Syntheses and Structural Characterizations of the Three-dimensional Polymers [(R2Sn)3{Co(CN)6}2·X] (R = Vinyl, Propyl, Butyl; X = Solvent)

Three coordination polymers with the general formula [(R2Sn)3{Co(CN)6}2·X], R = vinyl(1), butyl(2), and propyl
(3), were synthesized and structurally characterized. The three compounds are homologues with similar cell
dimensions. They all crystallize in space group P63/mcm [1, a = 13.034(1) Å, c = 13.678(1) Å; 2, a = 13.741(1)
Å, c = 13.363(1) Å; 3, a = 13.477(1) Å, c = 13.362(1) Å]. The structures are formed by linking R2Sn units with
distorted octahedral Co(CN)6 fragments. Each tin atom is coordinated by four Co(CN)6 units and adopts an
octahedral SnN4C2 arrangement. Channels along the c axis are occupied by disordered alkyl groups. The channels
have “bottlenecks” which in 1 prevent facile release of solvent molecules. No solvent molecules are found in 2
and 3, since the channel space is occupied by the alkyl groups.

三种通式为 [(R2Sn)3{Co(CN)6}2·X] 的配位聚合物，其中 R 分别为乙烯基(1)、丁基(2)和丙基(3)，已被合成并进行了结构表征。这三种化合物为同系物，其晶胞尺寸相似。它们均以 P63/mcm 空间群结晶[1，a = 13.034(1) Å, c = 13.678(1) Å；2，a = 13.741(1) Å, c = 13.363(1) Å；3，a = 13.477(1) Å, c = 13.362(1) Å]。结构通过将 R2Sn 单元与畸变的八面体 Co(CN)6 片段连接而成。每个锡原子由四个 Co(CN)6 单元配位，形成八面体 SnN4C2 的排列。沿 c 轴的通道被无序的烷基团占据，这些通道存在‘瓶颈’结构，在 1 中阻止了溶剂分子的轻易释放。在 2 和 3 中未发现溶剂分子，因为通道空间被烷基团所占据。]