ChemInform Abstract The title compound (IV) crystallizes in the space group P1 with Z=1. Its structure consists of (Na-15-crown-5)+ ions, embedded MeCN molecules and centrosym. dimeric anions (MoNF4)22-. Short Na•••F contacts (electrostatic bonds) between the a+ and the four axial F atoms of the anions allow formulation of an ion triple.

MoCl3(N3S2) is synthesized by the improved method outlined in the scheme and converted into the donor‐acceptor complexes (VIIa) and (VIIb) by reaction with Py and THF in CH2Cl2 suspension.

ChemInform Abstract The black, moisture-sensitive crystals of the title complex, obtained as outlined in the scheme, belong to the space group P21/n with Z=4. The structure consists of (Na-15-crown-5)+ cations associated with (µ-(NSN)(MoF5)2)2-anions via Na•••F contacts of 215 to 265 pm length. The coordination of the Na+ ion by an F atom of the anion via the very short contact of 215 pm must be described by 6, whereas the coordination number of the Na+ forming contacts to two F atoms of the anion is 6 + 1.

The title compounds are prepared according to the scheme.