The reaction of 1,8-diaminooctane with hydroiodic acid in the presence of iodine gave a new polyiodide-containing salt: 1,8-diaminiumoctane bis(triiodide), (H 3N-(CH 2) 8-NH 3)[I 3] 2. The title compound has been characterized by crystallographic and spectroscopic methods. The polyiodide ion is the first example of a hydrogen bonded I 6 2？ dianion consisting of two very asymmetric triiodide components with I？I distances of 2.7739(4) and 3.1778(4) ？ interacting by a weak halogen bond (I···I: 3.5017(2) ？). The structural parameters of the triiodide anions, derived from X-ray crystallographic data, are in good agreement with the Raman and Far-IR spectroscopic results.
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