Cs6Nb4Se22 and K12Nb6Se35.3: two new compounds containing the M4Q22 building block.

The title compounds, namely hexacaesium tetraniobium docosaselenide and dodecapotassium hexaniobium pentatriacontaselenide, were formed from their respective alkali chalcogenide reactive flux and niobium metal. Both compounds fall into the larger family of solid-state compounds that contain the M(2)Q(11) building block (M = Nb, Ta; Q = Se, S), where the metal chalcogenide forms dimers of face-shared pentagonal bipyramids. Cs(6)Nb(4)Se(22) contains two Nb(2)Se(11) building blocks linked by an Se-Se bond to form isolated Nb(4)Se(22) tetrameric building blocks surrounded by caesium ions. K(12)Nb(6)Se(35.3) contains similar Nb(4)Se(22) tetramers that are linked by an Se-Se-Se unit to an Nb(2)Se(11) dimer to form one-dimensional anionic chains surrounded by potassium ions. Further crystallographic studies of K(12)Nb(6)Se(35.3) demonstrate a new M(2)Se(12) building block because of disorder between an Se(2-) site (85%) and an (Se-Se)(2-) unit (15%). The subtle differences between the structures are discussed.