Crystal Engineering Based on Polymeric Hydrogen-Bonded Supramolecules by Self-Assembling of 9, 10-Bis(3,5- dihydroxyphenyl)anthracene and 2,2′,4,4′- Tetrahydroxybenzophenone with Bipyridines

Xiaokang Li,Qingdao Zeng,Xiaolin Fan,Lvyin Zhen,Yulan Fan

doi:10.3390/i8030241

Abstract

9, 10-bis(3,5-dihydroxyphenyl)anthracene (BDHA) and 2,2′,4,4′-tetrahydroxybenzophenone (THB) are crystallized with bipyridine bases 4,4 ́-bipyridyl(bipy), 1,2-bis(4-pyridyl)ethane (bipy-eta), 1,2-di(4-pyridyl)ethylene (dipy-ete), 1,3-di(4-pyridyl)propane (dipy-pra), 4,4 ́-dipyridyl sulfide (dipy-sul), and 4,4 ́-dipyridyl disulfide(dipy-dis) to afford molecular complexes (BDHA)·(bipy)2 1, (BDHA)·(bipy-eta)2 2,(BDHA)0.5·(dipy-pra)·CH3CH2OH 3, (BDHA)0.5·(dipy-sul)·H2O 4, (BDHA)0.5·(dipy-dis)·CH3CH2OH 5 and (THB)·(dipy-ete)2·H2O 6. The crystal structures of 1–6 have beendetermined by single-crystal X-ray diffraction. All these molecular complexes exhibitpolymeric supramolecular structures via O–H···N or O–H···O hydrogen-bonding. 1 and 2form infinitely rectangular macrocycles linked with one another, whose sizes are ca.12.477 å× 4.802 å and ca.14.575 å × 4.809 å, respectively. 3, 5 and 6 form the one-dimensionalzigzag chain structure. 4 forms a ladder structure, and two dipy-sul molecules were includedin a frame.

Highlights

Crystal engineering has attracted a great deal of interest because of their potential applications, such as in magnetism, catalysis, molecular recognition, ion exchange, small molecule inclusion, nonlinear optics, molecular sensing, and, in general, the rational design of new materials [1,2,3,4,5,6,7,8,9,10,11]
We have recently studied the supramolecular chemistry based on 4, 4′-(9-fluorenylidene)diphenol, 4, 4′-cyclohexylidenebisphenol, bis(2-hydroxy-5-chlorophenyl) sulfide, spirobicromane and adamantane derivatives with bipyridines via O–H···N or O–H···O hydrogen-bonding [29,30,31]
9, 10-bis(3,5-dihydroxyphenyl)anthracene (BDHA) and 2,2′,4,4′tetrahydroxybenzophenone (THB) are used to construct supramolecular architecture based on crystal engineering

Summary

Introduction

Crystal engineering has attracted a great deal of interest because of their potential applications, such as in magnetism, catalysis, molecular recognition, ion exchange, small molecule inclusion, nonlinear optics, molecular sensing, and, in general, the rational design of new materials [1,2,3,4,5,6,7,8,9,10,11]. We will report the preparation, and crystal structures of six related acid-base cocrystals based on 9, 10bis(3,5-dihydroxyphenyl)anthracene (BDHA) and 2,2′,4,4′-tetrahydroxybenzophenone (THB) with bipyridine bases 4,4 ́-bipyridyl (bipy), 1,2-bis(4-pyridyl)ethane (bipy-eta), 1,2-di(4-pyridyl)ethylene (dipy-ete), 1,3-di(4-pyridyl)propane (dipy-pra), 4,4 ́-dipyridyl sulfide (dipy-sul), and 4,4 ́-dipyridyl disulfide (dipy-dis). This provides an opportunity to elucidate the difference in the formation of novel topologies in these six cocrystals. We anticipated that 1-D supramolecular hydrogen-bonded polymer would be formed With this in mind, we prepared six polymeric hydrogen-bonded supramolecules by selfassembling of BDHA or THB with 4,4 ́-bipyridyl (bipy), 1,2-bis(4-pyridyl)ethane (bipy-eta), 1,2-di(4pyridyl)ethylene (dipy-ete), 1,3-di(4-pyridyl)propane (dipy-pra), 4,4 ́-dipyridyl sulfide (dipy-sul), and 4,4 ́-dipyridyl disulfide (dipy-dis), respectively. Crystal system space group T (K) a (Å) b (Å) c (Å) α (o) β (o) γ (o) Z Volume (Å3) Dcalc (g cm-3) μ (mm-1) 2θ scan range (o) range h range k range l reflns collected unique reflns observed reflns Goodness-offit R1, wR2 [I>2σ(I)]

Results and Discussion

Conclusions

Syntheses of cocrystals 1-6

X-ray Crystallographic Analyses