N 2,N 2′-Bis(2-hydroxy­benzyl­idene)-2,2′-bipyridyl-3,3′-dicarbohydrazide

Shao-Bin Miao; Lu-Lu Zang; Ya-Wei Fan; Bao-Ming Ji

doi:10.1107/S1600536808038087

. 2008 Dec 10;65(Pt 1):o75. doi: 10.1107/S1600536808038087

N ²,N ^2′-Bis(2-hydroxybenzylidene)-2,2′-bipyridyl-3,3′-dicarbohydrazide

Shao-Bin Miao ^a, Lu-Lu Zang ^a, Ya-Wei Fan ^a, Bao-Ming Ji ^a,^*

PMCID: PMC2967985 PMID: 21581714

Abstract

In the title compound, C₂₆H₂₀N₆O₄, the two aroylhydrazone side groups exist as diastereomeres, both in the keto form in the crystal structure. The aroylhydrazone units support the molecular conformation through an intramolecular N—H⋯O hydrogen bond. Two molecules are connected into a centrosymmetric dimer by intermolecular N—H⋯N hydrogen bonds. These dimers are connected into chains along the a axis by intermolecular O—H⋯O hydrogen bonds. The combination of these hydrogen bonds results in layers in the bc plane. The layers are further linked by weak C—H⋯π contacts to form a three-dimensional network structure.

Related literature

For syntheses, structures and ligand conformations of Ag^I complexes with flexible N,N′-di(2-pyridyl)adipoamide ligands, see: Chen et al. (2007 ▶). For palladium-catalysed allylic alkylation using chiral hydrazones as ligands, see: Mino et al. (2001 ▶). For the biological activity of hydrazones and their metal complexes, see: Rodriguez-Argüelles et al. (2004 ▶); Wiley & Clevenger (1962 ▶). For coordinated hydrazone ligands as nucleophiles, see: Wood et al. (2004 ▶). For a new fluorescent rhodamine hydrazone chemosensor for Cu^II, see: Xiang et al. (2006 ▶).

Experimental

Crystal data

C₂₆H₂₀N₆O₄
M _r = 480.48
Triclinic,
a = 9.4251 (13) Å
b = 11.7642 (16) Å
c = 12.0384 (16) Å
α = 98.842 (2)°
β = 108.895 (2)°
γ = 104.591 (2)°
V = 1181.1 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 (2) K
0.37 × 0.25 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.956, T _max = 0.991
8593 measured reflections
4281 independent reflections
3119 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.111
S = 1.02
4281 reflections
327 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: SMART (Bruker, 1999 ▶); cell refinement: SAINT (Bruker, 1999 ▶); 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 and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808038087/si2129sup1.cif

e-65-00o75-sup1.cif^{(23.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808038087/si2129Isup2.hkl

e-65-00o75-Isup2.hkl^{(209.7KB, hkl)}

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

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

Cg3 and Cg4 are the centroids of the benzene rings C1–C6 and C21–C26, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5D⋯O2	0.86	2.15	2.962 (2)	157
N2—H2D⋯N4ⁱ	0.86	2.17	2.985 (2)	159
O4—H4⋯O3ⁱⁱ	0.82	1.92	2.736 (2)	172
O1—H1⋯N1	0.82	1.95	2.663 (2)	145
C10—H10⋯Cg3ⁱⁱⁱ	0.93	2.76	3.458 (2)	133
C11—H11⋯Cg4^iv	0.93	2.73	3.588 (2)	154

Open in a new tab

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

Acknowledgments

This work was supported by the Natural Science Foundation of Henan (grant No. 082300420040).

supplementary crystallographic information

Comment

Hydrazones and their metal complexes have gained a special attraction due to their biological activity (Rodriguez-Argüelles et al., 2004; Wiley & Clevenger, 1962). These compounds have also been proposed as chemosensors (Xiang et al., 2006), catalysts (Mino et al., 2001) and nucleophiles (Wood et al., 2004). Hydrazone ligands can coordinate with metal ions to produce stable metal complexes owing to their facile keto–enol tautomerism.

As shown in Fig. 1, two aroylhydrazone units are situated on both sides of the 2,2'-dipyridyl linking group which can decrease the steric hindrance among the pyridyl rings. The two aroylhydrazone side groups exist as diastereomeres, both in the keto form in the crystal structure. The aroylhydrazone units support the molecular conformation through an intramolecular N—H···O hydrogen bond (Table 1).

The dihedral angle between two pyridine rings of the 2,2'-dipyridyl group is 105.26 (2)°. The bond distances and angles are all in normal ranges. The distances of the C8—O2, C19—O3, N1—C7 and N6—C20 are 1.226 (2), 1.229 (2), 1.279 (2) and 1.280 (2) Å, respectively, which have the features of typical C═O and C═N double bonds (Chen et al., 2007). This confirms that the compound exists in the keto form.

A pair of intermolecular N—H···N hydrogen bonds connect two adjacent molecules into dimers via inversion centres (Fig. 2). These dimers are connected into chains along a axis by intermolecular O4—H4···O3 hydrogen bonds. The combination of both hydrogen bonds generate layers which extend along the b+c direction (Fig. 3). The layers are linked by weak C—H···π contacts (Table 1) to form a three-dimensional network structure. Cg3 and Cg4 are the centroids of the benzene rings C1–C6 and C21–C26, respectively. There is another intramolecular hydrogen bond, O1—H1···N1, which results from the planar geometry in the H1–O1–C1–C6–C7–N1 ring system (Table 1).

Experimental

A mixture of 2,2'-bipyridyl-3,3'-diformylhydrazide (0.272 g, 1 mmol), salicylaldehyde (2.5 mmol, 0.26 ml) and a drop of glacial acetic acid in ethanol (20 ml) was stirred at reflux temperature for 3 h. The solution was filtered and the filtrate was set aside to be crystallized. Yellow crystals suitable for the X-ray diffraction study were obtained after 5 d.