Abstract: | 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]4P2S6] · 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. |