Synthesis and Crystal Structures of Cadmium(II) Cyanide with Branched-Butoxyethanol

Takeshi Kawasaki,Takafumi Kitazawa

doi:10.3390/cryst8050221

Abstract

Two novel 3D cadmium(II) cyanide coordination polymers with branched-butoxyethanol compounds (iBucel = iso-butoxyethanol, tBucel = tert-butoxyethanol), [{Cd(CN)2(iBucel)2}{Cd(CN)2(H2O)(iBucel)}2{Cd(CN)2}6∙2(iBucel)]n I and [{Cd(CN)2(H2O)1.06(tBucel)0.94}{Cd(CN)2(tBucel)}2{Cd(CN)2}2∙1.06(tBucel)]n II, were synthesized and characterized by structural determination. Complex I contains two distinct Cd(II) coordination geometries: octahedral and tetrahedral. In contrast, complex II contains three distinct Cd(II) coordination geometries: octahedral, square-pyramidal, and tetrahedral. In the two complexes, branched-butoxyethanol molecules behave as both a ligand and a guest in the Cd(CN)2 cavities. The framework in I contains octahedral and tetrahedral Cd(II) in a 3:6 ratio. In I, the coordination environments of octahedral Cd(II) are cis-O-Cd-O. The framework in II contains octahedral, square-pyramidal, and tetrahedral Cd(II) in a 1:2:2 ratio. In II, the coordination environment of octahedral Cd(II) is disordered trans-O-Cd-O and the axial oxygen ligand is either a water or tBucel molecule. In II, the square-pyramidal Cd(II) geometry is formed by one tBucel ligand and four cyanide ligands. The Cd(CN)2 frameworks of the two complexes exhibit different structures.

Highlights

We recently reported three crystal structures of cadmium cyanide coordination reported three crystal structures of cadmium cyanide coordination polymers with an alkoxyethanol polymers with an alkoxyethanol of normal-alkyl that is, [Cd(CN)
The synthesis and the synthesis and crystal structures of two novel cadmium(II) cyanide complexes with crystal structures of two novel cadmium(II)
Nishikiori et al [13,30,31] showed that the arrangements of cyanides in a Cd(CN)2 host are disordered, by 113 Cd–CP/MAS NMR

Summary

Introduction

Because of their unique chemical properties, cadmium cyanide systems included with various guest species have been found to be one of the most important and mineralomimetic materials since the discovery of the clathrate complexes [1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22]. Cadmium(II) cyanide is a 3D porous coordination polymer clathrating various guest molecules (for example, CCl4 [4,5,6], C6 H6 [9] CH2 ClCHCl2 [10], and Bu2 O [10]) by van der. For Cd(CN) clathrates containing a lipophilic guest, the coordination geometries of Cd(II). The Cd(CN) clathrates with the water molecule(s) coordinating to Cd(II) ion contain alcohol or short dialkyl-ether (alkyl group with a carbon number less than 3) as a guest, and Crystals 2018, 8, 221 ; doi:10.3390/cryst8050221 www.mdpi.com/journal/crystals. For Cd(CN)2,for there was no there was no guest molecule found to facilitate a doubly interpenetrated diamond-like framework. Guest molecule found to facilitate a doubly interpenetrated diamond‐like framework. Thewe hydrophilic of hydrophilic groups of guest molecules influence the coordination environment. Alkoxyethanol (Rcel) has groups both hydroxyl andinetheric groups shown (Rcel) has both hydroxyl and etheric as shown

Weasrecently in

Synthesis

Results

C54 H88 Cd9 N18 O14

Conclusions