Yellow needles-like single crystals of Li4P2S6 were obtained serendipitously during the preparation of Li7P3S10O. The twinned crystal structure of Li4P2S6 was determined from single-crystal X-ray diffraction data [wR(F 2) = 0.069, 716 reflections, 40 variables]. Li4P2S6 crystallizes in the trigonal system, space group P 3 ‾ m 1 $P\overline{3}m1$ (N° 164), a = 10.5042(8) Å, c = 6.5837(6) Å, V = 629.11(9) Å3 and Z = 2. The lithium octahedra form a [Li4S6]8− honeycomb-like structure within which diphosphate units are located. The comparison of our crystal structure to those of P63/mcm-, P 3 ‾ 1 m $P\overline{3}1m$ -, and P321-Li4P2S6 demonstrated group-subgroup relationships and associated the disorder or order of the phosphorus atoms within the identical [Li4S6]8− 3d-frameworks to the choice of the unit cell (the subcell with a ∼ 6.07 Å vs. the supercell with a ∼ 10.5 Å).

中文翻译：

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Li4P2S6的孪晶单晶结构

黄色针状锂单晶4个P2个小号6个在准备李的过程中偶然获得7P3个小号10O. Li的孪晶结构4个P2个小号6个由单晶 X 射线衍射数据 [wR(F 2个) = 0.069，716 次反射，40 个变量]。李4个P2个小号6个结晶于三方系，空间群 P 3个 ‾ 米 1个 $P\overline{3}m1$ (N° 164),A= 10.5042(8) Å,C= 6.5837(6) Å,V= 629.11(9) Å3个和Z= 2. 锂八面体形成 [Li4个小号6个]8−蜂窝状结构，其中包含二磷酸盐单元。我们的晶体结构与那些的比较P6个3个/米厘米-, P 3个 ‾ 1个 米 $P\overline{3}1m$ -， 和P321锂4个P2个小号6个证明了组-亚组关系，并与相同[Li]内磷原子的无序或顺序相关联4个小号6个]8−3d-frameworks 到单位单元的选择（子单元与A∼ 6.07 埃对比超级电池与A∼ 10.5 Å)。