0892 (18)	166
N3—H3A⋯O2	0.86	1.91	2.7729 (16)	178
N3—H3B⋯O2ⁱⁱ	0.86	2.06	2.8936 (17)	162
O3—H4A⋯O1ⁱⁱⁱ	0.829 (17)	1.688 (17)	2.5099 (15)	171 (3)
O5—H5A⋯O4^iv	0.824 (16)	1.972 (17)	2.7773 (15)	165 (2)
O5—H5B⋯O5^v	0.824 (19)	2.00 (2)	2.804 (3)	164 (5)
O5—H5C⋯O5^iv	0.823 (19)	2.01 (2)	2.819 (3)	168 (5)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

The author acknowledges the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS II diffractometer (purchased under grant F.279 of the University Research Fund). The author also thanks Professor Dr O. Büyükgüngör for collection of the X-ray data and Professor Dr M. Odabaşoğlu for the synthesis of the title compound.

supplementary crystallographic information

Comment

The title crystal is obtained with the reaction of 2-aminopyridine (used in hair and other dyes) and adipic acid (used to esters for plasticizers and as food additive). In addition, The cupper(II) complexes of 2-aminopyridinium carboxylates have important properties in the applications of pharmaceuticals, fungicides, oxygen transfer, oxidative addition, homogenous hydrogenation, gas occlusion compounds, and solvent extractions processes (Lah et al., 2001; Yang et al., 1995). Hydrogen bonding plays a key role in molecular recognition (Goswami & Ghosh, 1997). The design of highly specific solid-state structure is of considerable significance in organic chemistry due to their important applications in the development of new optical, magnetic and electronic systems (Lehn, 1990). This report concerns the x-ray structure analysis of the title complex. In the structure investigations show that the 2-aminopyridinium ions are linked to the adipate ions by N1—H1···O1 and N3—H3···O2 hydrogen bonds through the formation of cyclic eight-membered hydrogen bonded rings.

An ORTEP diagram of (I) with numbering scheme is shown in Fig. 1. The bond lengths and angles in the structure is within the normally expected ranges. Similar C1—N3 and C5—N2 bonds were observed in other 2-aminopyridine containing molecules (Büyükgüngör & Odabaşoğlu, 2002; Odabaşoğlu & Büyükgüngör, 2006; Shanmuga Sundara Raj et al., 2000). Furthermore, these bond angle and length agrees with that similar bond angle and length values of 2,6-diaminopyridinium hydrogen fumarate complex (Büyükgüngör & Odabaşoğlu, 2006).

2-Aminopyridine and derivatives, are protonated in acidic solution. As for mono-aminopyridinium adipate-adipic acid and in some 2-aminopyridine-containing molecules, the bonding of the H atom to the ring N atom of 2-aminopyridine rather than the amine N atom gives an ion for which an additional resonance structure can be written.

The packing of the molecules is shown in Figure 2. In (I), the 2,6-diaminopyridinium ions are linked to the adipate-adipic ions through N—H···O, O—H···O hydrogen bonds (Table 1). The dihedral angles between the aminopyridinium ring and the O1/O2/C9/C10/C11 and O3/O4/C6/C7/C8 groups are 3.31 (7) and 7.25 (8)° respectively.

The H atoms between the water molecules are distorted because of the mutual repulsive interactions. So, H5B and H5C atoms are the same H-atom in the water molecule, and this H-atom makes a flip-flop motion between the two positions with site occupation factors of 0.50 (4) and 0.50 (4), respectively. The other H-atom (H5A) of the water molecule is localized due to the O5—H5A···O4 intermolecular hydrogen bond between adipic acid molecules (Fig. 3).

Experimental

The title compound was prepared by as described by Odabaşoğlu & Büyükgüngör (2006), using 2,6-diaminopyridine and adipic acid as starting materials. Crystals were obtained by slow evaporation from an aqueous solution.