Add time:07/15/2019         Source:sciencedirect.com

Three new mixed nickel-gallium chalcogenides, Ni6.10GaS2 (I4/mmm, a = 3.5310(5) Å, c = 17.968(4) Å, Z = 2, R1 = 0.014), Ni5.63GaSe2 (I4/mmm, a = 3.5995(3) Å, c = 18.517(3) Å, Z = 2, R1 = 0.018), and Ni8.54Ga2Se2 (I4/mmm, a = 3.5810(5) Å, c = 25.506(5) Å, Z = 2, R1 = 0.028), have been synthesized by a high-temperature ampoule route and characterized from single-crystal diffraction data, with their compositions supported by the EDS data. They belong to the relatively rare Ni7−xMQ2/Ni10−xM2Q2 type of structures (MGe, Sn, Sb, In), and are built from gallium-centered nickel cuboctahedra of the Cu3Au type, alternating along the c axis with either nickel-sulfur fragments of the Li2O and Cu2Sb/NaCl types, or with nickel-selenium fragments of the Cu2Sb/NaCl type. DFT calculations show close relationship of electronic structures of these ternary compounds to their parent intermetallic, Ni3Ga. Metallic conductivity and paramagnetic properties are predicted for all three. The bonding pattern, investigated via the ELI-D topological analysis, shows the multi-centered nickel-gallium bonds in the Cu3Au-type fragments. Magnetic measurements on Ni5.63GaSe2 show it to have an antiferromagnetic transition at 7 K and to obey the Curie-Weiss law above 160 K.

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