ZrVNi crystallizes in the orthorhombic Amm2 space group. There are six inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 16-coordinate geometry to one Zr(1); three Zr(2,2); one V(3); two equivalent V(1); two equivalent V(2); three equivalent Ni(1); and four equivalent Ni(2) atoms. In the second Zr site, Zr(2) is bonded in a 16-coordinate geometry to one Zr(2), three equivalent Zr(1), one V(1), two equivalent V(3), four equivalent V(2), two equivalent Ni(2), and three equivalent Ni(1) atoms. In the third Zr site, Zr(1) is bonded in a 16-coordinate geometry to one Zr(1); three Zr(2,2); one V(3); two equivalent V(1); two equivalent V(2); three equivalent Ni(1); and four equivalent Ni(2) atoms. In the fourth Zr site, Zr(2) is bonded in a 16-coordinate geometry to one Zr(2), three equivalent Zr(1), one V(1), two equivalent V(3), four equivalent V(2), two equivalent Ni(2), and three equivalent Ni(1) atoms. In the fifth Zr site, Zr(2) is bonded in a 16-coordinate geometry to one Zr(2); three Zr(1,1); one V(1); two equivalent V(3); four equivalent V(2); two equivalent Ni(2); and three equivalent Ni(1) atoms. In the sixth Zr site, Zr(1) is bonded in a 16-coordinate geometry to one Zr(1); three Zr(2,2); one V(3); two equivalent V(1); two equivalent V(2); three equivalent Ni(1); and four equivalent Ni(2) atoms. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent Zr(2); four Zr(1,1); two equivalent Ni(1); and four equivalent Ni(2) atoms to form distorted VZr6Ni6 cuboctahedra that share corners with two equivalent V(3)Zr6V4Ni2 cuboctahedra, corners with four equivalent V(1)Zr6Ni6 cuboctahedra, corners with four equivalent Ni(1)Zr6V4Ni2 cuboctahedra, corners with eight equivalent V(2)Zr6V4Ni2 cuboctahedra, edges with two equivalent V(1)Zr6Ni6 cuboctahedra, edges with four equivalent V(3)Zr6V4Ni2 cuboctahedra, faces with four equivalent V(2)Zr6V4Ni2 cuboctahedra, faces with six equivalent Ni(1)Zr6V4Ni2 cuboctahedra, and faces with eight equivalent Ni(2)Zr6V2Ni4 cuboctahedra. In the second V site, V(2) is bonded to two Zr(1,1); four Zr(2,2,2); two equivalent V(2); two equivalent V(3); and two equivalent Ni(1) atoms to form VZr6V4Ni2 cuboctahedra that share corners with four equivalent V(1)Zr6Ni6 cuboctahedra, corners with four equivalent V(2)Zr6V4Ni2 cuboctahedra, corners with four equivalent Ni(1)Zr6V4Ni2 cuboctahedra, corners with six equivalent Ni(2)Zr6V2Ni4 cuboctahedra, edges with two equivalent V(2)Zr6V4Ni2 cuboctahedra, edges with four equivalent Ni(2)Zr6V2Ni4 cuboctahedra, faces with two equivalent V(1)Zr6Ni6 cuboctahedra, faces with two equivalent Ni(2)Zr6V2Ni4 cuboctahedra, faces with four equivalent V(2)Zr6V4Ni2 cuboctahedra, faces with four equivalent V(3)Zr6V4Ni2 cuboctahedra, and faces with six equivalent Ni(1)Zr6V4Ni2 cuboctahedra. In the third V site, V(3) is bonded to two Zr(1,1); four Zr(2,2); four equivalent V(2); and two equivalent Ni(1) atoms to form VZr6V4Ni2 cuboctahedra that share corners with two equivalent V(1)Zr6Ni6 cuboctahedra, corners with four equivalent V(3)Zr6V4Ni2 cuboctahedra, corners with four equivalent Ni(1)Zr6V4Ni2 cuboctahedra, corners with eight equivalent Ni(2)Zr6V2Ni4 cuboctahedra, edges with two equivalent V(3)Zr6V4Ni2 cuboctahedra, edges with four equivalent V(1)Zr6Ni6 cuboctahedra, faces with four equivalent Ni(2)Zr6V2Ni4 cuboctahedra, faces with six equivalent Ni(1)Zr6V4Ni2 cuboctahedra, and faces with eight equivalent V(2)Zr6V4Ni2 cuboctahedra. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to three equivalent Zr(1); three Zr(2,2); one V(1); one V(3); two equivalent V(2); and two equivalent Ni(2) atoms to form distorted NiZr6V4Ni2 cuboctahedra that share corners with two equivalent V(1)Zr6Ni6 cuboctahedra, corners with two equivalent V(3)Zr6V4Ni2 cuboctahedra, corners with four equivalent V(2)Zr6V4Ni2 cuboctahedra, corners with four equivalent Ni(2)Zr6V2Ni4 cuboctahedra, edges with six equivalent Ni(1)Zr6V4Ni2 cuboctahedra, faces with two equivalent Ni(1)Zr6V4Ni2 cuboctahedra, faces with three equivalent V(1)Zr6Ni6 cuboctahedra, faces with three equivalent V(3)Zr6V4Ni2 cuboctahedra, faces with six equivalent V(2)Zr6V4Ni2 cuboctahedra, and faces with six equivalent Ni(2)Zr6V2Ni4 cuboctahedra. In the second Ni site, Ni(2) is bonded to two equivalent Zr(2); four Zr(1,1,1); two equivalent V(1); two equivalent Ni(1); and two equivalent Ni(2) atoms to form distorted NiZr6V2Ni4 cuboctahedra that share corners with four equivalent V(3)Zr6V4Ni2 cuboctahedra, corners with four equivalent Ni(2)Zr6V2Ni4 cuboctahedra, corners with four equivalent Ni(1)Zr6V4Ni2 cuboctahedra, corners with six equivalent V(2)Zr6V4Ni2 cuboctahedra, edges with two equivalent Ni(2)Zr6V2Ni4 cuboctahedra, edges with four equivalent V(2)Zr6V4Ni2 cuboctahedra, faces with two equivalent V(2)Zr6V4Ni2 cuboctahedra, faces with two equivalent V(3)Zr6V4Ni2 cuboctahedra, faces with four equivalent V(1)Zr6Ni6 cuboctahedra, faces with four equivalent Ni(2)Zr6V2Ni4 cuboctahedra, and faces with six equivalent Ni(1)Zr6V4Ni2 cuboctahedra.
ZrVNi crystallizes in the orthorhombic Amm2 space group. There are six inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 16-coordinate geometry to one Zr(1); three Zr(2,2); one V(3); two equivalent V(1); two equivalent V(2); three equivalent Ni(1); and four equivalent Ni(2) atoms. The Zr(1)-Zr(1) bond length is 3.04 Å. All Zr(1)-Zr(2,2) bond lengths are 3.09 Å. The Zr(1)-V(3) bond length is 2.98 Å. Both Zr(1)-V(1) bond lengths are 2.97 Å. Both Zr(1)-V(2) bond lengths are 3.04 Å. There is one shorter (2.89 Å) and two longer (2.99 Å) Zr(1)-Ni(1) bond lengths. There are two shorter (2.84 Å) and two longer (3.03 Å) Zr(1)-Ni(2) bond lengths. In the second Zr site, Zr(2) is bonded in a 16-coordinate geometry to one Zr(2), three equivalent Zr(1), one V(1), two equivalent V(3), four equivalent V(2), two equivalent Ni(2), and three equivalent Ni(1) atoms. The Zr(2)-Zr(2) bond length is 3.25 Å. The Zr(2)-V(1) bond length is 3.02 Å. Both Zr(2)-V(3) bond lengths are 3.02 Å. There are two shorter (2.97 Å) and two longer (3.00 Å) Zr(2)-V(2) bond lengths. Both Zr(2)-Ni(2) bond lengths are 2.92 Å. There is one shorter (2.94 Å) and two longer (2.96 Å) Zr(2)-Ni(1) bond lengths. In the third Zr site, Zr(1) is bonded in a 16-coordinate geometry to one Zr(1); three Zr(2,2); one V(3); two equivalent V(1); two equivalent V(2); three equivalent Ni(1); and four equivalent Ni(2) atoms. All Zr(1)-Zr(2,2) bond lengths are 3.09 Å. The Zr(1)-V(3) bond length is 2.98 Å. Both Zr(1)-V(1) bond lengths are 2.97 Å. Both Zr(1)-V(2) bond lengths are 3.04 Å. There is one shorter (2.89 Å) and two longer (2.99 Å) Zr(1)-Ni(1) bond lengths. There are two shorter (2.84 Å) and two longer (3.03 Å) Zr(1)-Ni(2) bond lengths. In the fourth Zr site, Zr(2) is bonded in a 16-coordinate geometry to one Zr(2), three equivalent Zr(1), one V(1), two equivalent V(3), four equivalent V(2), two equivalent Ni(2), and three equivalent Ni(1) atoms. The Zr(2)-Zr(2) bond length is 3.25 Å. The Zr(2)-V(1) bond length is 3.02 Å. Both Zr(2)-V(3) bond lengths are 3.02 Å. There are two shorter (2.97 Å) and two longer (3.00 Å) Zr(2)-V(2) bond lengths. Both Zr(2)-Ni(2) bond lengths are 2.92 Å. There is one shorter (2.94 Å) and two longer (2.96 Å) Zr(2)-Ni(1) bond lengths. In the fifth Zr site, Zr(2) is bonded in a 16-coordinate geometry to one Zr(2); three Zr(1,1); one V(1); two equivalent V(3); four equivalent V(2); two equivalent Ni(2); and three equivalent Ni(1) atoms. The Zr(2)-Zr(1) bond length is 3.09 Å. The Zr(2)-V(1) bond length is 3.02 Å. Both Zr(2)-V(3) bond lengths are 3.02 Å. There are two shorter (2.97 Å) and two longer (3.00 Å) Zr(2)-V(2) bond lengths. Both Zr(2)-Ni(2) bond lengths are 2.92 Å. There is one shorter (2.94 Å) and two longer (2.96 Å) Zr(2)-Ni(1) bond lengths. In the sixth Zr site, Zr(1) is bonded in a 16-coordinate geometry to one Zr(1); three Zr(2,2); one V(3); two equivalent V(1); two equivalent V(2); three equivalent Ni(1); and four equivalent Ni(2) atoms. The Zr(1)-Zr(1) bond length is 3.04 Å. Both Zr(1)-Zr(2) bond lengths are 3.09 Å. The Zr(1)-V(3) bond length is 2.98 Å. Both Zr(1)-V(1) bond lengths are 2.97 Å. Both Zr(1)-V(2) bond lengths are 3.04 Å. There is one shorter (2.89 Å) and two longer (2.99 Å) Zr(1)-Ni(1) bond lengths. There are two shorter (2.84 Å) and two longer (3.03 Å) Zr(1)-Ni(2) bond lengths. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent Zr(2); four Zr(1,1); two equivalent Ni(1); and four equivalent Ni(2) atoms to form distorted VZr6Ni6 cuboctahedra that share corners with two equivalent V(3)Zr6V4Ni2 cuboctahedra, corners with four equivalent V(1)Zr6Ni6 cuboctahedra, corners with four equivalent Ni(1)Zr6V4Ni2 cuboctahedra, corners with eight equivalent V(2)Zr6V4Ni2 cuboctahedra, edges with two equivalent V(1)Zr6Ni6 cuboctahedra, edges with four equivalent V(3)Zr6V4Ni2 cuboctahedra, faces with four equivalent V(2)Zr6V4Ni2 cuboctahedra, faces with six equivalent Ni(1)Zr6V4Ni2 cuboctahedra, and faces with eight equivalent Ni(2)Zr6V2Ni4 cuboctahedra. Both V(1)-Ni(1) bond lengths are 2.44 Å. There are two shorter (2.49 Å) and two longer (2.52 Å) V(1)-Ni(2) bond lengths. In the second V site, V(2) is bonded to two Zr(1,1); four Zr(2,2,2); two equivalent V(2); two equivalent V(3); and two equivalent Ni(1) atoms to form VZr6V4Ni2 cuboctahedra that share corners with four equivalent V(1)Zr6Ni6 cuboctahedra, corners with four equivalent V(2)Zr6V4Ni2 cuboctahedra, corners with four equivalent Ni(1)Zr6V4Ni2 cuboctahedra, corners with six equivalent Ni(2)Zr6V2Ni4 cuboctahedra, edges with two equivalent V(2)Zr6V4Ni2 cuboctahedra, edges with four equivalent Ni(2)Zr6V2Ni4 cuboctahedra, faces with two equivalent V(1)Zr6Ni6 cuboctahedra, faces with two equivalent Ni(2)Zr6V2Ni4 cuboctahedra, faces with four equivalent V(2)Zr6V4Ni2 cuboctahedra, faces with four equivalent V(3)Zr6V4Ni2 cuboctahedra, and faces with six equivalent Ni(1)Zr6V4Ni2 cuboctahedra. There is one shorter (2.50 Å) and one longer (2.58 Å) V(2)-V(2) bond length. There is one shorter (2.42 Å) and one longer (2.59 Å) V(2)-V(3) bond length. Both V(2)-Ni(1) bond lengths are 2.60 Å. In the third V site, V(3) is bonded to two Zr(1,1); four Zr(2,2); four equivalent V(2); and two equivalent Ni(1) atoms to form VZr6V4Ni2 cuboctahedra that share corners with two equivalent V(1)Zr6Ni6 cuboctahedra, corners with four equivalent V(3)Zr6V4Ni2 cuboctahedra, corners with four equivalent Ni(1)Zr6V4Ni2 cuboctahedra, corners with eight equivalent Ni(2)Zr6V2Ni4 cuboctahedra, edges with two equivalent V(3)Zr6V4Ni2 cuboctahedra, edges with four equivalent V(1)Zr6Ni6 cuboctahedra, faces with four equivalent Ni(2)Zr6V2Ni4 cuboctahedra, faces with six equivalent Ni(1)Zr6V4Ni2 cuboctahedra, and faces with eight equivalent V(2)Zr6V4Ni2 cuboctahedra. Both V(3)-Ni(1) bond lengths are 2.63 Å. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to three equivalent Zr(1); three Zr(2,2); one V(1); one V(3); two equivalent V(2); and two equivalent Ni(2) atoms to form distorted NiZr6V4Ni2 cuboctahedra that share corners with two equivalent V(1)Zr6Ni6 cuboctahedra, corners with two equivalent V(3)Zr6V4Ni2 cuboctahedra, corners with four equivalent V(2)Zr6V4Ni2 cuboctahedra, corners with four equivalent Ni(2)Zr6V2Ni4 cuboctahedra, edges with six equivalent Ni(1)Zr6V4Ni2 cuboctahedra, faces with two equivalent Ni(1)Zr6V4Ni2 cuboctahedra, faces with three equivalent V(1)Zr6Ni6 cuboctahedra, faces with three equivalent V(3)Zr6V4Ni2 cuboctahedra, faces with six equivalent V(2)Zr6V4Ni2 cuboctahedra, and faces with six equivalent Ni(2)Zr6V2Ni4 cuboctahedra. Both Ni(1)-Ni(2) bond lengths are 2.56 Å. In the second Ni site, Ni(2) is bonded to two equivalent Zr(2); four Zr(1,1,1); two equivalent V(1); two equivalent Ni(1); and two equivalent Ni(2) atoms to form distorted NiZr6V2Ni4 cuboctahedra that share corners with four equivalent V(3)Zr6V4Ni2 cuboctahedra, corners with four equivalent Ni(2)Zr6V2Ni4 cuboctahedra, corners with four equivalent Ni(1)Zr6V4Ni2 cuboctahedra, corners with six equivalent V(2)Zr6V4Ni2 cuboctahedra, edges with two equivalent Ni(2)Zr6V2Ni4 cuboctahedra, edges with four equivalent V(2)Zr6V4Ni2 cuboctahedra, faces with two equivalent V(2)Zr6V4Ni2 cuboctahedra, faces with two equivalent V(3)Zr6V4Ni2 cuboctahedra, faces with four equivalent V(1)Zr6Ni6 cuboctahedra, faces with four equivalent Ni(2)Zr6V2Ni4 cuboctahedra, and faces with six equivalent Ni(1)Zr6V4Ni2 cuboctahedra. There is one shorter (2.50 Å) and one longer (2.57 Å) Ni(2)-Ni(2) bond length.