Why Do Five Ga+ Cations Form a Ligand-Stabilized [Ga5 ]5+ Pentagon and How Does a 5:1 Salt Pack in the Solid State?

The reaction of the Ga+ source [Ga(PhF)2 ]+ [Al(ORF )4 ]- with the neutral σ-donor ligand dmap (4-Me2 N-C6 H4 N) produces the unexpectedly large and fivefold positively charged cluster cation salt [Ga5 (dmap)10 ]5+ ([Al(ORF )4 ]- )5 . It includes a regular and planar Ga5 pentagon with strong metal-metal bonding. Additionally, the compound represents the first salt in which an ionic 1:5 packing is realized. We discuss the nature of this structure which results from the conversion of the non-bonding 4s2 lone-pair orbitals into fully Ga-Ga-bonding orbitals and the solid-state arrangement of the ions constituting the lattice as an almost orthohexagonal AX5 lattice, possibly the aristotype of any 5:1 salt.