In the ternary (Sr/Ca)‐Au‐Al phase space for 5–8 at % Sr/Ca and nearly equimolar mixture of Au and Al, five new NaZn₁₃‐derivatives Sr/Ca(Au_xAl_1–x)_12–13 were discovered and their atomic site preferences and electronic structures were studied: (1) at higher Au content, cubic SrAu_xAl_13–x [7.24(2) ≥ x ≥ 6.68(2)] shows no obvious atomic site preferences; (2) at lower Au content, tetragonal SrAu_xAl_13–x [6.59(1) ≥ x ≥ 6.35(3)] shows icosahedra exclusively centered by Al and preferential atomic arrangements to maximize the number of Au–Al (or Al‐rich) shortest distances; (3) a monoclinic SrAu_6.10(3)Al_6.40 compound was uncovered from studies of a single crystal specimen with problematic refinement issues but more detailed powder X‐ray diffraction analysis which suggest even more pronounced geometric distortion from the NaZn₁₃‐type structure as well as preferential arrangements for Au–Al nearest contacts; (4) tetragonal SrAu_5.75(2)Al_6.25 with all empty icosahedra; and (5) orthorhombic CaAu_6.09(2)Al_6.01(1) with icosahedra that are half empty and half partially occupied by Al. Electronic DOS and COHP curves were used to rationalize the structural depiction of Sr/Ca(Au_xAl_1–x)_12–13 as icosahedra packing of (Au_xAl_1–x)_12–13 with voids filled by the electropositive Sr/Ca.

中文翻译：

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Sr / Ca（AuxAl1-x）12-13的NaZn13型衍生物的结构组成微妙之处

在5–8 at％Sr / Ca和几乎等摩尔的Au和Al的三元（Sr / Ca）-Au-Al相空间中，五种新的NaZn ₁₃衍生物Sr / Ca（Au _x Al _{1– x}）_{12 -13}被发现和它们的原子的网站偏好和电子结构进行了研究：（1）在Au含量较高，立方SrAu _X的Al _{13- X} [7.24（2）≥ X ≥6.68（2）]示出了没有明显的原子网站偏好; （2）在较低的Au含量，四方SrAu _X的Al _{13- X} [6.59（1）≥ X≥6.35（3）]显示二十面体仅以Al为中心，并具有优先的原子排列以最大化Au-Al（或富含Al的）最短距离的数量；（3）从单晶样品的细化问题中发现单斜SrAu _6.10（3） Al _6.40化合物，但更详细的粉末X射线衍射分析表明，NaZn ₁₃型结构的几何变形甚至更为明显，因为以及对金铝最近接触者的优惠安排；（4）四角形SrAu _5.75（2） Al _6.25，所有空的二十面体；和（5）正交晶CaAu _6.09（2） Al _6.01（1）二十面体的一半是空的，一半被Al占据。电子DOS和COHP曲线用于合理化Sr的结构描绘/钙（AU _X的Al _{1- X}）_12-13作为二十面体包装（AU _X的Al _{1- X}）_12-13与由正电SR /填充的空穴钙