4,4′-Bipyridine–cyano­acetic acid (1/2)

Ge Song; Er-Jun Hao; Wei Li

doi:10.1107/S1600536808031322

. 2008 Oct 4;64(Pt 11):o2058. doi: 10.1107/S1600536808031322

4,4′-Bipyridine–cyanoacetic acid (1/2)

Ge Song ^a, Er-Jun Hao ^a, Wei Li ^a,^*

PMCID: PMC2959634 PMID: 21580924

Abstract

Crystals of the title adduct, C₁₀H₈N₂·2C₃H₃NO₂, were obtained from a methanol/water solution of cyanoacetic acid and 4,4′-bipyridine at room temperature. In the crystal structure, cyanoacetic acid and centrosymmetric 4,4′-bipyridine molecules are linked by O—H⋯N hydrogen bonds to form three-component supramolecular adducts. The acidic H atom is almost midway between the O and N atoms of the cyanoacetic acid and bipyridine molecules, with O—H and N—H distances of 1.19 (3) and 1.39 (3) Å, respectively, so that the H-atom transfer is best regarded as partial. The three-component adducts are further interconnected with neighboring molecules by weak intermolecular C—H⋯O and C—H⋯N hydrogen bonds and by π–π stacking interactions [centroid–centroid distance = 3.7200 (11) Å] to generate a three-dimensional supramolecular structure.

Related literature

For similar partial proton transfer from a carbonic acid towards a nitrogen base, see: Farrell et al. (2002a ▶,b ▶); For C—H⋯O and C—H⋯N hydrogen bonds, see: Balakrishna et al. (2005 ▶); Wang et al. (2008 ▶).

Experimental

Crystal data

C₁₀H₈N₂·2C₃H₃NO₂
M _r = 326.31
Monoclinic,
a = 4.887 (2) Å
b = 21.383 (10) Å
c = 7.921 (4) Å
β = 100.664 (8)°
V = 813.4 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 291 (2) K
0.34 × 0.26 × 0.19 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T _min = 0.952, T _max = 0.982
3537 measured reflections
1487 independent reflections
1153 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.133
S = 1.04
1487 reflections
112 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); 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/S1600536808031322/zl2142sup1.cif

e-64-o2058-sup1.cif^{(13.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808031322/zl2142Isup2.hkl

e-64-o2058-Isup2.hkl^{(73.4KB, 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
C7—H7A⋯N2ⁱ	0.97	2.92	3.420 (3)	113
C2—H2⋯O2ⁱⁱ	0.93	2.62	3.361 (3)	137
C2—H2⋯N2ⁱⁱⁱ	0.93	2.75	3.322 (3)	121
O1—H1D⋯N1	1.19 (3)	1.39 (3)	2.566 (2)	170 (2)

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

supplementary crystallographic information

Comment

A view of the title structure is shown in Fig. 1. The asymmetric unit consists of one cyanoacetic acid molecule and half a 4,4'-bipyridine molecule. The H1D was found in a Fourier map and its position was refined freely. Within the asymmetric unit, atom H1D is almost mid-way between atoms O1 and N1, so that the H-atom transfer is best regarded as partial. The distances of O1—H1D and N1—H1D are 1.19 (3) Å and 1.39 (3) Å, respectively, which are comparable with literature data (Farrell et al., 2002a,b). Cyanoacetic acid and 4,4'-bipyridine molecules are linked by these O—H···N hydrogen bonds to form 3-component supramolecular adducts.

The 3-compenent adducts interact with neigboring molecules via by weak intermolecular C—H···O and C—H···N hydrogen bonds, and by π-π stacking interactions. Within the asymmetric unit, the atoms C2 and C7 act as hydrogen-bond donors, via atoms H2, H2, and H7A, to atoms O2ⁱⁱ , N2ⁱⁱⁱ and N2ⁱ, respectively (symmetry operators: i = x + 1/2,-y + 1/2,z + 1/2; ii = x - 1,y,z -1; iii = x - 3/2,-y + 1/2,z - 1/2). The bond lengths and angles of the above three hydrogen bonds (Table 1) are comparable with literature data (Balakrishna et al., 2005; Wang et al., 2008). These hydrogen bonds, albeit rather weak, link the 3-component supramolecular adducts into a three-dimensional supramolecular structure, which is further stabilized by weak intermolecular π-π stacking interactions, formed by adjacent bipyridine rings (centroid–centroid distance = 3.7200 (11) Å) (Fig. 2 and Fig. 3).

Experimental

Cyanoacetic acid (0.2 mmol) and 4,4'-bipyridine (0.2 mmol) were dissolved in methanol (5 ml) and water (1 ml) at room temperature. The single crystals of the title compound were obtained from the solution after ten days.