Synthesis, Crystal and Electronic Structure of [Hg7As4](AgI3)2, a Novel Supramolecular Complex with the Off-Plane AgI32- Guest Anion.

✍ Scribed by Andrei V. Olenev; Alexei I. Baranov; Olga S. Oleneva; Ivan I. Vorontsov; Mikhail Yu. Antipin; Andrei V. Shevelkov

• Publisher: John Wiley and Sons
• Year: 2003
• Weight: 6 KB
• Volume: 34
• Category: Article
• ISSN: 0931-7597
• DOI: 10.1002/chin.200322009

✦ Synopsis

Synthesis, Crystal and Electronic Structure of [Hg 7 As 4 ](AgI 3 ) 2 , a Novel Supramolecular Complex with the Off-Plane Guest Anion. -The title compound is synthesized from a stoichiometric mixture of HgI2, As, Ag, and liquid Hg (775 K for 2 d, 575 K for 2 d). As revealed by single crystal XRD, Hg7As42 crystallizes in the cubic space group Pa3 with Z = 4. The structure comprises a three-dimensional positively charged host framework [Hg 7 As 4 ] 4+ with guest anions trapped in each cavity of the framework. The guest anion exhibits an unusual off-plane C3v geometry. RHF, MP2, and EH band structure calculations show that, although the host-guest interaction is weak and diffuse, it governs both the geometry of the guest anion and its positioning within the framework cavities.