Diversification of Hydrothermal Reaction Products Induced by Naphthalene Molecules

Hydrothermal reactions in the system of Ni(II), 1,3,5-benzenetricarboxylic acid (btcH3), and 4,4‘-bipyridine (bpy)
with or without naphthalene produced three new coordination polymers, [Ni2(bpy)3(btcH)2·(H2O)]·(H2O) (2), [Ni2(bpy)2(btcH)2]·(C10H8)3 (3), and Ni(bpy)(btcH2)2 (4), in addition to previously reported [Ni2(bpy)2(btcH)2]·(C10H8)0.75·H2O
(1). Polymer 2 is the only product when naphthalene is absent in the reaction, and it is composed of 2D layers of
coordination polymers with guest water molecules between them. When naphthalene is added to the system,
compounds 1, 3, or 4 are formed depending on composition. Compound 3 has a 3D framework structure with
naphthalene guests, and 4 has a 1D chainlike structure with no guest. Details of the synthesis condition and
crystal structures of each compound are discussed. Crystallographic data:  2, C2/c, a = 22.500(3) Å, b = 20.053(3)
Å, c = 19.625(3) Å, β = 99.314(3)°; 3, P21/c, a = 11.248(2) Å, b = 16.801(4) Å, c = 14.945(3) Å, β = 103.732(4)°;
4, C2/c, a = 10.692(2) Å, b = 11.114(3) Å, c = 21.962(5) Å, β = 106.268(11)°

在以Ni(II)、1,3,5-苯三甲酸（btcH3）和4,4'-联吡啶（bpy）为反应组分的体系中，开展加入萘或不加入萘的水热反应。除此前已报道的[Ni2(bpy)2(btcH)2]·(C10H8)0.75·H2O（1）外，还得到三种新型配位聚合物：[Ni2(bpy)3(btcH)2·(H2O)]·(H2O)（2）、[Ni2(bpy)2(btcH)2]·(C10H8)3（3）与Ni(bpy)(btcH2)2（4）。当反应体系不含萘时，仅得到聚合物2，其由二维层状配位聚合物结构构成，层间存在客体水分子。当体系中添加萘时，根据反应组成的差异，可分别生成化合物1、3或4。其中化合物3具有三维骨架结构，骨架内部封装有萘客体分子；化合物4则为一维链状结构，无客体分子存在。本文对各化合物的合成条件与晶体结构进行了详细探讨。晶体学数据：2，空间群C2/c，晶胞参数a=22.500(3) Å，b=20.053(3) Å，c=19.625(3) Å，β=99.314(3)°；3，空间群P21/c，a=11.248(2) Å，b=16.801(4) Å，c=14.945(3) Å，β=103.732(4)°；4，空间群C2/c，a=10.692(2) Å，b=11.114(3) Å，c=21.962(5) Å，β=106.268(11)°