Recently lithium phosphidogermanates were discovered as fast lithium ion conductors for potential usage as solid electrolytes in all solid‐state batteries. In this context we also studied sodium phosphidogermanates since sodium ion conductors are of equal interest. Na₂Ge₃P₃ and Na₅Ge₇P₅ both crystallize in the monoclinic space group C2/m with unit cell parameters of a = 17.639(4) Å, b = 3.6176(7) Å, c = 11.354(2) Å, β = 92.74(3)° and a = 16.168(5) Å, b = 3.6776(7) Å, c = 12.924(4) Å, β = 91.30(3)°, respectively. Both show linearly condensed 9‐atom cages of four Ge / five P and five Ge / four P atoms, respectively. These cages contain Ge–Ge bonds and form one‐dimensional tubes by sharing three atoms. The parallel tubes are paired through further Ge–Ge bonds. Both structures are closely related to the one of the fibrous type of crystalline red phosphorus. A comparison with other compounds such as NaGe₃P₃ and GeP reveals recurring structural motifs with a broad variety of connection patterns. According to the general formula Na_4+xGe_6+xP_6–x with x = 0 and 1, the two novel structures hint for the possibility of a variable Na content which might allow Na ion mobility.

中文翻译：

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Na2Ge3P3和Na5Ge7P5包含模仿纤维状红磷结构的杂原子聚阴离子

最近，人们发现磷酸锗锗酸锂是快速的锂离子导体，可在所有固态电池中用作固体电解质。在这种情况下，我们还研究了磷酸锗锗酸钠，因为钠离子导体具有同等的意义。Na ₂ Ge ₃ P ₃和Na ₅ Ge ₇ P ₅均在单斜晶空间群C 2 / m中结晶，其晶胞参数为a = 17.639（4）Å，b = 3.6176（7）Å，c = 11.354（2） ）Å，β = 92.74（3）°和a = 16.168（5）Å，b = 3.6776（7）Å，c = 12.924（4）Å，β = 91.30（3）°。两者都分别显示了四个Ge /五个P和五个Ge /四个P原子的线性缩合9原子笼。这些笼包含Ge-Ge键，并通过共享三个原子形成一维管。平行管通过进一步的Ge-Ge键配对。两种结构都与一种纤维类型的结晶性红磷密切相关。与其他化合物（如NaGe ₃ P ₃和GeP）的比较表明，具有多种连接模式的重复结构基序。根据通式Na _{4+ x} Ge _{6+ x} P _{6– x}与x = 0和1，这两种新颖的结构暗示了Na含量可变的可能性，这可能会导致Na离子迁移。