Na3Hf is beta Cu3Ti-like structured and crystallizes in the hexagonal P6_3/mmc space group. Na(1) is bonded to eight equivalent Na(1) and four equivalent Hf(1) atoms to form distorted NaNa8Hf4 cuboctahedra that share corners with four equivalent Hf(1)Na12 cuboctahedra, corners with fourteen equivalent Na(1)Na8Hf4 cuboctahedra, edges with six equivalent Hf(1)Na12 cuboctahedra, edges with twelve equivalent Na(1)Na8Hf4 cuboctahedra, faces with four equivalent Hf(1)Na12 cuboctahedra, and faces with sixteen equivalent Na(1)Na8Hf4 cuboctahedra. Hf(1) is bonded to twelve equivalent Na(1) atoms to form HfNa12 cuboctahedra that share corners with six equivalent Hf(1)Na12 cuboctahedra, corners with twelve equivalent Na(1)Na8Hf4 cuboctahedra, edges with eighteen equivalent Na(1)Na8Hf4 cuboctahedra, faces with eight equivalent Hf(1)Na12 cuboctahedra, and faces with twelve equivalent Na(1)Na8Hf4 cuboctahedra.
Na3Hf is beta Cu3Ti-like structured and crystallizes in the hexagonal P6_3/mmc space group. Na(1) is bonded to eight equivalent Na(1) and four equivalent Hf(1) atoms to form distorted NaNa8Hf4 cuboctahedra that share corners with four equivalent Hf(1)Na12 cuboctahedra, corners with fourteen equivalent Na(1)Na8Hf4 cuboctahedra, edges with six equivalent Hf(1)Na12 cuboctahedra, edges with twelve equivalent Na(1)Na8Hf4 cuboctahedra, faces with four equivalent Hf(1)Na12 cuboctahedra, and faces with sixteen equivalent Na(1)Na8Hf4 cuboctahedra. There are a spread of Na(1)-Na(1) bond distances ranging from 3.44-3.49 Å. There are two shorter (3.45 Å) and two longer (3.46 Å) Na(1)-Hf(1) bond lengths. Hf(1) is bonded to twelve equivalent Na(1) atoms to form HfNa12 cuboctahedra that share corners with six equivalent Hf(1)Na12 cuboctahedra, corners with twelve equivalent Na(1)Na8Hf4 cuboctahedra, edges with eighteen equivalent Na(1)Na8Hf4 cuboctahedra, faces with eight equivalent Hf(1)Na12 cuboctahedra, and faces with twelve equivalent Na(1)Na8Hf4 cuboctahedra.