NaYb3 is beta Cu3Ti-like structured and crystallizes in the hexagonal P6_3/mmc space group. Na(1) is bonded to twelve Yb(1,1) atoms to form NaYb12 cuboctahedra that share corners with six equivalent Na(1)Yb12 cuboctahedra; corners with twelve Yb(1,1)Na4Yb8 cuboctahedra; edges with eighteen Yb(1,1)Na4Yb8 cuboctahedra; faces with eight equivalent Na(1)Yb12 cuboctahedra; and faces with twelve Yb(1,1)Na4Yb8 cuboctahedra. There are two inequivalent Yb sites. In the first Yb site, Yb(1) is bonded to four equivalent Na(1) and eight Yb(1,1) atoms to form YbNa4Yb8 cuboctahedra that share corners with four equivalent Na(1)Yb12 cuboctahedra; corners with fourteen Yb(1,1)Na4Yb8 cuboctahedra; edges with six equivalent Na(1)Yb12 cuboctahedra; edges with twelve Yb(1,1)Na4Yb8 cuboctahedra; faces with four equivalent Na(1)Yb12 cuboctahedra; and faces with sixteen Yb(1,1)Na4Yb8 cuboctahedra. In the second Yb site, Yb(1) is bonded to four equivalent Na(1) and eight Yb(1,1) atoms to form YbNa4Yb8 cuboctahedra that share corners with four equivalent Na(1)Yb12 cuboctahedra; corners with fourteen Yb(1,1)Na4Yb8 cuboctahedra; edges with six equivalent Na(1)Yb12 cuboctahedra; edges with twelve Yb(1,1)Na4Yb8 cuboctahedra; faces with four equivalent Na(1)Yb12 cuboctahedra; and faces with sixteen Yb(1,1)Na4Yb8 cuboctahedra.
NaYb3 is beta Cu3Ti-like structured and crystallizes in the hexagonal P6_3/mmc space group. Na(1) is bonded to twelve Yb(1,1) atoms to form NaYb12 cuboctahedra that share corners with six equivalent Na(1)Yb12 cuboctahedra; corners with twelve Yb(1,1)Na4Yb8 cuboctahedra; edges with eighteen Yb(1,1)Na4Yb8 cuboctahedra; faces with eight equivalent Na(1)Yb12 cuboctahedra; and faces with twelve Yb(1,1)Na4Yb8 cuboctahedra. There are six shorter (3.85 Å) and six longer (3.86 Å) Na(1)-Yb(1,1) bond lengths. There are two inequivalent Yb sites. In the first Yb site, Yb(1) is bonded to four equivalent Na(1) and eight Yb(1,1) atoms to form YbNa4Yb8 cuboctahedra that share corners with four equivalent Na(1)Yb12 cuboctahedra; corners with fourteen Yb(1,1)Na4Yb8 cuboctahedra; edges with six equivalent Na(1)Yb12 cuboctahedra; edges with twelve Yb(1,1)Na4Yb8 cuboctahedra; faces with four equivalent Na(1)Yb12 cuboctahedra; and faces with sixteen Yb(1,1)Na4Yb8 cuboctahedra. There are a spread of Yb(1)-Yb(1,1) bond distances ranging from 3.82-3.87 Å. In the second Yb site, Yb(1) is bonded to four equivalent Na(1) and eight Yb(1,1) atoms to form YbNa4Yb8 cuboctahedra that share corners with four equivalent Na(1)Yb12 cuboctahedra; corners with fourteen Yb(1,1)Na4Yb8 cuboctahedra; edges with six equivalent Na(1)Yb12 cuboctahedra; edges with twelve Yb(1,1)Na4Yb8 cuboctahedra; faces with four equivalent Na(1)Yb12 cuboctahedra; and faces with sixteen Yb(1,1)Na4Yb8 cuboctahedra. There is one shorter (3.82 Å) and one longer (3.87 Å) Yb(1)-Yb(1) bond length.