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VF6N2 is Fluorite structured and crystallizes in the cubic Fm-3m space group. The structure is zero-dimensional and consists of eight ammonia molecules and four VF6 clusters. In each VF6 cluster, V4+ is bonded in an octahedral geometry to six equivalent F1- atoms. All V–F bond lengths are 1.82 Å. F1- is bonded in a single-bond geometry to one V4+ atom.
(NH4)2NaVF6 is High-temperature superconductor-derived structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional and consists of eight ammonium molecules and one NaVF6 framework. In the NaVF6 framework, Na1+ is bonded to six equivalent F1- atoms to form NaF6 octahedra that share corners with six equivalent VF6 octahedra. The corner-sharing octahedral tilt angles are 0°. All Na–F bond lengths are 2.29 Å. V3+ is bonded to six equivalent F1- atoms to form VF6 octahedra that share corners with six equivalent NaF6 octahedra. The corner-sharing octahedral tilt angles are 0°. All V–F bond lengths are 2.00 Å. F1- is bonded in a linear geometry to one Na1+ and one V3+ atom.