VTiFe is alpha-derived structured and crystallizes in the orthorhombic Amm2 space group. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to four equivalent Ti(2), two equivalent V(2), four equivalent V(1), and two equivalent Fe(2) atoms to form distorted TiTi4V6Fe2 cuboctahedra that share corners with two equivalent Ti(3)V6Fe6 cuboctahedra, corners with four equivalent Ti(1)Ti4V6Fe2 cuboctahedra, corners with eight equivalent Fe(1)Ti2V6Fe4 cuboctahedra, edges with two equivalent Ti(1)Ti4V6Fe2 cuboctahedra, edges with four equivalent Ti(3)V6Fe6 cuboctahedra, faces with four equivalent Fe(1)Ti2V6Fe4 cuboctahedra, and faces with eight equivalent Ti(2)Ti4V6Fe2 cuboctahedra. In the second Ti site, Ti(2) is bonded to two equivalent Ti(1); two equivalent Ti(2); two equivalent V(2); four V(1,1); and two equivalent Fe(2) atoms to form distorted TiTi4V6Fe2 cuboctahedra that share corners with four equivalent Ti(2)Ti4V6Fe2 cuboctahedra, corners with four equivalent Ti(3)V6Fe6 cuboctahedra, corners with six equivalent Fe(1)Ti2V6Fe4 cuboctahedra, edges with two equivalent Ti(2)Ti4V6Fe2 cuboctahedra, edges with four equivalent Fe(1)Ti2V6Fe4 cuboctahedra, faces with two equivalent Ti(3)V6Fe6 cuboctahedra, faces with two equivalent Fe(1)Ti2V6Fe4 cuboctahedra, faces with four equivalent Ti(1)Ti4V6Fe2 cuboctahedra, and faces with four equivalent Ti(2)Ti4V6Fe2 cuboctahedra. In the third Ti site, Ti(3) is bonded to two equivalent V(1), four equivalent V(2), two equivalent Fe(2), and four equivalent Fe(1) atoms to form distorted TiV6Fe6 cuboctahedra that share corners with two equivalent Ti(1)Ti4V6Fe2 cuboctahedra, corners with four equivalent Ti(3)V6Fe6 cuboctahedra, corners with eight equivalent Ti(2)Ti4V6Fe2 cuboctahedra, edges with two equivalent Ti(3)V6Fe6 cuboctahedra, edges with four equivalent Ti(1)Ti4V6Fe2 cuboctahedra, faces with four equivalent Ti(2)Ti4V6Fe2 cuboctahedra, and faces with eight equivalent Fe(1)Ti2V6Fe4 cuboctahedra. There are four inequivalent V sites. In the first V site, V(1) is bonded in a 16-coordinate geometry to one Ti(3), two equivalent Ti(1), four equivalent Ti(2), one V(1), three equivalent V(2), two equivalent Fe(1), and three equivalent Fe(2) atoms. In the second V site, V(2) is bonded in a 16-coordinate geometry to one Ti(1), two equivalent Ti(2), two equivalent Ti(3), one V(2), three equivalent V(1), three equivalent Fe(2), and four equivalent Fe(1) atoms. In the third V site, V(2) is bonded in a 16-coordinate geometry to one Ti(1); two equivalent Ti(2); two equivalent Ti(3); one V(2); three V(1,1); three equivalent Fe(2); and four equivalent Fe(1) atoms. In the fourth V site, V(1) is bonded in a 16-coordinate geometry to one Ti(3); two equivalent Ti(1); four equivalent Ti(2); one V(1); three V(2,2); two equivalent Fe(1); and three equivalent Fe(2) atoms. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent Ti(3); two equivalent V(1); four V(2,2); two equivalent Fe(1); and two equivalent Fe(2) atoms to form distorted FeTi2V6Fe4 cuboctahedra that share corners with four equivalent Ti(1)Ti4V6Fe2 cuboctahedra, corners with four equivalent Fe(1)Ti2V6Fe4 cuboctahedra, corners with six equivalent Ti(2)Ti4V6Fe2 cuboctahedra, edges with two equivalent Fe(1)Ti2V6Fe4 cuboctahedra, edges with four equivalent Ti(2)Ti4V6Fe2 cuboctahedra, faces with two equivalent Ti(1)Ti4V6Fe2 cuboctahedra, faces with two equivalent Ti(2)Ti4V6Fe2 cuboctahedra, faces with four equivalent Ti(3)V6Fe6 cuboctahedra, and faces with four equivalent Fe(1)Ti2V6Fe4 cuboctahedra. In the second Fe site, Fe(2) is bonded in a 12-coordinate geometry to one Ti(1), one Ti(3), two equivalent Ti(2), three equivalent V(1), three equivalent V(2), and two equivalent Fe(1) atoms.
VTiFe is alpha-derived structured and crystallizes in the orthorhombic Amm2 space group. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to four equivalent Ti(2), two equivalent V(2), four equivalent V(1), and two equivalent Fe(2) atoms to form distorted TiTi4V6Fe2 cuboctahedra that share corners with two equivalent Ti(3)V6Fe6 cuboctahedra, corners with four equivalent Ti(1)Ti4V6Fe2 cuboctahedra, corners with eight equivalent Fe(1)Ti2V6Fe4 cuboctahedra, edges with two equivalent Ti(1)Ti4V6Fe2 cuboctahedra, edges with four equivalent Ti(3)V6Fe6 cuboctahedra, faces with four equivalent Fe(1)Ti2V6Fe4 cuboctahedra, and faces with eight equivalent Ti(2)Ti4V6Fe2 cuboctahedra. There are two shorter (2.47 Å) and two longer (2.52 Å) Ti(1)-Ti(2) bond lengths. Both Ti(1)-V(2) bond lengths are 2.86 Å. All Ti(1)-V(1) bond lengths are 2.93 Å. Both Ti(1)-Fe(2) bond lengths are 2.37 Å. In the second Ti site, Ti(2) is bonded to two equivalent Ti(1); two equivalent Ti(2); two equivalent V(2); four V(1,1); and two equivalent Fe(2) atoms to form distorted TiTi4V6Fe2 cuboctahedra that share corners with four equivalent Ti(2)Ti4V6Fe2 cuboctahedra, corners with four equivalent Ti(3)V6Fe6 cuboctahedra, corners with six equivalent Fe(1)Ti2V6Fe4 cuboctahedra, edges with two equivalent Ti(2)Ti4V6Fe2 cuboctahedra, edges with four equivalent Fe(1)Ti2V6Fe4 cuboctahedra, faces with two equivalent Ti(3)V6Fe6 cuboctahedra, faces with two equivalent Fe(1)Ti2V6Fe4 cuboctahedra, faces with four equivalent Ti(1)Ti4V6Fe2 cuboctahedra, and faces with four equivalent Ti(2)Ti4V6Fe2 cuboctahedra. There is one shorter (2.48 Å) and one longer (2.50 Å) Ti(2)-Ti(2) bond length. Both Ti(2)-V(2) bond lengths are 2.83 Å. There are two shorter (2.90 Å) and two longer (2.97 Å) Ti(2)-V(1,1) bond lengths. Both Ti(2)-Fe(2) bond lengths are 2.44 Å. In the third Ti site, Ti(3) is bonded to two equivalent V(1), four equivalent V(2), two equivalent Fe(2), and four equivalent Fe(1) atoms to form distorted TiV6Fe6 cuboctahedra that share corners with two equivalent Ti(1)Ti4V6Fe2 cuboctahedra, corners with four equivalent Ti(3)V6Fe6 cuboctahedra, corners with eight equivalent Ti(2)Ti4V6Fe2 cuboctahedra, edges with two equivalent Ti(3)V6Fe6 cuboctahedra, edges with four equivalent Ti(1)Ti4V6Fe2 cuboctahedra, faces with four equivalent Ti(2)Ti4V6Fe2 cuboctahedra, and faces with eight equivalent Fe(1)Ti2V6Fe4 cuboctahedra. Both Ti(3)-V(1) bond lengths are 2.72 Å. All Ti(3)-V(2) bond lengths are 2.82 Å. Both Ti(3)-Fe(2) bond lengths are 2.38 Å. There are two shorter (2.44 Å) and two longer (2.55 Å) Ti(3)-Fe(1) bond lengths. There are four inequivalent V sites. In the first V site, V(1) is bonded in a 16-coordinate geometry to one Ti(3), two equivalent Ti(1), four equivalent Ti(2), one V(1), three equivalent V(2), two equivalent Fe(1), and three equivalent Fe(2) atoms. The V(1)-V(1) bond length is 3.10 Å. There is one shorter (2.93 Å) and two longer (3.06 Å) V(1)-V(2) bond lengths. Both V(1)-Fe(1) bond lengths are 2.61 Å. There are two shorter (2.83 Å) and one longer (3.05 Å) V(1)-Fe(2) bond length. In the second V site, V(2) is bonded in a 16-coordinate geometry to one Ti(1), two equivalent Ti(2), two equivalent Ti(3), one V(2), three equivalent V(1), three equivalent Fe(2), and four equivalent Fe(1) atoms. The V(2)-V(2) bond length is 2.67 Å. There is one shorter (2.88 Å) and two longer (2.95 Å) V(2)-Fe(2) bond lengths. There are two shorter (2.80 Å) and two longer (2.85 Å) V(2)-Fe(1) bond lengths. In the third V site, V(2) is bonded in a 16-coordinate geometry to one Ti(1); two equivalent Ti(2); two equivalent Ti(3); one V(2); three V(1,1); three equivalent Fe(2); and four equivalent Fe(1) atoms. The V(2)-Ti(1) bond length is 2.86 Å. Both V(2)-Ti(2) bond lengths are 2.83 Å. Both V(2)-Ti(3) bond lengths are 2.82 Å. The V(2)-V(2) bond length is 2.67 Å. There is one shorter (2.93 Å) and two longer (3.06 Å) V(2)-V(1,1) bond lengths. There is one shorter (2.88 Å) and two longer (2.95 Å) V(2)-Fe(2) bond lengths. There are two shorter (2.80 Å) and two longer (2.85 Å) V(2)-Fe(1) bond lengths. In the fourth V site, V(1) is bonded in a 16-coordinate geometry to one Ti(3); two equivalent Ti(1); four equivalent Ti(2); one V(1); three V(2,2); two equivalent Fe(1); and three equivalent Fe(2) atoms. The V(1)-Ti(3) bond length is 2.72 Å. Both V(1)-Ti(1) bond lengths are 2.93 Å. The V(1)-V(1) bond length is 3.10 Å. The V(1)-V(2) bond length is 2.93 Å. Both V(1)-Fe(1) bond lengths are 2.61 Å. There are two shorter (2.83 Å) and one longer (3.05 Å) V(1)-Fe(2) bond length. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent Ti(3); two equivalent V(1); four V(2,2); two equivalent Fe(1); and two equivalent Fe(2) atoms to form distorted FeTi2V6Fe4 cuboctahedra that share corners with four equivalent Ti(1)Ti4V6Fe2 cuboctahedra, corners with four equivalent Fe(1)Ti2V6Fe4 cuboctahedra, corners with six equivalent Ti(2)Ti4V6Fe2 cuboctahedra, edges with two equivalent Fe(1)Ti2V6Fe4 cuboctahedra, edges with four equivalent Ti(2)Ti4V6Fe2 cuboctahedra, faces with two equivalent Ti(1)Ti4V6Fe2 cuboctahedra, faces with two equivalent Ti(2)Ti4V6Fe2 cuboctahedra, faces with four equivalent Ti(3)V6Fe6 cuboctahedra, and faces with four equivalent Fe(1)Ti2V6Fe4 cuboctahedra. There is one shorter (2.44 Å) and one longer (2.54 Å) Fe(1)-Fe(1) bond length. Both Fe(1)-Fe(2) bond lengths are 2.36 Å. In the second Fe site, Fe(2) is bonded in a 12-coordinate geometry to one Ti(1), one Ti(3), two equivalent Ti(2), three equivalent V(1), three equivalent V(2), and two equivalent Fe(1) atoms.