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The new Zintl compounds RbNa8Ga3Pn6 (Pn = P, As) and Na10NbGaAs6 have been synthesized from the corresponding elements at high temperatures. RbNa8Ga3P6 and RbNa8Ga3As6 crystallize with a novel structure type that features trigonal planar [Ga3P6]9– and [Ga3As6]9– motifs, which are isosteric with the 1,3,5-trioxanetrione (a cyclic trimer of carbon dioxide). Na10NbGaAs6, an unforeseen side product of the same reactions boasts a structure, which is based on NbAs4 and GaAs4 tetrahedra, condensed by sharing common edges into [NbGaAs6]10– dimers. The bonding characteristics of both structures are discussed. All three compounds reported herein represent the first compounds found in the respective quaternary systems

Synthesis and Crystal Structures of the Quaternary Zintl Phases RbNa8Ga3Pn6 (Pn = P, As) and Na10NbGaAs6