4,4′-Bipyridine–3-(thio­phen-3-yl)acrylic acid (1/2)

Palanisamy Rajakannu; Firasat Hussain; Malaichamy Sathiyendiran

doi:10.1107/S1600536811035823

. 2011 Sep 14;67(Pt 10):o2595. doi: 10.1107/S1600536811035823

4,4′-Bipyridine–3-(thiophen-3-yl)acrylic acid (1/2)

Palanisamy Rajakannu ^a, Firasat Hussain ^a,^*, Malaichamy Sathiyendiran ^a,^*

PMCID: PMC3201325 PMID: 22065617

Abstract

In the title 1/2 adduct, C₁₀H₈N₂·2C₇H₆O₂S, the dihedral angle between the pyridine rings is 18.41 (11)°. In the thiopheneacrylic acid molecules, the dihedral angles between the respective thiophene and acrylic acid units are 5.52 (17)° and 23.92 (9)°. In the crystal, the components are linked via O—H⋯N hydrogen-bonding interactions, forming units of two 3-thiopheneacrylic acid molecules and one 4,4′-bipyridine molecule.

Related literature

For the synthesis and in vitro antibacterial activity of oxazolidines, see: Srivastava et al. (2008 ▶). For crystal engineering co-crystal and polymorph architectures, see: Friščić & MacGillivray (2009 ▶); Eccles et al. (2010 ▶). For the supramolecular construction of molecular ladders, see: Gao et al. (2004 ▶); MacGillivray et al. (2008 ▶); Friščić & MacGillivray (2005 ▶). For C—H⋯O hydrogen bonds in supramolecular design, see: Desiraju (1996 ▶) and for C—H⋯π interactions in crystal engineering, see: Desiraju (2002 ▶). graphic file with name e-67-o2595-scheme1.jpg

Experimental

Crystal data

C₁₀H₈N₂·2C₇H₆O₂S
M _r = 464.54
Triclinic,
a = 7.3454 (5) Å
b = 10.7319 (8) Å
c = 15.0196 (11) Å
α = 102.518 (6)°
β = 103.648 (6)°
γ = 94.892 (6)°
V = 1111.54 (14) Å³
Z = 2
Cu Kα radiation
μ = 2.46 mm⁻¹
T = 293 K
0.37 × 0.15 × 0.10 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.692, T _max = 1.000
9038 measured reflections
4344 independent reflections
3498 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.132
S = 1.05
4344 reflections
291 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction 2009) ▶; cell refinement: CrysAlis RED (Oxford Diffraction, 2009) ▶; data reduction: CrysAlis RED ▶; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811035823/si2368sup1.cif

e-67-o2595-sup1.cif^{(19.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811035823/si2368Isup2.hkl

e-67-o2595-Isup2.hkl^{(208.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811035823/si2368Isup3.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⋯N1ⁱ	0.82	1.86	2.668 (2)	168
O4—H4A⋯N2ⁱⁱ	0.82	1.87	2.684 (2)	174

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

Acknowledgments

The authors are grateful to the University Sophisticated Instrument Center (USIC), University of Delhi, Delhi, India, for providing the single-crystal X-ray diffractometer facility. They also thank the Department of Science & Technology for financial support.

supplementary crystallographic information

Comment

Supramolecular synthons that are based upon hydrogen bonds represent a prototypal tool for crystal engineering (Desiraju, 1996; 2002). Supramolecular heterosynthons formed from pyridine/amide and carboxylic acids have previously been exploited for liquid crystalline materials, two-dimensional beta networks, two-dimensional corrugated sheets and ternary supramolecules (MacGillivray et al., 2008; Gao et al., 2004; Friščić & MacGillivray, 2005; 2009). Recently, pharmaceutical molecules such as aspirin, rac-ibuprofen, and rac-flurbiprofen form heterosynthons with ditopic pyridine donors. Herein, we report co-crystal 1 synthesized and characterized by FT—IR, UV-Vis, ¹H-NMR spectroscopy, EA, DSC, and TGA.

The co-crystal 1 of the 2:1 adduct of 3-thiopheneacrylic acid with 4,4'-bipyridine was obtained by layering methanolic solution of 4,4'-bipyridyl to the methanolic solution of 3-thiopheneacrylic acid at room temperature. Each 3-thiopheneacrylic acid molecule forms a moderate intermolecular O—H···N bond with pyridine (Table 1). The 4,4'-bipyridine molecule in the adduct is non-planar with the two pyridine rings forming a dihedral angle of 18.41 (11)°. The two thiophene and the bipyridine are not coplanar and the dihedral angles between the S1 thiophene/N1 pyridine and S2 thiophene/ N2 pyridine are 30.14 (11)° and 47.64 (7)°, respectively. The heterosynthon extends to one-dimensional latterane like sheets held together by moderate π-π stacking interactions (Fig. 2). The Cg1–Cg2ⁱⁱ distance (between the N1,C8-C12 and N2,C13-C17 4,4'-bipyridine moieties) and the dihedral angle between pyridine planes α are 4.1411 (13)Å and 18.4 (1)°, respectively. [Symmetry code ii: (-1+x,y,z).

Experimental

All starting materials and products were found to be stable towards moisture and air. Starting materials such as 4,4'-bipyridyl (bpy) and 3-thiopheneacrylic acid (taa) were procured from commercial sources and used as received. Commercial grade solvents e.g. methanol was used as received further purification. The mixture of 1:2 ratio of 4,4'-bipyridyl (100.1 mg, 0.6409 mmol) and 3-thiopheneacrylic acid (197.8 mg, 1.2828 mmol) in methanol was stirred for 3 h at room temperature. The clear solution was obtained by filtration and that solution was kept at room temperature for several days. The white colored crystals were obtained. Yield: 83% (248.3 mg, 0.5344 mmol). Anal. Calcd for C₂₄H₂₀N₂O₄S₂: C, 62.05; H, 4.34; N, 6.03; S, 13.8. Found: C, 60.93; H, 4.13; N, 5.87; S, 12.93. ¹H NMR (CDCl₃,): 8.72 (dd, J = 4.7 Hz, 4H, H^α, bpy), 7.71 (d, J = 1.54 Hz, 2H, H⁴, taa), 7.53 (dd, J = 4.7 Hz, 4H, H^β, bpy), 7.47 (dd, J = 1.32 Hz, 2H, H¹, taa), 7.29 (m, 4H, H^2,3, taa), 6.20 (d, J = 15.44 Hz, 2H, H⁵, taa).