4,4′-Bipyridine–pyridine-3,5-dicarb­oxy­lic acid (3/4)

Sheng-Bo Liu; Chao Xu; Taike Duan; Qun Chen; Qian-Feng Zhang

doi:10.1107/S160053681102719X

. 2011 Jul 13;67(Pt 8):o2033. doi: 10.1107/S160053681102719X

4,4′-Bipyridine–pyridine-3,5-dicarboxylic acid (3/4)

Sheng-Bo Liu ^a, Chao Xu ^a, Taike Duan ^a, Qun Chen ^b, Qian-Feng Zhang ^a,^b,^*

PMCID: PMC3213482 PMID: 22091061

Abstract

In the title compound, 3C₁₀H₈N₂·4C₇H₅NO₄, the asymmetric unit contains two molecules of pyridine-3,5-dicarboxylic acid and one molecule of 4,4′-bipyridine in general positions together with one molecule of 4,4′-bipyridine lying across a centre of inversion, thus giving a 4:3 molar ratio of pyridine-3,5-dicarboxylic acid to 4,4′-bipyridine. The dihedral angle between the bipyridine rings on general positions is 21.2 (2)°. These molecular units are linked by O—H⋯N hydrogen bonds forming an extended two-dimensional framework in the crystal.

Related literature

For structures and properties of self-assembled supermolecular compounds, see: Lehn (1990 ▶). For hydrogen bonds and π–π stacking interactions in supermolecular compounds, see: Roesky & Andruh (2003 ▶). For related structures, see: Soleimannejad et al. (2009 ▶); Jiang et al. (2010 ▶).

Experimental

Crystal data

3C₁₀H₈N₂·4C₇H₅NO₄
M _r = 1137.04
Monoclinic,
a = 13.8461 (4) Å
b = 11.0564 (3) Å
c = 18.1060 (4) Å
β = 110.511 (1)°
V = 2596.09 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 296 K
0.14 × 0.12 × 0.05 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ▶) T _min = 0.985, T _max = 0.995
24265 measured reflections
5918 independent reflections
4086 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.118
S = 1.03
5918 reflections
379 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); 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 datablock(s) I, global. DOI: 10.1107/S160053681102719X/bx2358sup1.cif

e-67-o2033-sup1.cif^{(21.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681102719X/bx2358Isup2.hkl

e-67-o2033-Isup2.hkl^{(289.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681102719X/bx2358Isup3.cml

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
O2—H2⋯N5ⁱ	0.82	1.80	2.5928 (17)	162
O4—H4⋯N4ⁱⁱ	0.82	1.79	2.6037 (18)	172
O5—H5⋯N3ⁱⁱⁱ	0.82	1.78	2.5956 (17)	173
O7—H7⋯N2ⁱⁱ	0.82	1.83	2.5862 (16)	152

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

Acknowledgments

This project was supported by the Program for New Century Excellent Talents in Universities of China (NCET-08–0618).

supplementary crystallographic information

Comment

In the past decades, the field of self-assembled supermolecular chemistry attracted increasing concerns due to their interesting structures and unique properties (Lehn, 1990). Hydrogen-bonds and pi—pi stacking are the most two important interactions in supermolecular compounds (Roesky & Andruh, 2003). As well known, many organic molecules with N– and O-donors such as bipyridine and pyridine-carboxylate acid have been wildly employed for constructing supermolecular complexes. In this paper, we report the hydrothermal synthesis and co-crystal structure of a two-dimensional framework of 4,4'-bipyridine (4,4'-bipy) and pyridine-3,5-dicarboxylic acid (3,5-pydcH₂) assembled by the intermolecular hydrogen-bonding interactions. In the title compound, the asymmetric unit is formed by two molecules of pyridine-3,5-dicarboxylic acid and one molecule of 4,4'-bipyridine lying in general positions, together with one molecule of 4,4'-bipyridine lying across a centre of inversion, thus giving a 4:3 molar ratio of pyridine-3,5-dicarboxylic acid to 4,4'-bipyridine. These molecular units are linked by O—H···N hydrogen-bonds forming an extended two-dimensional framework, Table 1, Fig.2. The geometric parameters are in normal range.

Experimental

4, 4'-bipyridine (31.2 mg, 0.2 mmol) and 3, 5-pyridinedicarboxylic acid (50.1 mg, 0.3 mmol) were mixed in 2.5 ml water solution and the mixture was stirred for a while. The solution was transferred to a 23 ml Teflon-lined stainless autoclave. The vessel was sealed and heated to 110 C° for 2 days. The autoclave was cooled to ambient temperature. Colorless flake crystals of title co-crystal compound were obtained and air dried. Yield: 43.2 mg, ca 67%. Anal. Calcd. for C₂₉H₂₁O₈N₅: C, 61.4; H, 3.71; N, 12.3%. Found: C, 61.1; H, 3.65; N, 12.1%.