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Solvent Direction of Molecular Architectures in Group 1 Metal Pentacyanocyclopentadienides
Author(s) -
Less Robert J.,
Wilson Thomas C.,
Guan Bihan,
McPartlin Mary,
Steiner Alexander,
Wood Paul T.,
Wright Dominic S.
Publication year - 2013
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201201342
Subject(s) - chemistry , rubidium , crystallography , caesium , alkali metal , solvent , crystal structure , supramolecular chemistry , nitromethane , solvation , crystallization , inorganic chemistry , potassium , organic chemistry
A series of group 1 metal salts of the pentacyanocyclopentadienide anion [Cp(CN) 5 – ] ( 1 ) have been crystallised from two distinct solvent systems and the structures of the resulting species investigated by single‐crystal X‐ray diffraction. The structural results show that the bonding mode of 1 and the architecture of the resulting lattice is subtly influenced by the alkali metal and the presence of coordination or lattice solvation. The crystallisation of Na[ 1 ] from propan‐2‐ol/ n ‐pentane produces an open clathrate‐type structure of hexagonal type HS‐I composed of fullerene‐like units in which 1 behaves as a planar five‐fold symmetric node with solvent‐filled lattice voids. In contrast, crystallisation of the sodium, potassium, rubidium and caesium salts from the same solvent system results in highly condensed, unsolvated phases in which 1 adopts a variety of non‐planar coordination modes involving four or five of the CN groups. When crystallised from nitromethane/diethyl ether, the potassium, rubidium and caesium complexes form solvated arrangements with coordinated MeNO 2 that contain helical subunits.