Abstract: | Binary and multicomponent intermetallic compounds based on lithium and p‐elements of Groups III–V of the Periodic Table are useful as modern electrode materials in lithium‐ion batteries. However, the interactions between the components in the Li–Ge–B ternary system have not been reported. The structure of tetralithium digermanium boride, Li4Ge2B, exhibits a new structure type, in the noncentrosymmetric space group R3m, in which all the Li, Ge and B atoms occupy sites with 3m symmetry. The title structure is closely related to the Mo2B5 and Li5Sn2 structure types, which crystallize in the centrosymmetric space group R m. All the atoms in the title structure are coordinated by rhombic dodecahedra (coordination number = 14), similar to the atoms in related structures. According to electronic structure calculations using the tight‐binding–linear muffin‐tin orbital–atomic spheres approximation (TB–LMTO–ASA) method, strong covalent Ge—Ge and Ge—B interactions were established. |