Synthesis,Structural Characterization,Electronic Structure,and Magnetic Properties of the Zintl Phase Eu10Cd6Bi12

A new transition‐metal‐containing Zintl phase, Eu₁₀Cd₆Bi₁₂, was synthesized by combining the elements in excess molten Cd. Single‐crystal X‐ray diffraction studies indicated that this compound crystallizes in the orthorhombic space group Cmmm (No. 65) with a=7.840(2), b=24.060(7), and c=4.7809(14) Å. The crystal structure of Eu₁₀Cd₆Bi₁₂ can be viewed as a stacking of a series of Cd₆Bi₁₂] double layers, which are arranged alternately along the b axial direction. The layers are composed of corner‐ and edge‐shared CdBi₄ tetrahedra, a common feature in the crystal chemistry of many transition‐metal Zintl phases. Electronic‐band‐structure calculations confirm the closed‐shell configuration of all constituent elements and corroborate the electron count inferred by the Zintl formalism, that is, Eu²⁺]₁₀Cd²⁺]₆Bi^3?]₈Bi^2?]₄. Magnetic‐susceptibility measurements confirm the divalency of europium and show the existence of a long‐range antiferromagnetic order of the Eu spins below 12.3 K.