4′-(2,5,8,11,14-Penta­oxabicyclo­[13.4.0]nona­deca-15,17,19-trien-17-yl­oxy)-2,2′:6′,2′′-terpyridine: a powder study

Nadezhda M Logacheva; Tamara P Puryaeva; Aslan Yu Tsivadze; Yurii A Velikodny; Vladimir V Chernyshev

doi:10.1107/S1600536807064999

. 2007 Dec 6;64(Pt 1):o225. doi: 10.1107/S1600536807064999

4′-(2,5,8,11,14-Pentaoxabicyclo[13.4.0]nonadeca-15,17,19-trien-17-yloxy)-2,2′:6′,2′′-terpyridine: a powder study

Nadezhda M Logacheva ^a, Tamara P Puryaeva ^a, Aslan Yu Tsivadze ^a, Yurii A Velikodny ^b, Vladimir V Chernyshev ^a,^b,^*

PMCID: PMC2915286 PMID: 21200792

Abstract

The central pyridine ring of the 2,2′:6′,2′′-terpyridine fragment of the title compound, C₂₉H₂₉N₃O₆, forms dihedral angles of 5.2 (5), 10.1 (5) and 86.0 (6)°, respectively, with the two outer pyridine rings and the benzene ring of the benzo-15-crown-5 fragment.

Related literature

For related crystal structures determined from synchrotron powder diffraction data, see Dorokhov et al. (2007 ▶). For useful applications of 2,2′:6′,2"-terpyridine derivatives, see Andres et al. (2003 ▶). For details of the synthesis of the title compound, see: Constable & Ward (1990 ▶); Chitta et al. (2004 ▶); Kobayashi (2001 ▶). For details of the indexing algorithm, see Visser (1969 ▶).

Experimental

Crystal data

C₂₉H₂₉N₃O₆
M _r = 515.55
Orthorhombic,
a = 58.347 (11) Å
b = 33.712 (3) Å
c = 5.3211 (8) Å
V = 10467 (3) Å³
Z = 16
Cu Kα₁ radiation
λ = 1.54059 Å
μ = 0.76 mm⁻¹
T = 295 (2) K
Specimen shape: flat sheet
15 × 1 × 1 mm
Specimen prepared at 295 (2) K and 101 kPa
Particle morphology: no specific habit, colourless

Data collection

G670 Guinier camera diffractometer
Specimen mounting: thin layer in the specimen holder of the camera
Specimen mounted in transmission mode
Scan method: continuous
Absorption correction: none
2θ_min = 4.5, 2θ_max = 75.0°
Increment in 2θ = 0.01°

Refinement

R _p = 0.019
R _wp = 0.024
R _exp = 0.018
R _B = 0.023
S = 1.36
Excluded region(s): none
Profile function: split-type pseudo-Voigt (Toraya, 1986 ▶)
148 parameters
173 restraints
H-atom parameters not refined
Preferred orientation correction: none

Data collection: local program (Huber, 2002 ▶); cell refinement: MRIA (Zlokazov & Chernyshev, 1992 ▶); data reduction: local program (Huber, 2002 ▶); program(s) used to solve structure: grid search (Chernyshev & Schenk, 1998 ▶); program(s) used to refine structure: MRIA; molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: MRIA, SHELXL97 (Sheldrick, 1997 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807064999/ya2062sup1.cif

e-64-0o225-sup1.cif^{(16.8KB, cif)}

Rietveld powder data: contains datablocks I. DOI: 10.1107/S1600536807064999/ya2062Isup2.rtv

e-64-0o225-Isup2.rtv^{(289.7KB, rtv)}

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

supplementary crystallographic information

Comment

Ability of 2,2':6',2"-terpyridines to form complexes with transition metals, such as Zn(II), Fe(II), Co(II), Ni(II) and Ru(II) is widely used in supramolecular chemistry to control self organization processes. Introduction of additional fragments with various coordinating groups to a molecule of 2,2':6',2"-terpyridine opens broad prospects for purposeful design of supramolecular compounds (Andres et al., 2003). 4'-(Benzo-15-crown-5) substituted 2,2':6',2"-terpyridines represent a new interesting class of compounds involving both terpyridine fragment, which selectively binds the d-element cations, and benzo-15-crown-5 with unique ability for complexation of cations of alkaline, alkaline-earth metals as well as those of organic amines. Compounds of this class offer new opportunities for use of metal-ligand interactions for controllable assembly of the supramolecular complexes. We present here the structure of title compound, (I).

In (I) (Fig. 1), all bond lengths and angles are comparable with those reported earlier for the related compounds (Dorokhov et al., 2007). The six-membered rings N2/C5—C9 (A), N3/C10—C14 (B), N4/C15—C19 (C) and C25—C30 (D) form the following dihedral angles - A/B 5.2 (5)°, A/C 10.1 (5)° and A/D 86.0 (6)°.

Experimental

The synthesis of 2,2':6',2"-terpyridine was carried out according to Constable & Ward (1990). 4'-Hydroxy-benzo-15-crown-5 was obtained on the basis of commercially accessible benzo-15-crown-5 by the formylation reaction (Chitta et al., 2004) and the subsequent oxidizing decarbonylation (Kobayashi, 2001). 4'-(4'''-Benzo-15-crown-5)-oxy-2,2':6',2''-terpyridine has been synthesized using reaction of nucleophilic replacement of 4'-chloro-2,2':6',2''-terpyridine with 4'-hydroxy-benzo-15-crown-5 in the dry DMSO in the presence of a base (KOH).

The synthesis of 4'-(4'''-benzo-15-crown-5)-oxy-2,2':6',2''-terpyridine (Scheme 2): to a stirred suspension of powdered KOH (890 mg, 15,90 mmol) in dry DMSO (12 ml) in the argon atmosphere at 70 °C, the 4'-hydroxy-benzo-15-crown-5 (928 mg, 3,269 mmol) was added. After 30 min, 4'-chloro-2,2':6',2''-terpyridine (873 mg, 3,269 mmol) was added and the mixture was stirred for 8 h at 70 °C and then poured into 150 ml of ice water. The water phase was extracted with chloroform (150 x 100 x 50 x 50 ml), dried over MgSO₄ and evaporated in vacuum. The residue (20 ml) was purified by column chromatography on the neutral Al₂O₃ (CHCl₃). After evaporation, the product, obtained as a yellowish oil, was crystallized from diethyl ether, then filtered and washed on the filter by the cooled diethyl ether, recrystallized from methyl alcohol (25 ml) and dried in vacuum at 60 °C. The yield of the target product as white solid was 623 mg (37,2%). (M. p. = 151 °C)