Bis(2,6-diamino­pyridinium) hydrogen phthalate nitrate monohydrate

Akbar Raissi Shabari; Maryam Safaeimovahed; Mehrdad Pourayoubi

doi:10.1107/S1600536810004150

. 2010 Feb 6;66(Pt 3):o551. doi: 10.1107/S1600536810004150

Bis(2,6-diaminopyridinium) hydrogen phthalate nitrate monohydrate

Akbar Raissi Shabari ^a, Maryam Safaeimovahed ^a, Mehrdad Pourayoubi ^b,^*

PMCID: PMC2983748 PMID: 21580321

Abstract

The title hydrated salt, 2C₅H₈N₃ ⁺·C₈H₅O₄ ⁻·NO₃ ⁻·H₂O, was obtained fortuitously from the reaction between 2,6-diaminopyridine, phthalic acid and Co(NO₃)₂·6H₂O at 343 K. The asymmetric unit consists of two crystallographically independent 2,6-diaminopyridinium cations, a hydrogen phthalate anion, a nitrate ion and a water molecule of crystallization which in the crystal structure are linked by intermolecular O—H⋯O and N—H⋯O hydrogen bonds into a three-dimensional network. In the hydrogen phthalate anion, there is a very strong intramolecular O—H⋯O hydrogen bond.

Related literature

For a related structure, see: Al-Dajani et al. (2009 ▶). For a study of strong O—H⋯O hydrogen bonds, see: Gilli et al. (1994 ▶).

Experimental

Crystal data

2C₅H₈N₃ ⁺·C₈H₅O₄ ⁻·NO₃ ⁻·H₂O
M _r = 465.43
Monoclinic,
a = 3.6923 (3) Å
b = 37.857 (3) Å
c = 14.8415 (10) Å
β = 95.111 (2)°
V = 2066.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 120 K
0.29 × 0.26 × 0.22 mm

Data collection

Bruker SMART 1000 diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.966, T _max = 0.974
15097 measured reflections
2737 independent reflections
2309 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.093
S = 1.01
2737 reflections
298 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT-Plus (Bruker, 1998 ▶); data reduction: SAINT-Plus; 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.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810004150/lh2987sup1.cif

e-66-0o551-sup1.cif^{(21.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810004150/lh2987Isup2.hkl

e-66-0o551-Isup2.hkl^{(134.4KB, 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
O1—H1⋯O3	1.13	1.25	2.373 (4)	173
N1—H1NA⋯O1	0.90	2.10	2.950 (4)	157
N1—H1NB⋯O5	0.90	2.06	2.940 (4)	165
N2—H2NA⋯O1	0.90	2.48	3.259 (4)	146
N2—H2NA⋯O2	0.90	2.00	2.846 (3)	157
N3—H3NB⋯O5ⁱ	0.90	2.09	2.921 (4)	154
N3—H3NA⋯O2	0.90	2.25	3.074 (4)	153
N4—H4NA⋯O3ⁱⁱ	0.90	2.18	2.979 (4)	147
N4—H4NB⋯O6	0.90	2.02	2.891 (4)	163
N5—H5NA⋯O3ⁱⁱ	0.90	2.35	3.167 (4)	150
N5—H5NA⋯O4ⁱⁱ	0.90	2.07	2.889 (4)	150
N6—H6NB⋯O1Wⁱⁱⁱ	0.90	1.98	2.825 (4)	157
N6—H6NA⋯O4ⁱⁱ	0.90	2.21	2.988 (4)	144
O1W—H1WA⋯O6^iv	0.85	1.99	2.834 (4)	169
O1W—H1WB⋯O6	0.85	2.59	3.258 (4)	136
O1W—H1WB⋯O7	0.85	2.06	2.885 (3)	165

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

Acknowledgments

Support of this investigation by Islamic Azad University-North Tehran Branch is gratefully acknowledged.

supplementary crystallographic information

Comment

In previous work, the crystal structure of tetrakis(2,6-diaminopyridinium) diphthalate 2,6-diaminopyridine (Al-Dajani et al., 2009) was investigated; we report here on the synthesis and crystal structure of a new proton-transfer salt of 2,6-diaminopyridine and phthalic acid. In the title compound (Fig. 1), phthalic acid is mono-deprotonated while the two 2,6-diaminopyridine components are protonated at the pyridine nitrogen atom. The two 2,6-diaminopyridinium cations are crystallographically independent. In the mono-anion, there is a very strong intramolecular [O—H···O]^- hydrogen bond (O1···O3 = 2.373 (4) Å) which is a result of the negative charge-assisted effect described by Gilli et al. (1994). The cations, anions and water molecules are liked into a 3-D network by O—H···O and N—H···O hydrogen bonds. A view of crystal packing is shown in Fig. 2.

Experimental

The title compound was prepared according to the following procedure: A solution of phthalic acid (0.83 g, 5 mmol) in H₂O (20 ml) was added to a solution of 2,6-diaminopyridine (0.545 g, 5 mmol) in H₂O (5 ml) and stirred. To this solution, a solution of Co(NO₃)₂.6H₂O (1.45 g, 5 mmol) in H₂O (5 ml) was added and stirred at 343 K (20 minutes). The mixture was filtered and single crystals were obtained after slow evaporation at room temperature. IR (KBr, cm^-1): 3436, 2347, 1650, 1385, 1053, 984, 773, 731, 485.