Description:
<jats:title>Abstract</jats:title><jats:p>The gold‐rich intermetallic phase Ca<jats:sub>4</jats:sub>Au<jats:sub>10</jats:sub>Zn<jats:sub>3</jats:sub> was synthesized from the elements by high‐frequency melting in sealed tantalum ampoules. Analyses of the sample by X‐ray powder and single crystal diffraction indicated a new structure type with a small homogeneity range resulting from Au/Zn mixing: <jats:italic>C</jats:italic>2/<jats:italic>c</jats:italic>, <jats:italic>a</jats:italic> = 1598.4(2), <jats:italic>b</jats:italic> = 819.7(1), <jats:italic>c</jats:italic> = 1188.2(2) pm, <jats:italic>β</jats:italic> = 120.93(1)°, <jats:italic>wR</jats:italic><jats:sub>2</jats:sub> = 0.0397, 2292 <jats:italic>F</jats:italic><jats:sup>2</jats:sup> values, 83 variables for Ca<jats:sub>4</jats:sub>Au<jats:sub>9.66(1)</jats:sub>Zn<jats:sub>3.34(1)</jats:sub>, and <jats:italic>a</jats:italic> = 1596.6(2), <jats:italic>b</jats:italic> = 818.8(2), <jats:italic>c</jats:italic> = 1187.1(2) pm, <jats:italic>β</jats:italic> = 120.91(2)°, <jats:italic>wR</jats:italic><jats:sub>2</jats:sub> = 0.0280, 2296 <jats:italic>F</jats:italic><jats:sup>2</jats:sup> values, 83 variables for Ca<jats:sub>4</jats:sub>Au<jats:sub>9.98(1)</jats:sub>Zn<jats:sub>3.02(1)</jats:sub>. The gold atoms built up a three‐dimensional distorted tetrahedral network with Au–Au distances ranging from 274–294 pm. The cavities within this network are filled by calcium atoms and Zn<jats:sub>3</jats:sub> triangles (272–279 pm Zn–Zn) in an ordered manner. The small homogeneity range Ca<jats:sub>4</jats:sub>Au<jats:sub>10–<jats:italic>x</jats:italic></jats:sub>Zn<jats:sub>3+<jats:italic>x</jats:italic></jats:sub> concerns Au/Zn mixing within the triangles and the tetrahedral network as well. The crystal chemical relationship with the aristotype AlB<jats:sub>2</jats:sub> is discussed on the basis of a group‐subgroup scheme.</jats:p>