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The title compound, hexa-kis-[μ 3 -1,2-bis-(tri-fluoro-meth-yl)ethene-1,2-di-thiol-ato]- octa-hedro -hexa-palladium(II), [Pd(C 4 F 6 S 2 )] 6 , crystallizes as its benzene solvate, [Pd(tfd)] 6 ·2.5C 6 H 6 , where tfd is the di-thiol-ene S 2 C 2 (CF 3 ) 2 . The mol-ecular structure of [Pd(tfd)] 6 is of the hexa-metallic cube type seen previously in three examples of hexa-meric homoleptic palladium monodi-thiol-ene structures. All structures have in common: ( a ) the cluster closely approximates a cube containing six Pd II atoms, one at the centre of each cube face; ( b ) 12 S atoms occupy the mid-points of all 12 cube edges, providing for each Pd II atom an approximately square-planar S  4 environment; ( c ) each S atom is part of a di-thiol-ene mol-ecule, where the size of the di-thiol-ene ligand necessitates that only sulfur atoms on adjacent cube edges can be part of the same di-thiol-ene. This general cube-type framework has so far given rise to two isomeric types: an S  6 -symmetric isomer and a C  2 -chiral type (two isomers that are enanti-omers of each other). The structure of [Pd(tfd)] 6 is of the C  2 -type. Out of the 12 CF 3 groups, three are rotationally disordered over two positions. Further, we answer the question of whether additional, previously undiscovered, isomers could follow from the cube rules ( a ) through ( c ) above. An exhaustive analysis shows that no additional isomers are possible and that the list of isomers (one S  6 isomer, two C  2 enanti-omers) is complete. Each isomer type could give rise to an unlimited number of compounds if the specific di-thiol-ene used is varied.

acta crystallographica. section e, crystallographic communications

C2-isomer of [Pd(tfd)]6[tfd is S2C2(CF3)2] as its benzene solvate: a new member of the small but growing class of homoleptic palladium(II) monodithiolenes in the form of hexameric cubes