两种反式-9,10-二氢-9,10-二乙基蒽-11,12-二羧酸为主体的氢键包合物的合成与晶体结构

Synthesis and Crystal Structure of Inclusion Compounds:trans-9,10-Dihydro-9,10-ethanoanthracene-11,12-dicarboxylic Acid with Boric Acid and Tetrabutylammonium Salt

合成了反式-9,10-二氢-9,10-二乙基蒽-11,12-二羧酸(EADA)及其与硼酸共同构建主体晶格的正四丁基铵阳离子管状包合物(n-C4H9)4N+C18H13O-4?B(OH)3(1)和(n-C4H9)4N+C18H13O-4(2),并通过单晶X射线衍射法对其进行了晶体结构测定.结果表明,晶体1属单斜晶系,P2(1)/c空间群,晶胞参数a=1.5699(1)nm,b=0.9955(6)nm,c=2.2933(1)nm,β=109.962(3)°,Z=4,R1=0.0434,wR=0.0759;晶体2属单斜晶系,C2/c空间群,晶胞参数a=1.4005(3)nm,b=1.2821(2)nm,c=1.7657(3)nm,β=100.388(1)°,Z=4,R1=0.0584,wR=0.0966.在晶体1中,EADA阴离子和硼酸分子的氢键四聚体链交错平行排列,生成具有矩形截面的管道式主体晶格,每个管道内包含了两列规则排列的正四丁基铵阳离子(n-C4H9)4N+.在晶体2中,相互独立的EADA阴离子交错排列形成类蜂巢形截面的管道式主体晶格,正四丁基铵阳离子形成Z形长列被包合在这些管道里,阳离子的烃链穿插在管道壁中.

New inclusion complexes （n-C4H9）4N^＋ClsH13O4^-·B（OH）3 （1） and （n-C4H9）4N^＋C18H13O4^- （2） have been prepared and characterized by X-ray crystallography. Crystal data： compound 1, monoclinic P2（1）/c, α= 1.5699（1） nm, b=0.9955（6） nm, c=2.2933（1） nm, β=109.962（3）°, Z=4, and R1 =0.0434, wR =0.0759; compound 2, monoclinic C2/c, α= 1.4005（3） nm, b=1.2821（2） nm, c= 1.7657（3） nm, β= 100.388（1）°, Z=4, and R1 =0.0584, wR=0.0966. In the crystal structure of 1, the tetramers formed by two trans-9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboxylic acid （EADA） anions and two boric acid molecules are connected through O-H···O hydrogen bonds to generate a channel type host lattice. The tetra-n-butylammonium cations are stacked in double columns within each channel with cross-sectional size of about 2.30 nm×0.93 nm. In the crystal structure of 2, similar honeycomb host lattices with big size are also formed along the [101] direction by three-dimensional accumulation of EADA anions. The tetra-n-butylammonium cations are accommodated in a zigzag fashion within each channel.