Dimethyl 6,6′-dicyano-2,2′-bipyridine-3,3′-dicarboxyl­ate

Xiao He; Gui-Rong Qu; Dongsheng Deng; Baoming Ji

doi:10.1107/S1600536809012446

. 2009 Apr 8;65(Pt 5):o985. doi: 10.1107/S1600536809012446

Dimethyl 6,6′-dicyano-2,2′-bipyridine-3,3′-dicarboxylate

Xiao He ^a,^b, Gui-Rong Qu ^a, Dongsheng Deng ^b, Baoming Ji ^b,^*

PMCID: PMC2977680 PMID: 21584023

Abstract

In the title compound, C₁₆H₁₀N₄O₄, the two pyridine rings are twisted by 44.41 (2)° and the ester groups form dihedral angles of 48.77 (4) and 45.75 (2)° with the corresponding pyridine rings. The crystal structure is stabilized by intermolecular C—H⋯O hydrogen bonds and π–π stacking interactions between the pyridine rings [centroid-to-centroid distance 3.797 (2) Å].

Related literature

For the synthetic procedures relevant to preparation of the title compound, see: Tichy et al. (1995 ▶); Glaup et al. (2005 ▶); Heirtzler (1999 ▶)

Experimental

Crystal data

C₁₆H₁₀N₄O₄
M _r = 322.28
Triclinic,
a = 8.201 (3) Å
b = 10.302 (6) Å
c = 10.768 (3) Å
α = 109.148 (4)°
β = 106.091 (3)°
γ = 100.404 (5)°
V = 787.9 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.49 × 0.45 × 0.41 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.952, T _max = 0.960
5613 measured reflections
2845 independent reflections
2391 reflections with I > 2σ(I)
R _int = 0.014

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.094
S = 1.05
2845 reflections
218 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.12 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXS97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809012446/gk2200sup1.cif

e-65-0o985-sup1.cif^{(18.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809012446/gk2200Isup2.hkl

e-65-0o985-Isup2.hkl^{(139.6KB, 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
C4—H4A⋯O4ⁱ	0.93	2.39	3.222 (3)	149

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Symmetry code: (i) Inline graphic .

Acknowledgments

We are grateful to the National Natural Science Foundation of China (grant No. 20872057) and the Natural Science Foundation of Henan Province (No. 082300420040) for financial support.

supplementary crystallographic information

Comment

Binicotinic acid and its derivatives have been proved to be a kind of multifunctional and flexible ligand in the construction of complexes possessing novel and interesting topological structures. Our interest in these compounds has led us to prepare the title compound. First, we synthesized dimethyl 2,2'-bipyridine-3,3'-dicarboxylate 1,1'-dioxide according to the reported method (Tichy et al. 1995). Second, the incorporation of cyano group onto 6 and 6' positions of the above compound could be readily performed when adopting the literature methods (Glaup et al. 2005; Heirtzler 1999). In this contribution, we report the synthesis and crystal structure of the title compound.

The asymmetric unit of the title compound contains one molecule (Fig. 1.). In the crystal structure, the most striking feature of the title compound is the interesting arrangement of the title molecules, which are linked into centrosymmetric dimers by formation of intermolecular C—H···O hydrogen bonds, in which C4—H4A is a donor and O4 is an acceptor (Table 1, Fig. 2). Short π···π contacts between two pyridine rings with centroid-centroid distance of 3.797 (2) Å are observed in the structure.

Experimental

To an ice-cooled solution of dimethyl 2,2'-bipyridine-3,3'-dicarboxylate 1,1'-dioxide (1.22 g, 4 mmol) and trimethylsilyl cyanide (5.2 ml, 40 mmol) in ca 40 ml dry CH₂Cl₂ under N₂ was carefully added benzoyl chloride (1.9 ml, 17 mmol). After stirring overnight at room temperature, 10% aq Na₂CO₃ was carefully added to the chilled reaction mixture and it was concentrated at 200 mbar to complete crude product precipitation. This was collected by filtration, washed with water and dried. Purification by silica gel chromatography using 100 ~200 mesh ZCX II eluted by hexane-ethyl acetate (3:1, v/v) gave the yellow solid. The crystalline compound was obtained by slow evaporation of CH₂Cl₂ solution containing the title compound.