PrVGe3 crystallizes in the hexagonal P6_3/mmc space group. Pr(1) is bonded to twelve equivalent Ge(1) atoms to form distorted PrGe12 cuboctahedra that share corners with six equivalent Pr(1)Ge12 cuboctahedra, corners with six equivalent V(1)Ge6 octahedra, faces with eight equivalent Pr(1)Ge12 cuboctahedra, and faces with six equivalent V(1)Ge6 octahedra. The corner-sharing octahedral tilt angles are 29°. V(1) is bonded to six equivalent Ge(1) atoms to form VGe6 octahedra that share corners with six equivalent Pr(1)Ge12 cuboctahedra, faces with six equivalent Pr(1)Ge12 cuboctahedra, and faces with two equivalent V(1)Ge6 octahedra. Ge(1) is bonded in a 8-coordinate geometry to four equivalent Pr(1), two equivalent V(1), and two equivalent Ge(1) atoms.
PrVGe3 crystallizes in the hexagonal P6_3/mmc space group. Pr(1) is bonded to twelve equivalent Ge(1) atoms to form distorted PrGe12 cuboctahedra that share corners with six equivalent Pr(1)Ge12 cuboctahedra, corners with six equivalent V(1)Ge6 octahedra, faces with eight equivalent Pr(1)Ge12 cuboctahedra, and faces with six equivalent V(1)Ge6 octahedra. The corner-sharing octahedral tilt angles are 29°. There are six shorter (3.13 Å) and six longer (3.24 Å) Pr(1)-Ge(1) bond lengths. V(1) is bonded to six equivalent Ge(1) atoms to form VGe6 octahedra that share corners with six equivalent Pr(1)Ge12 cuboctahedra, faces with six equivalent Pr(1)Ge12 cuboctahedra, and faces with two equivalent V(1)Ge6 octahedra. All V(1)-Ge(1) bond lengths are 2.57 Å. Ge(1) is bonded in a 8-coordinate geometry to four equivalent Pr(1), two equivalent V(1), and two equivalent Ge(1) atoms. Both Ge(1)-Ge(1) bond lengths are 2.55 Å.