2,2′-Azanediyl­diethanaminium pyridine-2,5-dicarboxyl­ate

Hossein Aghabozorg; Maryam Saemi; Zeynab Khazaei; Vahid Amani; Behrouz Notash

doi:10.1107/S1600536810054413

. 2011 Jan 8;67(Pt 2):o292. doi: 10.1107/S1600536810054413

2,2′-Azanediyldiethanaminium pyridine-2,5-dicarboxylate

Hossein Aghabozorg ^a,^*, Maryam Saemi ^a, Zeynab Khazaei ^a, Vahid Amani ^b, Behrouz Notash ^b

PMCID: PMC3051686 PMID: 21522984

Abstract

The crystal structure of the title compound, C₄H₁₅N₃ ²⁺·C₇H₃NO₄ ²⁻, consists of diethylenetriaminium (2,2′-azanediyldiethanaminium) cations and pyridine-2,5-dicarboxylate anions, which are linked by N—H⋯O, N—H⋯N and C—H⋯O hydrogen bonds. C—H⋯π interactions are also observed. In the anion, the carboxylate groups are oriented at dihedral angles of 11.04 (15) and 6.31 (14)° with respect to the pyridine ring.

Related literature

For general background to proton-transfer compounds, see: Sheshmani et al. (2007 ▶); Aghabozorg et al. (2008a ▶,b ▶,c ▶); Derikvand et al. (2009 ▶).

Experimental

Crystal data

C₄H₁₅N₃ ²⁺·C₇H₃NO₄ ²⁻
M _r = 270.29
Monoclinic,
a = 10.485 (2) Å
b = 7.7016 (15) Å
c = 17.254 (4) Å
β = 106.67 (3)°
V = 1334.7 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 K
0.3 × 0.3 × 0.15 mm

Data collection

Stoe IPDS II diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2005 ▶) T _min = 0.967, T _max = 0.983
14267 measured reflections
3593 independent reflections
2523 reflections with I > 2σ(I)
R _int = 0.099

Refinement

R[F ² > 2σ(F ²)] = 0.087
wR(F ²) = 0.184
S = 1.18
3593 reflections
200 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2005 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2005 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810054413/xu5129sup1.cif

e-67-0o292-sup1.cif^{(18.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810054413/xu5129Isup2.hkl

e-67-0o292-Isup2.hkl^{(176.2KB, hkl)}

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

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

Cg is the centroid of the pyridine ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O3ⁱ	0.96 (3)	2.56 (3)	3.254 (3)	130 (2)
N2—H2A⋯O4ⁱ	0.96 (3)	1.94 (3)	2.886 (3)	169 (3)
N2—H2B⋯O1	0.90 (3)	1.98 (3)	2.821 (4)	155 (3)
N2—H2C⋯O3ⁱⁱ	0.99 (4)	1.87 (4)	2.843 (3)	167 (3)
N3—H3A⋯O2ⁱⁱⁱ	0.97 (4)	2.38 (4)	3.223 (3)	145 (3)
N4—H4A⋯O2	0.95 (4)	1.91 (4)	2.807 (4)	158 (3)
N4—H4B⋯O4ⁱⁱ	0.94 (4)	1.92 (3)	2.840 (3)	167 (4)
N4—H4C⋯O2^iv	0.91 (4)	1.98 (4)	2.823 (4)	154 (4)
N4—H4C⋯N1^iv	0.91 (4)	2.57 (4)	3.253 (4)	133 (3)
C8—H8A⋯O1^v	0.97	2.49	3.218 (4)	132
C3—H3⋯Cgⁱ	0.93	2.83	3.588 (3)	139
C10—H10B⋯Cgⁱⁱⁱ	0.97	2.91	3.846 (3)	161

Open in a new tab

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

Acknowledgments

We are grateful to Tarbiat Moallem University for financial support.

supplementary crystallographic information

Comment

Proton transfer is very important in physics, chemistry and biochemistry. In order to develop new types of proton transfer compounds and hydrogen bonding systems, our research group has already synthesized proton transfer compounds with different proton donors and acceptors (Sheshmani et al., 2007; Aghabozorg et al., 2008a; Aghabozorg et al., 2008b; Aghabozorg et al., 2008c; Derikvand et al., 2009). We herein report the crystal structure of the title compound.

The molecular structure of the title compound is shown in Fig. 1. The crystal structure shows that two protons from two carboxylic acid groups are transferred to two N atoms of the diethylenetriamine.

As can be seen from the packing diagram (Fig. 2), there are variety intera and intermolecular N—H···O, N—H···N and C—H···O hydrogen bonds (Table 1) in the crystal structure

Also, as shown in Fig. 3, there are C—H···π interactions between C10—H10B bond of diethylenetriaminium ion and pyridine ring and C3—H3 bond of pyridine-2,5-dicarboxylate ion and symmetry-related pyridine ring in the crystal structure [distance from centroid = 2.91 and 2.83 Å; angle = 161 and 139 ° and symmetry codes: 1 - x, -y, -z and 2 - x, -1/2 + y, 1/2 - z, respectively].

Intermolecular N—H···O, N—H···N and C—H···O hydrogen bonds and C—H···π interactions in this compound seem to be effective in the stabilization of the crystal structure, resulting in the formation of a three-dimensional supramolecular structure.

Experimental

Diethylenetriamine (0.28 g, 0.29 ml, 2.66 mmol) was added to a solution of pyridine-2,5-dicarboxylic acid (0.45 g, 2.66 mmol) in methanol (50 ml) at room temperature. The suitable crystals for X-ray diffraction experiment were obtained by methanol diffusion to a pale yellow solution in water. Suitable crystals were isolated after one week (yield; 0.55 g, 76.5%).