Solvent Direction of Molecular Architectures in Group 1 Metal Pentacyanocyclopentadienides. Issue 7 (21st December 2012)

• Record Type: Journal Article
• Authors: Less, Robert J.; Wilson, Thomas C.; Guan, Bihan; McPartlin, Mary; Steiner, Alexander; Wood, Paul T.; Wright, Dominic S.
• Is Part Of: European journal of inorganic chemistry. Issue 7(2013)
• Page Start: 1161
• Page End: 1169
• Publication Date: 2012-12-21
• Subjects: Cage compounds -- Inclusion compounds -- Metal‐organic frameworks -- Alkali metals -- Structure elucidation; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201201342
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: 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 of1 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 which1 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 which1 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 MeNO2 that contain helical subunits. Abstract : The crystallisation of Na[Cp(CN)5 ] from propan‐2‐ol/ n ‐pentane produces an open clathrate‐type structure of hexagonal type HS‐I composed of fullerene‐like units in which Cp(CN)5 – behaves as a planar five‐fold symmetric node. In contrast, crystallisation of the sodium, potassium, rubidium and caesium salts from the same solvent system results in highly condensed, unsolvated phases.