ThFe3Al2 crystallizes in the orthorhombic Cmmm space group. Th(1) is bonded in a 18-coordinate geometry to four equivalent Fe(2), six equivalent Fe(1), and eight equivalent Al(1) atoms. There are two inequivalent Fe sites. In the first Fe site, Fe(2) is bonded to four equivalent Th(1), four equivalent Fe(1), and four equivalent Al(1) atoms to form distorted FeTh4Al4Fe4 cuboctahedra that share corners with eight equivalent Fe(2)Th4Al4Fe4 cuboctahedra, corners with eight equivalent Al(1)Th4Al2Fe6 cuboctahedra, edges with two equivalent Fe(2)Th4Al4Fe4 cuboctahedra, edges with eight equivalent Al(1)Th4Al2Fe6 cuboctahedra, faces with two equivalent Fe(2)Th4Al4Fe4 cuboctahedra, and faces with eight equivalent Al(1)Th4Al2Fe6 cuboctahedra. In the second Fe site, Fe(1) is bonded in a 9-coordinate geometry to three equivalent Th(1), two equivalent Fe(2), and four equivalent Al(1) atoms. Al(1) is bonded to four equivalent Th(1), two equivalent Fe(2), four equivalent Fe(1), and two equivalent Al(1) atoms to form distorted AlTh4Al2Fe6 cuboctahedra that share corners with four equivalent Fe(2)Th4Al4Fe4 cuboctahedra, corners with twelve equivalent Al(1)Th4Al2Fe6 cuboctahedra, edges with four equivalent Fe(2)Th4Al4Fe4 cuboctahedra, edges with six equivalent Al(1)Th4Al2Fe6 cuboctahedra, faces with four equivalent Fe(2)Th4Al4Fe4 cuboctahedra, and faces with six equivalent Al(1)Th4Al2Fe6 cuboctahedra.
ThFe3Al2 crystallizes in the orthorhombic Cmmm space group. Th(1) is bonded in a 18-coordinate geometry to four equivalent Fe(2), six equivalent Fe(1), and eight equivalent Al(1) atoms. All Th(1)-Fe(2) bond lengths are 3.41 Å. There are two shorter (3.03 Å) and four longer (3.05 Å) Th(1)-Fe(1) bond lengths. All Th(1)-Al(1) bond lengths are 3.32 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(2) is bonded to four equivalent Th(1), four equivalent Fe(1), and four equivalent Al(1) atoms to form distorted FeTh4Al4Fe4 cuboctahedra that share corners with eight equivalent Fe(2)Th4Al4Fe4 cuboctahedra, corners with eight equivalent Al(1)Th4Al2Fe6 cuboctahedra, edges with two equivalent Fe(2)Th4Al4Fe4 cuboctahedra, edges with eight equivalent Al(1)Th4Al2Fe6 cuboctahedra, faces with two equivalent Fe(2)Th4Al4Fe4 cuboctahedra, and faces with eight equivalent Al(1)Th4Al2Fe6 cuboctahedra. All Fe(2)-Fe(1) bond lengths are 2.50 Å. All Fe(2)-Al(1) bond lengths are 2.60 Å. In the second Fe site, Fe(1) is bonded in a 9-coordinate geometry to three equivalent Th(1), two equivalent Fe(2), and four equivalent Al(1) atoms. All Fe(1)-Al(1) bond lengths are 2.60 Å. Al(1) is bonded to four equivalent Th(1), two equivalent Fe(2), four equivalent Fe(1), and two equivalent Al(1) atoms to form distorted AlTh4Al2Fe6 cuboctahedra that share corners with four equivalent Fe(2)Th4Al4Fe4 cuboctahedra, corners with twelve equivalent Al(1)Th4Al2Fe6 cuboctahedra, edges with four equivalent Fe(2)Th4Al4Fe4 cuboctahedra, edges with six equivalent Al(1)Th4Al2Fe6 cuboctahedra, faces with four equivalent Fe(2)Th4Al4Fe4 cuboctahedra, and faces with six equivalent Al(1)Th4Al2Fe6 cuboctahedra. Both Al(1)-Al(1) bond lengths are 2.71 Å.