The lithium ytterbium ortho -thiophosphates Li 9 Yb 2 [PS 4 ] 5 and Li 6 Yb 3 [PS 4 ] 5 were prepared through the reaction of stoichiometric amounts of ytterbium metal, elemental sulfur, red phosphorus and lithium hemisulfide at elevated temperatures in sealed silica tubes. The compounds occur as dark red single crystals which crystallize monoclinically in space group C 2/ c with the lattice parameters a = 1487.98(9), b = 978.63(6), c = 2046.75(12) pm and β = 96.142(3)° for Li 9 Yb 2 [PS 4 ] 5 ( Z = 4) and a = 2814.83(16), b = 997.34(6), c = 3338.52(19) pm and β = 113.685(3)° for Li 6 Yb 3 [PS 4 ] 5 ( Z = 12). Li 9 Yb 2 [PS 4 ] 5 can be assigned to the structure type of Li 9 Nd 2 [PS 4 ] 5 , whereas the structure of Li 6 Yb 3 [PS 4 ] 5 the structure is similar to that of the prototypic Li 6 Gd 3 [PS 4 ] 5 . Both structures feature discrete [PS 4 ] 3– tetrahedra ( d (P–S) = 202–207 pm) and strands of [YbS 8 ] 13− polyhedra ( d (Yb–S) = 271–319 pm) propagating along [010]. When attributed to the general formula (Li 3 [PS 4 ]) x (Yb[PS 4 ]) y , ideas of the dimensionality of both structures can be derived. Whilst the lithium-richer Li 9 Yb 2 [PS 4 ] 5 ( x/y = 1.5) develops planes with the composition ∞2{[Yb[PS4]3]6−}${}_{\infty }^{2}\left\{{\left[\mathrm{Y}\mathrm{b}{\left[\mathrm{P}{\mathrm{S}}_{4}\right]}_{3}\right]}^{6-}\right\}$, Li 6 Yb 3 [PS 4 ] 5 ( x / y = 0.667) exhibits a rather complex three-dimensional network of ytterbium-centered polyhedra connected via [PS 4 ] 3– tetrahedra with lithium cations in the framework structure ∞3{[Yb3[PS4]5]6−}${}_{\infty }^{3}\left\{{\left[\mathrm{Y}{\mathrm{b}}_{\mathrm{3}}{\left[\mathrm{P}{\mathrm{S}}_{4}\right]}_{5}\right]}^{6-}\right\}$. These Li + cations are hard to locate in both compounds, but reside in four- to sixfold sulfur coordination ( d (Li–S) = 235–304 pm). Some Li + positions are underoccupied and some Li + cations share sites with Yb 3+ cations in Li 6 Yb 3 [PS 4 ] 5 , and even in Li 9 Yb 2 [PS 4 ] 5 their high displacement values suggest Li + cation mobility. According to the empirical formulae, three Li + cations have to be replaced with one Yb 3+ cation to reach the lithium-poorer compound and structure (Li 6 Yb 3 [PS 4 ] 5 ) starting from the lithium-richer one (Li 9 Yb 2 [PS 4 ] 5 ).

中文翻译：

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Li9Yb2 [PS4] 5和Li6Yb3 [PS4] 5：重新研究了两种含锂的硫代磷酸y（III）

通过化学计量的amounts金属，元素硫，红磷和半硫化锂在密封状态下反应，制得正硫代磷酸锂锂Li 9 Yb 2 [PS 4] 5和Li 6 Yb 3 [PS 4] 5。硅胶管。化合物以暗红色单晶形式出现，在空间组C 2 / c中单晶结晶，晶格参数为a = 1487.98（9），b = 978.63（6），c = 2046.75（12）pm和β= 96.142（3） Li 9 Yb 2 [PS 4] 5（Z = 4）和a = 2814.83（16），b = 997.34（6），c = 3338.52（19）pm和β= 113.685（3）°，对于Li 9 Yb 2 [PS 4] 5（Z = 4） 3 [PS 4] 5（Z = 12）。Li 9 Yb 2 [PS 4] 5可以分配给Li 9 Nd 2 [PS 4] 5的结构类型，而Li 6 Yb 3 [PS 4] 5的结构与原型Li的结构相似。 6 Gd 3 [PS 4] 5。两种结构均具有离散的[PS 4] 3–四面体（d（PS）= 202–207 pm）和[YbS 8] 13−多面体（d（Yb–S）= 271–319 pm）沿[[ 010]。当归因于通式（Li 3 [PS 4]）x（Yb [PS 4]）y时，可以得出两种结构的维数的思想。富含锂的Li 9 Yb 2 [PS 4] 5（x / y = 1.5）形成了成分为∞2{[Yb [PS4] 3] 6-} $ {} _ {\ infty} ^ {2的平面} \ left \ {{\ left [\ mathrm {Y} \ mathrm {b} {\ left [\ mathrm {P} {\ mathrm {S}} _ {4} \ right]} _ {3} \ right] } ^ {6-} \ right \} $，Li 6 Yb 3 [PS 4] 5（x / y = 0。667）在框架结构∞3{[Yb3 [PS4] 5] 6 −} $ {} _ {\ infty} ^ {3} \ left \ {{\ left [\ mathrm {Y} {\ mathrm {b}} _ {\ mathrm {3}}} {\ left [\ mathrm {P} {\ mathrm {S}} _ {4} \ right]} _ {5} \ right]} ^ {6-} \ right \} $。这些Li +阳离子很难在这两种化合物中找到，而是以四到六倍的硫配位形式存在（d（Li–S）= 235–304 pm）。Li 6 Yb 3 [PS 4] 5中某些Li +位置未被充分利用，并且某些Li +阳离子与Yb 3+阳离子共享位点，甚至在Li 9 Yb 2 [PS 4] 5中，它们的高位移值也表明Li +阳离子迁移率。根据经验公式，