4-[(E)-2-(Pyridin-2-yl)ethen­yl]pyridine–terephthalic acid (2/1)

Paola Castro-Montes; Jorge A Guerrero-Alvarez; Herbert Hopfl; Jose J Campos-Gaxiola; Adriana Cruz-Enriquez

doi:10.1107/S1600536812046284

. 2012 Nov 17;68(Pt 12):o3383–o3384. doi: 10.1107/S1600536812046284

4-[(E)-2-(Pyridin-2-yl)ethenyl]pyridine–terephthalic acid (2/1)

Paola Castro-Montes ^a, Jorge A Guerrero-Alvarez ^b, Herbert Hopfl ^b, Jose J Campos-Gaxiola ^a, Adriana Cruz-Enriquez ^a,^*

PMCID: PMC3588979 PMID: 23476215

Abstract

The title 2:1 co-crystal, 2C₁₂H₁₀N₂·C₈H₆O₄, crystallizes with one molecule of 4-[(E)-2-(pyridin-2-yl)ethenyl]pyridine (A) and one half-molecule of terephthalic acid (B) in the asymmetric unit. In the crystal, the components are linked through heterodimeric COOH⋯N_pyridine synthons, forming linear aggregates of composition –A–B–A–B–. Further linkage through weak C—H⋯O and C—H⋯π interactions gives two-dimensional hydrogen-bonded undulating sheets propagating in the [100] and [010] directions. These layers are connected through additional weak C—H⋯O contacts, forming a three-dimensional structure.

Related literature

For reports on supramolecular crystal engineering and potential applications of co-crystals, see: Desiraju (1995 ▶); Simon & Bassoul (2000 ▶); Bhogala & Nangia (2003 ▶); Weyna et al. (2009 ▶); Yan et al. (2012 ▶). For background to related co-crystals, see: Santra et al. (2008 ▶); Moon & Park (2012 ▶); Ebenezer & Muthiah (2012 ▶).

Experimental

Crystal data

C₁₂H₁₀N₂·0.5C₈H₆O₄
M _r = 265.28
Monoclinic,
a = 6.3821 (8) Å
b = 32.301 (4) Å
c = 6.8721 (8) Å
β = 111.440 (2)°
V = 1318.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.48 × 0.41 × 0.34 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.96, T _max = 0.97
12715 measured reflections
2328 independent reflections
2119 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.055
wR(F ²) = 0.149
S = 1.17
2328 reflections
184 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT-Plus (Bruker 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 2012 ▶) and Mercury (Macrae et al. 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Click here for additional data file.^{(18.2KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812046284/su2525sup1.cif

e-68-o3383-sup1.cif^{(18.2KB, cif)}

Click here for additional data file.^{(114.4KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812046284/su2525Isup2.hkl

e-68-o3383-Isup2.hkl^{(114.4KB, hkl)}

Click here for additional data file.^{(9.9KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812046284/su2525Isup3.cml

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

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

Cg is the centroid of the N2/C12–C16 pyridine ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1′⋯N1ⁱ	0.84	1.77	2.604 (2)	177
C9—H9⋯O2ⁱⁱ	0.93	2.67	3.285 (3)	125
C13—H13⋯O2ⁱⁱⁱ	0.93	2.52	3.396 (2)	157
C5—H5⋯O2^iv	0.93	2.64	3.135 (2)	114
C16—H16⋯Cg ^v	0.93	2.86	3.627 (3)	141

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

Acknowledgments

This work was supported financially by the Universidad Autónoma de Sinaloa (PROFAPI 2011/048). PCM thanks the Consejo Nacional de Ciencia y Tecnologia (CONACYT) for support in the form of a scholarship.

supplementary crystallographic information

Comment

Supramolecular crystal engineering has attracted growing interest over the past few decades because of its importance in biological systems, molecular recognition (Simon et al., 2000), pharmaceutical chemistry (Weyna et al., 2009) and materials chemistry (Yan et al., 2012). Aromatic carboxylic acids form reliable supramolecular synthons for the construction of novel organic networks by hydrogen bonding and π–π interactions (Desiraju, 1995), and numerous studies have focused on hydrogen bonding between carboxylic acids and pyridine molecules (Bhogala & Nangia, 2003; Santra et al., 2008; Moon & Park, 2012; Ebenezer & Muthiah, 2012). Herein, we report on the solid-state structure of a 2:1 co-crystal formed between an asymmetric bipyridine [4-((E)-2-(pyridin-2-yl)ethenyl)pyridine] and a symmetric dicarboxylic acid [terephthalic acid].

The molecular structure of the title compound is shown in Fig. 1. The asymmetric unit contains one molecule of 4-((E)-2-(pyridin-2-yl)ethenyl)pyridine and half a molecule of terephthalic acid located on a crystallographic inversion center. Both components have almost planar molecular structures as seen from the C10—C11—C12—N2 torsion angle of -4.2 (3)° for the bipyridine molecule and the O1—C4—C1—C2 torsion angle of -6.0 (3)° for the terephthalic acid.

In the crystal lattice, each terephthalic acid is linked to two bipyridine molecules through intermolecular O—H···N and C—H···O interactions giving the well known heterodimeric COOH···N_pyridine synthon. The so formed linear aggregates are connected through additional weak C—H···O contacts to generate tapes parallel to the (1–41) series of planes, which through C—H···π contacts generate undulating two-dimensional supramolecular layers (Fig. 2 and Table 1). In the third dimension, these layers are interconnected through additional weak C—H···O contacts. Interestingly, the 2-pyridine nitrogen atom is not involved in short intermolecular hydrogen bonding interactions.

Experimental

0.200 g (1.10 mmol) of 4-((E)-2-(pyridin-2-yl)ethenyl)pyridine and 0.180 g (1.10 mmol) of terephthalic acid were ground in a mortar for 20 min after adding 3 drops of CH₃OH. The resulting powder was then dissolved in 10 ml of CH₃OH and kept for crystallization by slow evaporation of the solvent at ambient conditions to give colourless block-like crystals, suitable for single-crystal X-ray diffraction analysis, after one week. Spectroscopic and TGA data for the title compound are available in the archived CIF.