  The synthesis and physical properties of the new distorted-Hollandite
PbIr4Se8 are reported. Powder X-ray diffraction and transmission electron
microscopy show that the structure consists of edge- and corner-sharing IrSe6
octahedra, with one-dimensional channels occupied by Pb. The structure contains
Se-Se anion-anion bonding, leading to an electron count of
Pb2+(Ir3+)4(Se2)2-(Se2-)6, confirmed by bond-valence sums and diamagnetic
behavior. Structural and heat capacity measurements demonstrate disorder on the
Pb site, due to the combination of lone-pair effects and the large size of the
one-dimensional channels. Comparisons are made to known Hollandite and
pseudo-Hollandite structures, which demonstrates that the anion-anion bonding
in PbIr4Se8 distorts its structure, to accommodate the Ir3+ state. An
electronic structure calculation indicates semiconductor character with a band
gap of 0.76(11) eV.
