Hexane-1,6-diammonium bis­(pyridine-2-carboxyl­ate)

Nam-Ho Kim; Kwang Ha

doi:10.1107/S1600536809019424

. 2009 May 29;65(Pt 6):o1415. doi: 10.1107/S1600536809019424

Hexane-1,6-diammonium bis(pyridine-2-carboxylate)

Nam-Ho Kim ^a, Kwang Ha ^a,^*

PMCID: PMC2969728 PMID: 21583258

Abstract

The title compound, C₆H₁₈N₂ ²⁺·2C₆H₄NO₂ ⁻, consists of a doubly protonated hexamethylenediammonium dication and two pyridine-2-carboxylate anions. These ions interact by means of intermolecular N—H⋯O and N—H⋯N hydrogen bonds to form a two-dimensional array. The carboxylate groups of the anions appear to be delocalized on the basis of the C—O bond lengths.

Related literature

For the crystal structures of (C₆H₁₈N₂)X ₂ (X = Cl, Br or I), see: Binnie & Robertson (1949a ▶,b ▶); Borkakoti et al. (1978 ▶); van Blerk & Kruger (2008 ▶). For details of some other hexane-1,6-diammonium compounds, see: Phan Thanh et al. (2000 ▶); Mousdis et al. (2000 ▶); Rakovský et al. (2002 ▶); Dammak et al. (2007 ▶); Sun et al. (2007 ▶); Yang et al. (2007 ▶); Wilkinson & Harrison (2007 ▶); Wang & Wei (2007 ▶). For the structure of pyridine-2-carboxylic acid, see: Hamazaki et al. (1998 ▶).

Experimental

Crystal data

C₆H₁₈N₂ ²⁺·2C₆H₄NO₂ ⁻
M _r = 362.43
Monoclinic,
a = 9.8182 (7) Å
b = 9.1569 (7) Å
c = 21.6423 (17) Å
β = 99.038 (2)°
V = 1921.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.33 × 0.25 × 0.18 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.685, T _max = 0.984
13964 measured reflections
4752 independent reflections
1740 reflections with I > 2σ(I)
R _int = 0.089

Refinement

R[F ² > 2σ(F ²)] = 0.057
wR(F ²) = 0.124
S = 0.93
4752 reflections
339 parameters
All H-atom parameters refined
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809019424/tk2459sup1.cif

e-65-o1415-sup1.cif^{(20.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809019424/tk2459Isup2.hkl

e-65-o1415-Isup2.hkl^{(232.8KB, 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
N3—H3A⋯O4	1.07 (3)	1.70 (3)	2.747 (3)	165 (3)
N3—H3B⋯O1ⁱ	0.96 (3)	2.29 (3)	3.088 (3)	140 (2)
N3—H3B⋯N1ⁱ	0.96 (3)	2.15 (3)	2.962 (3)	142 (2)
N3—H3C⋯O1ⁱⁱ	0.92 (3)	1.91 (3)	2.835 (3)	177 (3)
N4—H4A⋯O3ⁱⁱⁱ	0.97 (3)	2.27 (3)	3.064 (3)	139 (2)
N4—H4A⋯N2ⁱⁱⁱ	0.97 (3)	2.12 (3)	2.963 (3)	144 (2)
N4—H4B⋯O3^iv	1.07 (3)	1.67 (3)	2.740 (3)	175 (3)
N4—H4C⋯O2^v	1.05 (3)	1.70 (4)	2.754 (3)	179 (3)
C1—H1⋯O4^vi	1.02 (3)	2.45 (3)	3.328 (4)	145 (2)
C16—H16B⋯O3^iv	1.01 (3)	2.58 (3)	3.426 (4)	140.8 (18)

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

Acknowledgments

This work was supported by the Korea Research Foundation Grant funded by the Korean Government (MOEHRD) (grant No. KRF-2007–412-J02001).

supplementary crystallographic information

Comment

The title compound, C₆H₁₈N₂²⁺.2C₆H₄NO₂^-, consists of a doubly protonated hexamethylenediammonium dication and two pyridinecarboxylate anions (Fig. 1). The carboxylate groups of the anions appear to be delocalized on the basis of the C—O bond lengths (C—O: 1.241 (3)–1.247 (3) Å). The N3—C13—C14—C15 and C16—C17—C18—N4 torsion angles [64.9 (4)° and -66.6 (4)°, respectively] display the gauche conformation for the two groups within the dication, whereas C13—C14—C15—C16, C14—C15—C16—C17 and C15—C16—C17—C18 atoms show the anti conformation [their torsion angles lie in the range of 174.6 (3)°–177.3 (3)°]. In the crystal, the component ions interact by means of many intermolecular N—H···O and N—H···N hydrogen bonds and C—H···O contacts to form a 2-D array (Table 1 and Fig. 2).

Experimental

A solution of 1,6-diaminohexane (0.200 g, 1.721 mmol) and pyridine-2-carboxylic acid (1.180 g, 8.606 mmol) in H₂O (20 ml) was stirred for 2 h at 333 K. The solvent was removed under vacuum and the residue was washed with acetone to give a white powder (0.5972 g). Crystals were obtained by slow evaporation from an ethanol solution.