New Layered Boride NiPtB ( = 0.5) with a Ternary Derivative Structure of MoB.

A novel ternary boride, NiPtB ( = 0.5), was obtained by argon-arc melting of the elements followed by annealing at 750 °C. It exhibits a new structure type with the space group ( = 2.9835(3) Å, = 3.0470(3) Å, = 15.3843(3) Å; = 4; single-crystal X-ray data) and displays distinct layers of condensed [BNi] and [BPt] (and [Pt]) trigonal prisms with mutually perpendicular axes. Atoms of Pt and Ni from adjacent layers interlink to form empty tetragonal pyramids and tetrahedra. Two boron atom positions form two orthogonal zigzag chains; however, one boron position exhibits a partial boron occupancy. Considering B-deficiency, the platinum boride substructure in NiPtB quantitatively corresponds to a trigonal prismatic slab in the PtB structure, while the nickel boride partial structure is consistent with the CrB-type NiB binary. Cell parameters and atomic coordinates of NiPtB and PtB were refined in the scope of generalized gradient approximation. Chemical bonding analysis by means of the electron localizability approach, supported by Bader charge analysis, reveals a strong electron contribution of Ni atoms for stabilization of the boron zigzag chains, wherein boron atoms are bonded covalently. Bonding within the platinum boride partial structures in the studied compounds varies depending on the atom coordination of boron: from covalent in both the NiPtB structure and trigonal prismatic slabs in PtB to mixed metallic with covalent contributions in [BPt] octahedra in PtB. Electrical resistivity measurements characterize NiPtB as a metal with no phase transitions in the temperature range from 2 to 300 K, in concord with electronic band structure calculations and specific heat measurements. The compound is characterized by a positive Hall coefficient at 20 K. This work unveils a new elemental space on realizing novel layered boride structural arrangements and provides a reference for future experiments.