HfWSi crystallizes in the orthorhombic Amm2 space group. There are two inequivalent Hf sites. In the first Hf site, Hf(1) is bonded in a 12-coordinate geometry to one W(3), two equivalent W(1), two equivalent W(2), three equivalent Si(1), and four equivalent Si(2) atoms. In the second Hf site, Hf(2) is bonded in a 12-coordinate geometry to one W(1), two equivalent W(3), four equivalent W(2), two equivalent Si(2), and three equivalent Si(1) atoms. There are three inequivalent W sites. In the first W site, W(1) is bonded to two equivalent Hf(2), four equivalent Hf(1), two equivalent Si(1), and four equivalent Si(2) atoms to form WHf6Si6 cuboctahedra that share corners with two equivalent W(3)Hf6Si2W4 cuboctahedra, corners with four equivalent W(1)Hf6Si6 cuboctahedra, corners with four equivalent Si(1)Hf6Si2W4 cuboctahedra, corners with eight equivalent W(2)Hf6Si2W4 cuboctahedra, edges with two equivalent W(1)Hf6Si6 cuboctahedra, edges with four equivalent W(3)Hf6Si2W4 cuboctahedra, faces with four equivalent W(2)Hf6Si2W4 cuboctahedra, and faces with six equivalent Si(1)Hf6Si2W4 cuboctahedra. In the second W site, W(2) is bonded to two equivalent Hf(1), four equivalent Hf(2), two equivalent W(2), two equivalent W(3), and two equivalent Si(1) atoms to form distorted WHf6Si2W4 cuboctahedra that share corners with four equivalent W(2)Hf6Si2W4 cuboctahedra, corners with four equivalent W(1)Hf6Si6 cuboctahedra, corners with four equivalent Si(1)Hf6Si2W4 cuboctahedra, edges with two equivalent W(2)Hf6Si2W4 cuboctahedra, faces with two equivalent W(1)Hf6Si6 cuboctahedra, faces with four equivalent W(2)Hf6Si2W4 cuboctahedra, faces with four equivalent W(3)Hf6Si2W4 cuboctahedra, and faces with six equivalent Si(1)Hf6Si2W4 cuboctahedra. In the third W site, W(3) is bonded to two equivalent Hf(1), four equivalent Hf(2), four equivalent W(2), and two equivalent Si(1) atoms to form distorted WHf6Si2W4 cuboctahedra that share corners with two equivalent W(1)Hf6Si6 cuboctahedra, corners with four equivalent W(3)Hf6Si2W4 cuboctahedra, corners with four equivalent Si(1)Hf6Si2W4 cuboctahedra, edges with two equivalent W(3)Hf6Si2W4 cuboctahedra, edges with four equivalent W(1)Hf6Si6 cuboctahedra, faces with six equivalent Si(1)Hf6Si2W4 cuboctahedra, and faces with eight equivalent W(2)Hf6Si2W4 cuboctahedra. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to three equivalent Hf(1), three equivalent Hf(2), one W(1), one W(3), two equivalent W(2), and two equivalent Si(2) atoms to form distorted SiHf6Si2W4 cuboctahedra that share corners with two equivalent W(3)Hf6Si2W4 cuboctahedra, corners with two equivalent W(1)Hf6Si6 cuboctahedra, corners with four equivalent W(2)Hf6Si2W4 cuboctahedra, edges with six equivalent Si(1)Hf6Si2W4 cuboctahedra, faces with two equivalent Si(1)Hf6Si2W4 cuboctahedra, faces with three equivalent W(3)Hf6Si2W4 cuboctahedra, faces with three equivalent W(1)Hf6Si6 cuboctahedra, and faces with six equivalent W(2)Hf6Si2W4 cuboctahedra. In the second Si site, Si(2) is bonded in a 12-coordinate geometry to two equivalent Hf(2), four equivalent Hf(1), two equivalent W(1), two equivalent Si(1), and two equivalent Si(2) atoms.
HfWSi crystallizes in the orthorhombic Amm2 space group. There are two inequivalent Hf sites. In the first Hf site, Hf(1) is bonded in a 12-coordinate geometry to one W(3), two equivalent W(1), two equivalent W(2), three equivalent Si(1), and four equivalent Si(2) atoms. The Hf(1)-W(3) bond length is 3.08 Å. Both Hf(1)-W(1) bond lengths are 3.09 Å. Both Hf(1)-W(2) bond lengths are 3.07 Å. There are two shorter (3.07 Å) and one longer (3.12 Å) Hf(1)-Si(1) bond length. There are two shorter (3.05 Å) and two longer (3.07 Å) Hf(1)-Si(2) bond lengths. In the second Hf site, Hf(2) is bonded in a 12-coordinate geometry to one W(1), two equivalent W(3), four equivalent W(2), two equivalent Si(2), and three equivalent Si(1) atoms. The Hf(2)-W(1) bond length is 3.10 Å. Both Hf(2)-W(3) bond lengths are 3.10 Å. There are two shorter (3.05 Å) and two longer (3.09 Å) Hf(2)-W(2) bond lengths. Both Hf(2)-Si(2) bond lengths are 3.02 Å. There is one shorter (2.98 Å) and two longer (3.13 Å) Hf(2)-Si(1) bond lengths. There are three inequivalent W sites. In the first W site, W(1) is bonded to two equivalent Hf(2), four equivalent Hf(1), two equivalent Si(1), and four equivalent Si(2) atoms to form WHf6Si6 cuboctahedra that share corners with two equivalent W(3)Hf6Si2W4 cuboctahedra, corners with four equivalent W(1)Hf6Si6 cuboctahedra, corners with four equivalent Si(1)Hf6Si2W4 cuboctahedra, corners with eight equivalent W(2)Hf6Si2W4 cuboctahedra, edges with two equivalent W(1)Hf6Si6 cuboctahedra, edges with four equivalent W(3)Hf6Si2W4 cuboctahedra, faces with four equivalent W(2)Hf6Si2W4 cuboctahedra, and faces with six equivalent Si(1)Hf6Si2W4 cuboctahedra. Both W(1)-Si(1) bond lengths are 2.55 Å. There are two shorter (2.60 Å) and two longer (2.64 Å) W(1)-Si(2) bond lengths. In the second W site, W(2) is bonded to two equivalent Hf(1), four equivalent Hf(2), two equivalent W(2), two equivalent W(3), and two equivalent Si(1) atoms to form distorted WHf6Si2W4 cuboctahedra that share corners with four equivalent W(2)Hf6Si2W4 cuboctahedra, corners with four equivalent W(1)Hf6Si6 cuboctahedra, corners with four equivalent Si(1)Hf6Si2W4 cuboctahedra, edges with two equivalent W(2)Hf6Si2W4 cuboctahedra, faces with two equivalent W(1)Hf6Si6 cuboctahedra, faces with four equivalent W(2)Hf6Si2W4 cuboctahedra, faces with four equivalent W(3)Hf6Si2W4 cuboctahedra, and faces with six equivalent Si(1)Hf6Si2W4 cuboctahedra. There is one shorter (2.61 Å) and one longer (2.70 Å) W(2)-W(2) bond length. There is one shorter (2.57 Å) and one longer (2.66 Å) W(2)-W(3) bond length. Both W(2)-Si(1) bond lengths are 2.61 Å. In the third W site, W(3) is bonded to two equivalent Hf(1), four equivalent Hf(2), four equivalent W(2), and two equivalent Si(1) atoms to form distorted WHf6Si2W4 cuboctahedra that share corners with two equivalent W(1)Hf6Si6 cuboctahedra, corners with four equivalent W(3)Hf6Si2W4 cuboctahedra, corners with four equivalent Si(1)Hf6Si2W4 cuboctahedra, edges with two equivalent W(3)Hf6Si2W4 cuboctahedra, edges with four equivalent W(1)Hf6Si6 cuboctahedra, faces with six equivalent Si(1)Hf6Si2W4 cuboctahedra, and faces with eight equivalent W(2)Hf6Si2W4 cuboctahedra. Both W(3)-Si(1) bond lengths are 2.63 Å. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to three equivalent Hf(1), three equivalent Hf(2), one W(1), one W(3), two equivalent W(2), and two equivalent Si(2) atoms to form distorted SiHf6Si2W4 cuboctahedra that share corners with two equivalent W(3)Hf6Si2W4 cuboctahedra, corners with two equivalent W(1)Hf6Si6 cuboctahedra, corners with four equivalent W(2)Hf6Si2W4 cuboctahedra, edges with six equivalent Si(1)Hf6Si2W4 cuboctahedra, faces with two equivalent Si(1)Hf6Si2W4 cuboctahedra, faces with three equivalent W(3)Hf6Si2W4 cuboctahedra, faces with three equivalent W(1)Hf6Si6 cuboctahedra, and faces with six equivalent W(2)Hf6Si2W4 cuboctahedra. Both Si(1)-Si(2) bond lengths are 2.73 Å. In the second Si site, Si(2) is bonded in a 12-coordinate geometry to two equivalent Hf(2), four equivalent Hf(1), two equivalent W(1), two equivalent Si(1), and two equivalent Si(2) atoms. There is one shorter (2.46 Å) and one longer (2.85 Å) Si(2)-Si(2) bond length.