[(Flu)-(CH 2 ) 2 -(NHC)-CH 2 -(NHC)-(CH 2 ) 2 -(Flu)] 2- : an 'all-organic' hybrid and flexible ligand that enwraps a Ca 2+ pseudo-tetrahedrally.

A conformationally flexible ligand, [(Flu)-(CH 2 ) 2 -(NHC)-CH 2 -(NHC)-(CH 2 ) 2 -(Flu)] 2- (L), that offers four sequential organic donor modules and enwraps a Ca 2+ pseudo-tetrahedrally in a twisted 'S'-shape is devised. The [(L)Ca] synthesis is intriguingly stepwise involving the intermediate [(LH)Ca(HMDS)], whereas [(LH)Li 2 (HMDS)] shows the potential for bimetallic chemistry. The bonding is illustrated by energy decomposition analyses.