Synthesis and Crystal Structure of a New Salt of the Water‐Stable Hexathiohypodiphosphate Anion: [py2Li]4[P2S6] ·2 py

A new rare example of a synthetic route in solution to the hexathiohypodiphosphate anion P₂S₆⁴⁻ is presented. Starting from P₄S₃, Li₂S, and elemental sulfur in pyridine, this reaction yields yellow block‐shaped crystals of [py₂Li]₄[P₂S₆] · 2 py ( 1 ). The molecular structure of this hitherto unknown compound was determined by single crystal X‐ray diffraction and reveals a heteronorbornane skeleton within the Li₄P₂S₆ entity.