Klien Hendrik, Seichter Wilhelm, Skobridis Konstantinos, Weber Edwin
Institut für Organische Chemie, TU Bergakademie Freiberg, Leipziger Strasse 29, D-09596 Freiberg/Sachsen, Germany.
Department of Chemistry, University of Ioannina, GR-45110 Ioannina, Greece.
Acta Crystallogr C Struct Chem. 2015 Sep;71(Pt 9):768-75. doi: 10.1107/S2053229615014035. Epub 2015 Aug 8.
Having reference to an elongated structural modification of 2,2'-bis(hydroxydiphenylmethyl)biphenyl, (I), the two 1,1':4',1''-terphenyl-based diol hosts 2,2''-bis(hydroxydiphenylmethyl)-1,1':4',1''-terphenyl, C44H34O2, (II), and 2,2''-bis[hydroxybis(4-methylphenyl)methyl]-1,1':4',1''-terphenyl, C48H42O2, (III), have been synthesized and studied with regard to their crystal structures involving different inclusions, i.e. (II) with dimethylformamide (DMF), C44H34O2·C2H6NO, denoted (IIa), (III) with DMF, C48H42O2·C2H6NO, denoted (IIIa), and (III) with acetonitrile, C48H42O2·CH3CN, denoted (IIIb). In the solvent-free crystals of (II) and (III), the hydroxy H atoms are involved in intramolecular O-H···π hydrogen bonding, with the central arene ring of the terphenyl unit acting as an acceptor. The corresponding crystal structures are stabilized by intermolecular C-H···π contacts. Due to the distinctive acceptor character of the included DMF solvent species in the crystal structures of (IIa) and (IIIa), the guest molecule is coordinated to the host via O-H···O=C hydrogen bonding. In both crystal structures, infinite strands composed of alternating host and guest molecules represent the basic supramolecular aggregates. Within a given strand, the O atom of the solvent molecule acts as a bifurcated acceptor. Similar to the solvent-free cases, the hydroxy H atoms in inclusion structure (IIIb) are involved in intramolecular hydrogen bonding, and there is thus a lack of host-guest interaction. As a result, the solvent molecules are accommodated as C-H···N hydrogen-bonded inversion-symmetric dimers in the channel-like voids of the host lattice.
参照2,2'-双（羟基二苯甲基）联苯（I）的一种细长结构修饰，合成了两种基于1,1':4',1''-三联苯的二醇主体，即2,2''-双（羟基二苯甲基）-1,1':4',1''-三联苯（C44H34O2，II）和2,2''-双[羟基双（4-甲基苯基）甲基]-1,1':4',1''-三联苯（C48H42O2，III），并研究了它们涉及不同包合物的晶体结构，即（II）与二甲基甲酰胺（DMF）形成的包合物（C44H34O2·C2H6NO，记为（IIa））、（III）与DMF形成的包合物（C48H42O2·C2H6NO，记为（IIIa））以及（III）与乙腈形成的包合物（C48H42O2·CH3CN，记为（IIIb））。在（II）和（III）的无溶剂晶体中，羟基氢原子参与分子内O-H···π氢键作用，三联苯单元的中心芳烃环作为受体。相应的晶体结构通过分子间C-H···π接触得以稳定。由于（IIa）和（IIIa）晶体结构中所含DMF溶剂分子独特的受体特性，客体分子通过O-H···O=C氢键与主体配位。在这两种晶体结构中，由交替的主体和客体分子组成的无限链代表基本的超分子聚集体。在给定的链内，溶剂分子的O原子作为一个分叉受体。与无溶剂情况类似，包合结构（IIIb）中的羟基氢原子参与分子内氢键作用，因此不存在主体-客体相互作用。结果，溶剂分子以C-H···N氢键连接的反演对称二聚体形式容纳在主体晶格的通道状空隙中。
