VNiSi is Hexagonal Laves-derived structured and crystallizes in the orthorhombic Amm2 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded in a 16-coordinate geometry to one V(1), three equivalent V(2), three equivalent Ni(1), four equivalent Ni(2), one Si(3), two equivalent Si(1), and two equivalent Si(2) atoms. In the second V site, V(2) is bonded in a 16-coordinate geometry to one V(2); three V(1,1); two equivalent Ni(2); three equivalent Ni(1); one Si(1); two equivalent Si(3); and four equivalent Si(2) atoms. In the third V site, V(1) is bonded in a 16-coordinate geometry to one V(1), three equivalent V(2), three equivalent Ni(1), four equivalent Ni(2), one Si(3), two equivalent Si(1), and two equivalent Si(2) atoms. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to three V(1,1); three equivalent V(2); two equivalent Ni(2); one Si(1); one Si(3); and two equivalent Si(2) atoms to form NiV6Si4Ni2 cuboctahedra that share corners with two equivalent Si(1)V6Ni6 cuboctahedra, corners with two equivalent Si(3)V6Si4Ni2 cuboctahedra, corners with four equivalent Ni(2)V6Si2Ni4 cuboctahedra, corners with four equivalent Si(2)V6Si4Ni2 cuboctahedra, edges with six equivalent Ni(1)V6Si4Ni2 cuboctahedra, faces with two equivalent Ni(1)V6Si4Ni2 cuboctahedra, faces with three equivalent Si(1)V6Ni6 cuboctahedra, faces with three equivalent Si(3)V6Si4Ni2 cuboctahedra, faces with six equivalent Ni(2)V6Si2Ni4 cuboctahedra, and faces with six equivalent Si(2)V6Si4Ni2 cuboctahedra. In the second Ni site, Ni(2) is bonded to two equivalent V(2); four V(1,1); two equivalent Ni(1); two equivalent Ni(2); and two equivalent Si(1) atoms to form NiV6Si2Ni4 cuboctahedra that share corners with four equivalent Ni(2)V6Si2Ni4 cuboctahedra, corners with four equivalent Ni(1)V6Si4Ni2 cuboctahedra, corners with four equivalent Si(3)V6Si4Ni2 cuboctahedra, corners with six equivalent Si(2)V6Si4Ni2 cuboctahedra, edges with two equivalent Ni(2)V6Si2Ni4 cuboctahedra, edges with four equivalent Si(2)V6Si4Ni2 cuboctahedra, faces with two equivalent Si(2)V6Si4Ni2 cuboctahedra, faces with two equivalent Si(3)V6Si4Ni2 cuboctahedra, faces with four equivalent Ni(2)V6Si2Ni4 cuboctahedra, faces with four equivalent Si(1)V6Ni6 cuboctahedra, and faces with six equivalent Ni(1)V6Si4Ni2 cuboctahedra. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded to two equivalent V(2), four equivalent V(1), two equivalent Ni(1), and four equivalent Ni(2) atoms to form SiV6Ni6 cuboctahedra that share corners with two equivalent Si(3)V6Si4Ni2 cuboctahedra, corners with four equivalent Ni(1)V6Si4Ni2 cuboctahedra, corners with four equivalent Si(1)V6Ni6 cuboctahedra, corners with eight equivalent Si(2)V6Si4Ni2 cuboctahedra, edges with two equivalent Si(1)V6Ni6 cuboctahedra, edges with four equivalent Si(3)V6Si4Ni2 cuboctahedra, faces with four equivalent Si(2)V6Si4Ni2 cuboctahedra, faces with six equivalent Ni(1)V6Si4Ni2 cuboctahedra, and faces with eight equivalent Ni(2)V6Si2Ni4 cuboctahedra. In the second Si site, Si(2) is bonded to two V(1,1); four equivalent V(2); two equivalent Ni(1); two equivalent Si(2); and two equivalent Si(3) atoms to form SiV6Si4Ni2 cuboctahedra that share corners with four equivalent Ni(1)V6Si4Ni2 cuboctahedra, corners with four equivalent Si(1)V6Ni6 cuboctahedra, corners with four equivalent Si(2)V6Si4Ni2 cuboctahedra, corners with six equivalent Ni(2)V6Si2Ni4 cuboctahedra, edges with two equivalent Si(2)V6Si4Ni2 cuboctahedra, edges with four equivalent Ni(2)V6Si2Ni4 cuboctahedra, faces with two equivalent Ni(2)V6Si2Ni4 cuboctahedra, faces with two equivalent Si(1)V6Ni6 cuboctahedra, faces with four equivalent Si(2)V6Si4Ni2 cuboctahedra, faces with four equivalent Si(3)V6Si4Ni2 cuboctahedra, and faces with six equivalent Ni(1)V6Si4Ni2 cuboctahedra. In the third Si site, Si(3) is bonded to two V(1,1); four equivalent V(2); two equivalent Ni(1); and four equivalent Si(2) atoms to form SiV6Si4Ni2 cuboctahedra that share corners with two equivalent Si(1)V6Ni6 cuboctahedra, corners with four equivalent Ni(1)V6Si4Ni2 cuboctahedra, corners with four equivalent Si(3)V6Si4Ni2 cuboctahedra, corners with eight equivalent Ni(2)V6Si2Ni4 cuboctahedra, edges with two equivalent Si(3)V6Si4Ni2 cuboctahedra, edges with four equivalent Si(1)V6Ni6 cuboctahedra, faces with four equivalent Ni(2)V6Si2Ni4 cuboctahedra, faces with six equivalent Ni(1)V6Si4Ni2 cuboctahedra, and faces with eight equivalent Si(2)V6Si4Ni2 cuboctahedra.
VNiSi is Hexagonal Laves-derived structured and crystallizes in the orthorhombic Amm2 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded in a 16-coordinate geometry to one V(1), three equivalent V(2), three equivalent Ni(1), four equivalent Ni(2), one Si(3), two equivalent Si(1), and two equivalent Si(2) atoms. The V(1)-V(1) bond length is 2.75 Å. There is one shorter (2.87 Å) and two longer (2.93 Å) V(1)-V(2) bond lengths. All V(1)-Ni(1) bond lengths are 2.79 Å. There are two shorter (2.70 Å) and two longer (2.78 Å) V(1)-Ni(2) bond lengths. The V(1)-Si(3) bond length is 2.65 Å. Both V(1)-Si(1) bond lengths are 2.75 Å. Both V(1)-Si(2) bond lengths are 2.65 Å. In the second V site, V(2) is bonded in a 16-coordinate geometry to one V(2); three V(1,1); two equivalent Ni(2); three equivalent Ni(1); one Si(1); two equivalent Si(3); and four equivalent Si(2) atoms. The V(2)-V(2) bond length is 2.61 Å. Both V(2)-V(1) bond lengths are 2.93 Å. Both V(2)-Ni(2) bond lengths are 2.70 Å. There is one shorter (2.76 Å) and two longer (2.78 Å) V(2)-Ni(1) bond lengths. The V(2)-Si(1) bond length is 2.75 Å. Both V(2)-Si(3) bond lengths are 2.72 Å. There are two shorter (2.69 Å) and two longer (2.72 Å) V(2)-Si(2) bond lengths. In the third V site, V(1) is bonded in a 16-coordinate geometry to one V(1), three equivalent V(2), three equivalent Ni(1), four equivalent Ni(2), one Si(3), two equivalent Si(1), and two equivalent Si(2) atoms. All V(1)-Ni(1) bond lengths are 2.79 Å. There are two shorter (2.70 Å) and two longer (2.78 Å) V(1)-Ni(2) bond lengths. The V(1)-Si(3) bond length is 2.65 Å. Both V(1)-Si(1) bond lengths are 2.75 Å. Both V(1)-Si(2) bond lengths are 2.65 Å. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to three V(1,1); three equivalent V(2); two equivalent Ni(2); one Si(1); one Si(3); and two equivalent Si(2) atoms to form NiV6Si4Ni2 cuboctahedra that share corners with two equivalent Si(1)V6Ni6 cuboctahedra, corners with two equivalent Si(3)V6Si4Ni2 cuboctahedra, corners with four equivalent Ni(2)V6Si2Ni4 cuboctahedra, corners with four equivalent Si(2)V6Si4Ni2 cuboctahedra, edges with six equivalent Ni(1)V6Si4Ni2 cuboctahedra, faces with two equivalent Ni(1)V6Si4Ni2 cuboctahedra, faces with three equivalent Si(1)V6Ni6 cuboctahedra, faces with three equivalent Si(3)V6Si4Ni2 cuboctahedra, faces with six equivalent Ni(2)V6Si2Ni4 cuboctahedra, and faces with six equivalent Si(2)V6Si4Ni2 cuboctahedra. Both Ni(1)-Ni(2) bond lengths are 2.40 Å. The Ni(1)-Si(1) bond length is 2.33 Å. The Ni(1)-Si(3) bond length is 2.26 Å. Both Ni(1)-Si(2) bond lengths are 2.26 Å. In the second Ni site, Ni(2) is bonded to two equivalent V(2); four V(1,1); two equivalent Ni(1); two equivalent Ni(2); and two equivalent Si(1) atoms to form NiV6Si2Ni4 cuboctahedra that share corners with four equivalent Ni(2)V6Si2Ni4 cuboctahedra, corners with four equivalent Ni(1)V6Si4Ni2 cuboctahedra, corners with four equivalent Si(3)V6Si4Ni2 cuboctahedra, corners with six equivalent Si(2)V6Si4Ni2 cuboctahedra, edges with two equivalent Ni(2)V6Si2Ni4 cuboctahedra, edges with four equivalent Si(2)V6Si4Ni2 cuboctahedra, faces with two equivalent Si(2)V6Si4Ni2 cuboctahedra, faces with two equivalent Si(3)V6Si4Ni2 cuboctahedra, faces with four equivalent Ni(2)V6Si2Ni4 cuboctahedra, faces with four equivalent Si(1)V6Ni6 cuboctahedra, and faces with six equivalent Ni(1)V6Si4Ni2 cuboctahedra. There is one shorter (2.33 Å) and one longer (2.45 Å) Ni(2)-Ni(2) bond length. There is one shorter (2.29 Å) and one longer (2.43 Å) Ni(2)-Si(1) bond length. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded to two equivalent V(2), four equivalent V(1), two equivalent Ni(1), and four equivalent Ni(2) atoms to form SiV6Ni6 cuboctahedra that share corners with two equivalent Si(3)V6Si4Ni2 cuboctahedra, corners with four equivalent Ni(1)V6Si4Ni2 cuboctahedra, corners with four equivalent Si(1)V6Ni6 cuboctahedra, corners with eight equivalent Si(2)V6Si4Ni2 cuboctahedra, edges with two equivalent Si(1)V6Ni6 cuboctahedra, edges with four equivalent Si(3)V6Si4Ni2 cuboctahedra, faces with four equivalent Si(2)V6Si4Ni2 cuboctahedra, faces with six equivalent Ni(1)V6Si4Ni2 cuboctahedra, and faces with eight equivalent Ni(2)V6Si2Ni4 cuboctahedra. In the second Si site, Si(2) is bonded to two V(1,1); four equivalent V(2); two equivalent Ni(1); two equivalent Si(2); and two equivalent Si(3) atoms to form SiV6Si4Ni2 cuboctahedra that share corners with four equivalent Ni(1)V6Si4Ni2 cuboctahedra, corners with four equivalent Si(1)V6Ni6 cuboctahedra, corners with four equivalent Si(2)V6Si4Ni2 cuboctahedra, corners with six equivalent Ni(2)V6Si2Ni4 cuboctahedra, edges with two equivalent Si(2)V6Si4Ni2 cuboctahedra, edges with four equivalent Ni(2)V6Si2Ni4 cuboctahedra, faces with two equivalent Ni(2)V6Si2Ni4 cuboctahedra, faces with two equivalent Si(1)V6Ni6 cuboctahedra, faces with four equivalent Si(2)V6Si4Ni2 cuboctahedra, faces with four equivalent Si(3)V6Si4Ni2 cuboctahedra, and faces with six equivalent Ni(1)V6Si4Ni2 cuboctahedra. There is one shorter (2.31 Å) and one longer (2.46 Å) Si(2)-Si(2) bond length. There is one shorter (2.29 Å) and one longer (2.44 Å) Si(2)-Si(3) bond length. In the third Si site, Si(3) is bonded to two V(1,1); four equivalent V(2); two equivalent Ni(1); and four equivalent Si(2) atoms to form SiV6Si4Ni2 cuboctahedra that share corners with two equivalent Si(1)V6Ni6 cuboctahedra, corners with four equivalent Ni(1)V6Si4Ni2 cuboctahedra, corners with four equivalent Si(3)V6Si4Ni2 cuboctahedra, corners with eight equivalent Ni(2)V6Si2Ni4 cuboctahedra, edges with two equivalent Si(3)V6Si4Ni2 cuboctahedra, edges with four equivalent Si(1)V6Ni6 cuboctahedra, faces with four equivalent Ni(2)V6Si2Ni4 cuboctahedra, faces with six equivalent Ni(1)V6Si4Ni2 cuboctahedra, and faces with eight equivalent Si(2)V6Si4Ni2 cuboctahedra.