Dimers of heptapnictide anions: As14 4- and P14 4- in the crystal structures of [Rb(18-crown-6)]4As14.6NH3 and [Li(NH3)4]4P14.NH3

Tobias Hanauer; Jürgen C Aschenbrenner; Nikolaus Korber

doi:10.1021/ic060418j

Dimers of heptapnictide anions: As14 4- and P14 4- in the crystal structures of [Rb(18-crown-6)]4As14.6NH3 and [Li(NH3)4]4P14.NH3

Inorg Chem. 2006 Aug 21;45(17):6723-7. doi: 10.1021/ic060418j.

Authors

Tobias Hanauer¹, Jürgen C Aschenbrenner, Nikolaus Korber

Affiliation

¹ Institut für Anorganische Chemie der Universität Regensburg, Universitätsstrasse 31, D-93053 Regensburg, Germany.

PMID: 16903728
DOI: 10.1021/ic060418j

Abstract

Compounds [Rb(18-crown-6)]4As14.6NH3 (1) and [Li(NH3)4]4P14.NH3 (2) were prepared by the reaction of Rb4As6 with SbPh3 and 18-crown-6 and by the reduction of white phosphorus with elemental lithium in liquid ammonia, respectively. Both were characterized by low-temperature single-crystal X-ray structure analysis. They were found to contain the Ci symmetrical Pn14(4-) anion (Pn = P, As), which consists of two nortricyclane-like Pn7-cages connected by a single bond. Molecular complexes of [Rb(18-crown-6)(NH3)]2[Rb(18-crown-6)]2As14 are formed in 1, which are connected to fanfold sheets via N-H...O bonds. The anion is isolated in 2, and N-H...N bonds result in the formation of {[Li(NH3)4](mu-NH3)2[Li(NH3)4]}2+ cationic complexes.