4,4′-Bipyridinium bis­(2-carboxy­pyridine-3-carboxyl­ate)

Janet Soleimannejad; Hossein Aghabozorg; Ali Morsali; Foruzan Hemmati; Faranak Manteghi

doi:10.1107/S1600536808042220

. 2008 Dec 17;65(Pt 1):o153. doi: 10.1107/S1600536808042220

4,4′-Bipyridinium bis(2-carboxypyridine-3-carboxylate)

Janet Soleimannejad ^a,^*, Hossein Aghabozorg ^b, Ali Morsali ^c, Foruzan Hemmati ^d, Faranak Manteghi ^e

PMCID: PMC2968067 PMID: 21581611

Abstract

The title salt, C₁₀H₁₀N₂ ²⁺·2C₇H₄NO₄ ⁻ or (4,4′-bpyH₂)(py-2,3-dcH)₂, prepared by the reaction between pyridine-2,3-dicarboxylic acid (py-2,3-dcH₂) and 4,4′-bipyridine (4,4′-bpy), consists of two anions and one centrosymmetric dication. In the crystal, there are two strong O—H⋯O hydrogen bonds involving the two carboxylate groups, with an O⋯O distance of 2.478 (1) Å, and an N—H⋯N hydrogen bond between the anion and cation, with an N⋯N distance of 2.743 (1) Å. These interactions, along with other O—H⋯O and C—H⋯O hydrogen bonds, π–π stacking [centroid–centroid distances 3.621 (7) and 3.612 (7) Å] and ion pairing, lead to the formation of the three-dimensional structure.

Related literature

For proton-transfer ion pairs, see: Seethalakshmi et al. (2007 ▶); Manteghi et al. (2007 ▶); Aghabozorg, Manteghi & Ghadermazi (2008 ▶). For the use of ion pairs for the formation of metal organic frameworks, see: Aghabozorg, Manteghi & Sheshmani (2008 ▶). For hydrogen bonding, see: Desiraju & Steiner (1999 ▶).

Experimental

Crystal data

C₁₀H₁₀N₂ ²⁺·2C₇H₄NO₄ ⁻
M _r = 490.42
Monoclinic,
a = 6.6675 (2) Å
b = 13.7755 (5) Å
c = 11.5887 (4) Å
β = 106.310 (2)°
V = 1021.56 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 120 (2) K
0.33 × 0.25 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.904, T _max = 0.988
18931 measured reflections
2327 independent reflections
2053 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.105
S = 1.05
2327 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808042220/su2083sup1.cif

e-65-0o153-sup1.cif^{(16.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808042220/su2083Isup2.hkl

e-65-0o153-Isup2.hkl^{(114.4KB, 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
N2—H2A⋯N1	0.85	1.90	2.7430 (14)	175
O4—H4A⋯O2ⁱ	0.85	1.64	2.4782 (12)	171
C3—H3⋯O4ⁱⁱ	0.95	2.40	3.2055 (15)	143
C4—H4⋯O2ⁱⁱⁱ	0.95	2.55	3.4324 (15)	155
C9—H9⋯O1^iv	0.95	2.41	3.3405 (15)	166
C11—H11⋯O1^v	0.95	2.52	3.4610 (15)	170
C12—H12⋯O3^v	0.95	2.19	2.9004 (15)	131

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

Acknowledgments

The authors are grateful to Ilam University for financial support of this work.

supplementary crystallographic information

Comment

Up to now, pyridine-2,3-dicarboxylic acid has been used to synthesize a numer of proton transfer ion pairs, such as 1,4-Diazoniabicyclo[2.2.2]octane bis(3-carboxypyridine-2-carboxylate) 2.17-hydrate (Seethalakshmi et al., 2007), propane-1,3-diaminium pyridine-2,3-dicarboxylate monohydrate (Manteghi et al., 2007) and piperazinediium bis(2-carboxypyridine-3-carboxylate) (Aghabozorg, Manteghi & Ghadermazi, 2008). The last two have been used to synthesize some metal organic frameworks (Aghabozorg, Manteghi, Sheshmani, 2008) in which the acid acts as a mono- or dianionic fragment. In the title ion pair, (4,4'-bpyH₂)(py-2,3-dcH)₂, the centrosymmetric dicationic moiety is balanced by two acid moieties in the monoanionic form, as shown in Fig. 1.

In the crystal structure various O—H···O, N—H···N and C—H···O hydrogen bonds are present (Table 1 and Fig. 2). The N2—H2A···N1 hydrogen bond, classified as very strong (Desiraju & Steiner, 1999), links directly the cation and anion of the centrosymmetric unit, with a 5° deviation from linearity and a distance of 2.743 (4) Å.

There is also π-π stacking (Fig. 3) between the acid (N1/C1—C5) and the base (N2/C8—C12) rings with different symmetry codes (-x, 1 - y, 1 - z and 1 - x, 1 - y, 1 - z) at distances of 3.621 (7) and 3.612 (7) Å, respectively. As shown by the torsion angles, C2-C1-C6-O2 and C2-C1-C6-O1 [78.49 (14)° and -105.43 (3)°, respectively], it can be concluded that the carboxylate group, involving atoms O1 and O2, is almost perpendicular to the π-ring of the acid. However, torsion angles, C3-C2-C7-O4 and C3-C2-C7-O3 [15.5 (2)° and -162.6 (1)°, respectively], indicate that the carboxylate groups, involving atoms O3 and O4, are nearly coplanar with the ring.

Experimental

An aqueous solution (10 ml) of 4,4'-bipyridine (156 mg, 1 mmol) and pyridine-2,3-dicarboxylic acid (167 mg, 1 mmol) was refluxed for two hours. Yellow crystals of the title compound were obtained from the solution after two hours at room temperature.