Zr4Ni2Al crystallizes in the triclinic P1 space group. There are sixteen inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 6-coordinate geometry to one Ni(3), one Ni(4), one Ni(7), one Ni(8), one Al(3), and one Al(4) atom. In the second Zr site, Zr(2) is bonded in a distorted cuboctahedral geometry to one Ni(1), one Ni(2), one Ni(4), one Ni(5), one Ni(7), and one Ni(8) atom. In the third Zr site, Zr(3) is bonded in a 6-coordinate geometry to one Ni(2), one Ni(3), one Ni(5), one Ni(8), one Al(1), and one Al(3) atom. In the fourth Zr site, Zr(4) is bonded in a 6-coordinate geometry to one Ni(1), one Ni(4), one Ni(6), one Ni(7), one Al(1), and one Al(3) atom. In the fifth Zr site, Zr(5) is bonded in a 4-coordinate geometry to one Ni(5), one Ni(6), one Ni(7), one Ni(8), one Al(1), and one Al(4) atom. In the sixth Zr site, Zr(6) is bonded in a 4-coordinate geometry to one Ni(1), one Ni(2), one Ni(3), one Ni(4), one Al(1), and one Al(4) atom. In the seventh Zr site, Zr(7) is bonded in a 6-coordinate geometry to one Ni(1), one Ni(2), one Ni(5), one Ni(6), one Al(3), and one Al(4) atom. In the eighth Zr site, Zr(8) is bonded in a 4-coordinate geometry to one Ni(5), one Ni(6), one Ni(7), one Ni(8), one Al(2), and one Al(3) atom. In the ninth Zr site, Zr(9) is bonded in a 6-coordinate geometry to one Ni(2), one Ni(3), one Ni(5), one Ni(8), one Al(2), and one Al(4) atom. In the tenth Zr site, Zr(10) is bonded in a 4-coordinate geometry to one Ni(3), one Ni(4), one Ni(7), one Ni(8), one Al(1), and one Al(2) atom. In the eleventh Zr site, Zr(11) is bonded in a 6-coordinate geometry to one Ni(1), one Ni(4), one Ni(6), one Ni(7), one Al(2), and one Al(4) atom. In the twelfth Zr site, Zr(12) is bonded in a 6-coordinate geometry to one Ni(2), one Ni(3), one Ni(4), one Ni(5), one Ni(6), and one Ni(7) atom. In the thirteenth Zr site, Zr(13) is bonded in a 6-coordinate geometry to one Ni(1), one Ni(3), one Ni(4), one Ni(5), one Ni(6), and one Ni(8) atom. In the fourteenth Zr site, Zr(14) is bonded in a 6-coordinate geometry to one Ni(1), one Ni(2), one Ni(3), one Ni(6), one Ni(7), and one Ni(8) atom. In the fifteenth Zr site, Zr(15) is bonded in a 4-coordinate geometry to one Ni(1), one Ni(2), one Ni(5), one Ni(6), one Al(1), and one Al(2) atom. In the sixteenth Zr site, Zr(16) is bonded in a 4-coordinate geometry to one Ni(1), one Ni(2), one Ni(3), one Ni(4), one Al(2), and one Al(3) atom. There are eight inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a 12-coordinate geometry to one Zr(11), one Zr(13), one Zr(14), one Zr(15), one Zr(16), one Zr(2), one Zr(4), one Zr(6), one Zr(7), one Ni(3), one Ni(5), and one Ni(7) atom. In the second Ni site, Ni(2) is bonded in a 12-coordinate geometry to one Zr(12), one Zr(14), one Zr(15), one Zr(16), one Zr(2), one Zr(3), one Zr(6), one Zr(7), one Zr(9), one Ni(4), one Ni(6), and one Ni(8) atom. In the third Ni site, Ni(3) is bonded in a 12-coordinate geometry to one Zr(1), one Zr(10), one Zr(12), one Zr(13), one Zr(14), one Zr(16), one Zr(3), one Zr(6), one Zr(9), one Ni(1), one Ni(5), and one Ni(7) atom. In the fourth Ni site, Ni(4) is bonded in a 12-coordinate geometry to one Zr(1), one Zr(10), one Zr(11), one Zr(12), one Zr(13), one Zr(16), one Zr(2), one Zr(4), one Zr(6), one Ni(2), one Ni(6), and one Ni(8) atom. In the fifth Ni site, Ni(5) is bonded in a 12-coordinate geometry to one Zr(12), one Zr(13), one Zr(15), one Zr(2), one Zr(3), one Zr(5), one Zr(7), one Zr(8), one Zr(9), one Ni(1), one Ni(3), and one Ni(7) atom. In the sixth Ni site, Ni(6) is bonded in a 12-coordinate geometry to one Zr(11), one Zr(12), one Zr(13), one Zr(14), one Zr(15), one Zr(4), one Zr(5), one Zr(7), one Zr(8), one Ni(2), one Ni(4), and one Ni(8) atom. In the seventh Ni site, Ni(7) is bonded in a 12-coordinate geometry to one Zr(1), one Zr(10), one Zr(11), one Zr(12), one Zr(14), one Zr(2), one Zr(4), one Zr(5), one Zr(8), one Ni(1), one Ni(3), and one Ni(5) atom. In the eighth Ni site, Ni(8) is bonded in a 12-coordinate geometry to one Zr(1), one Zr(10), one Zr(13), one Zr(14), one Zr(2), one Zr(3), one Zr(5), one Zr(8), one Zr(9), one Ni(2), one Ni(4), and one Ni(6) atom. There are four inequivalent Al sites. In the first Al site, Al(1) is bonded to one Zr(10), one Zr(15), one Zr(3), one Zr(4), one Zr(5), and one Zr(6) atom to form distorted corner-sharing AlZr6 octahedra. The corner-sharing octahedral tilt angles range from 59-62°. In the second Al site, Al(2) is bonded to one Zr(10), one Zr(11), one Zr(15), one Zr(16), one Zr(8), and one Zr(9) atom to form distorted corner-sharing AlZr6 octahedra. The corner-sharing octahedral tilt angles range from 59-61°. In the third Al site, Al(3) is bonded to one Zr(1), one Zr(16), one Zr(3), one Zr(4), one Zr(7), and one Zr(8) atom to form distorted corner-sharing AlZr6 octahedra. The corner-sharing octahedral tilt angles range from 58-62°. In the fourth Al site, Al(4) is bonded to one Zr(1), one Zr(11), one Zr(5), one Zr(6), one Zr(7), and one Zr(9) atom to form distorted corner-sharing AlZr6 octahedra. The corner-sharing octahedral tilt angles range from 58-61°.
Zr4Ni2Al crystallizes in the triclinic P1 space group. There are sixteen inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 6-coordinate geometry to one Ni(3), one Ni(4), one Ni(7), one Ni(8), one Al(3), and one Al(4) atom. The Zr(1)-Ni(3) bond length is 2.97 Å. The Zr(1)-Ni(4) bond length is 3.32 Å. The Zr(1)-Ni(7) bond length is 2.98 Å. The Zr(1)-Ni(8) bond length is 3.35 Å. The Zr(1)-Al(3) bond length is 2.69 Å. The Zr(1)-Al(4) bond length is 2.69 Å. In the second Zr site, Zr(2) is bonded in a distorted cuboctahedral geometry to one Ni(1), one Ni(2), one Ni(4), one Ni(5), one Ni(7), and one Ni(8) atom. The Zr(2)-Ni(1) bond length is 2.79 Å. The Zr(2)-Ni(2) bond length is 2.78 Å. The Zr(2)-Ni(4) bond length is 2.80 Å. The Zr(2)-Ni(5) bond length is 2.81 Å. The Zr(2)-Ni(7) bond length is 2.79 Å. The Zr(2)-Ni(8) bond length is 2.78 Å. In the third Zr site, Zr(3) is bonded in a 6-coordinate geometry to one Ni(2), one Ni(3), one Ni(5), one Ni(8), one Al(1), and one Al(3) atom. The Zr(3)-Ni(2) bond length is 2.97 Å. The Zr(3)-Ni(3) bond length is 3.32 Å. The Zr(3)-Ni(5) bond length is 3.35 Å. The Zr(3)-Ni(8) bond length is 3.00 Å. The Zr(3)-Al(1) bond length is 2.70 Å. The Zr(3)-Al(3) bond length is 2.69 Å. In the fourth Zr site, Zr(4) is bonded in a 6-coordinate geometry to one Ni(1), one Ni(4), one Ni(6), one Ni(7), one Al(1), and one Al(3) atom. The Zr(4)-Ni(1) bond length is 2.98 Å. The Zr(4)-Ni(4) bond length is 3.34 Å. The Zr(4)-Ni(6) bond length is 3.32 Å. The Zr(4)-Ni(7) bond length is 2.96 Å. The Zr(4)-Al(1) bond length is 2.70 Å. The Zr(4)-Al(3) bond length is 2.69 Å. In the fifth Zr site, Zr(5) is bonded in a 4-coordinate geometry to one Ni(5), one Ni(6), one Ni(7), one Ni(8), one Al(1), and one Al(4) atom. The Zr(5)-Ni(5) bond length is 3.37 Å. The Zr(5)-Ni(6) bond length is 2.92 Å. The Zr(5)-Ni(7) bond length is 3.37 Å. The Zr(5)-Ni(8) bond length is 2.95 Å. The Zr(5)-Al(1) bond length is 2.70 Å. The Zr(5)-Al(4) bond length is 2.68 Å. In the sixth Zr site, Zr(6) is bonded in a 4-coordinate geometry to one Ni(1), one Ni(2), one Ni(3), one Ni(4), one Al(1), and one Al(4) atom. The Zr(6)-Ni(1) bond length is 2.94 Å. The Zr(6)-Ni(2) bond length is 3.37 Å. The Zr(6)-Ni(3) bond length is 2.91 Å. The Zr(6)-Ni(4) bond length is 3.38 Å. The Zr(6)-Al(1) bond length is 2.70 Å. The Zr(6)-Al(4) bond length is 2.69 Å. In the seventh Zr site, Zr(7) is bonded in a 6-coordinate geometry to one Ni(1), one Ni(2), one Ni(5), one Ni(6), one Al(3), and one Al(4) atom. The Zr(7)-Ni(1) bond length is 3.34 Å. The Zr(7)-Ni(2) bond length is 2.99 Å. The Zr(7)-Ni(5) bond length is 3.33 Å. The Zr(7)-Ni(6) bond length is 2.98 Å. The Zr(7)-Al(3) bond length is 2.69 Å. The Zr(7)-Al(4) bond length is 2.69 Å. In the eighth Zr site, Zr(8) is bonded in a 4-coordinate geometry to one Ni(5), one Ni(6), one Ni(7), one Ni(8), one Al(2), and one Al(3) atom. The Zr(8)-Ni(5) bond length is 2.95 Å. The Zr(8)-Ni(6) bond length is 3.34 Å. The Zr(8)-Ni(7) bond length is 2.93 Å. The Zr(8)-Ni(8) bond length is 3.39 Å. The Zr(8)-Al(2) bond length is 2.69 Å. The Zr(8)-Al(3) bond length is 2.69 Å. In the ninth Zr site, Zr(9) is bonded in a 6-coordinate geometry to one Ni(2), one Ni(3), one Ni(5), one Ni(8), one Al(2), and one Al(4) atom. The Zr(9)-Ni(2) bond length is 3.30 Å. The Zr(9)-Ni(3) bond length is 2.98 Å. The Zr(9)-Ni(5) bond length is 3.01 Å. The Zr(9)-Ni(8) bond length is 3.33 Å. The Zr(9)-Al(2) bond length is 2.69 Å. The Zr(9)-Al(4) bond length is 2.69 Å. In the tenth Zr site, Zr(10) is bonded in a 4-coordinate geometry to one Ni(3), one Ni(4), one Ni(7), one Ni(8), one Al(1), and one Al(2) atom. The Zr(10)-Ni(3) bond length is 3.37 Å. The Zr(10)-Ni(4) bond length is 2.93 Å. The Zr(10)-Ni(7) bond length is 3.38 Å. The Zr(10)-Ni(8) bond length is 2.93 Å. The Zr(10)-Al(1) bond length is 2.69 Å. The Zr(10)-Al(2) bond length is 2.69 Å. In the eleventh Zr site, Zr(11) is bonded in a 6-coordinate geometry to one Ni(1), one Ni(4), one Ni(6), one Ni(7), one Al(2), and one Al(4) atom. The Zr(11)-Ni(1) bond length is 3.33 Å. The Zr(11)-Ni(4) bond length is 3.02 Å. The Zr(11)-Ni(6) bond length is 2.99 Å. The Zr(11)-Ni(7) bond length is 3.29 Å. The Zr(11)-Al(2) bond length is 2.69 Å. The Zr(11)-Al(4) bond length is 2.69 Å. In the twelfth Zr site, Zr(12) is bonded in a 6-coordinate geometry to one Ni(2), one Ni(3), one Ni(4), one Ni(5), one Ni(6), and one Ni(7) atom. The Zr(12)-Ni(2) bond length is 2.79 Å. The Zr(12)-Ni(3) bond length is 2.77 Å. The Zr(12)-Ni(4) bond length is 2.78 Å. The Zr(12)-Ni(5) bond length is 2.79 Å. The Zr(12)-Ni(6) bond length is 2.76 Å. The Zr(12)-Ni(7) bond length is 2.80 Å. In the thirteenth Zr site, Zr(13) is bonded in a 6-coordinate geometry to one Ni(1), one Ni(3), one Ni(4), one Ni(5), one Ni(6), and one Ni(8) atom. The Zr(13)-Ni(1) bond length is 2.82 Å. The Zr(13)-Ni(3) bond length is 2.79 Å. The Zr(13)-Ni(4) bond length is 2.78 Å. The Zr(13)-Ni(5) bond length is 2.78 Å. The Zr(13)-Ni(6) bond length is 2.78 Å. The Zr(13)-Ni(8) bond length is 2.80 Å. In the fourteenth Zr site, Zr(14) is bonded in a 6-coordinate geometry to one Ni(1), one Ni(2), one Ni(3), one Ni(6), one Ni(7), and one Ni(8) atom. The Zr(14)-Ni(1) bond length is 2.79 Å. The Zr(14)-Ni(2) bond length is 2.76 Å. The Zr(14)-Ni(3) bond length is 2.81 Å. The Zr(14)-Ni(6) bond length is 2.80 Å. The Zr(14)-Ni(7) bond length is 2.78 Å. The Zr(14)-Ni(8) bond length is 2.78 Å. In the fifteenth Zr site, Zr(15) is bonded in a 4-coordinate geometry to one Ni(1), one Ni(2), one Ni(5), one Ni(6), one Al(1), and one Al(2) atom. The Zr(15)-Ni(1) bond length is 2.93 Å. The Zr(15)-Ni(2) bond length is 3.39 Å. The Zr(15)-Ni(5) bond length is 2.91 Å. The Zr(15)-Ni(6) bond length is 3.36 Å. The Zr(15)-Al(1) bond length is 2.69 Å. The Zr(15)-Al(2) bond length is 2.69 Å. In the sixteenth Zr site, Zr(16) is bonded in a 4-coordinate geometry to one Ni(1), one Ni(2), one Ni(3), one Ni(4), one Al(2), and one Al(3) atom. The Zr(16)-Ni(1) bond length is 3.39 Å. The Zr(16)-Ni(2) bond length is 2.94 Å. The Zr(16)-Ni(3) bond length is 3.35 Å. The Zr(16)-Ni(4) bond length is 2.94 Å. The Zr(16)-Al(2) bond length is 2.69 Å. The Zr(16)-Al(3) bond length is 2.69 Å. There are eight inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a 12-coordinate geometry to one Zr(11), one Zr(13), one Zr(14), one Zr(15), one Zr(16), one Zr(2), one Zr(4), one Zr(6), one Zr(7), one Ni(3), one Ni(5), and one Ni(7) atom. The Ni(1)-Ni(3) bond length is 2.75 Å. The Ni(1)-Ni(5) bond length is 2.74 Å. The Ni(1)-Ni(7) bond length is 2.74 Å. In the second Ni site, Ni(2) is bonded in a 12-coordinate geometry to one Zr(12), one Zr(14), one Zr(15), one Zr(16), one Zr(2), one Zr(3), one Zr(6), one Zr(7), one Zr(9), one Ni(4), one Ni(6), and one Ni(8) atom. The Ni(2)-Ni(4) bond length is 2.75 Å. The Ni(2)-Ni(6) bond length is 2.77 Å. The Ni(2)-Ni(8) bond length is 2.75 Å. In the third Ni site, Ni(3) is bonded in a 12-coordinate geometry to one Zr(1), one Zr(10), one Zr(12), one Zr(13), one Zr(14), one Zr(16), one Zr(3), one Zr(6), one Zr(9), one Ni(1), one Ni(5), and one Ni(7) atom. The Ni(3)-Ni(5) bond length is 2.75 Å. The Ni(3)-Ni(7) bond length is 2.77 Å. In the fourth Ni site, Ni(4) is bonded in a 12-coordinate geometry to one Zr(1), one Zr(10), one Zr(11), one Zr(12), one Zr(13), one Zr(16), one Zr(2), one Zr(4), one Zr(6), one Ni(2), one Ni(6), and one Ni(8) atom. The Ni(4)-Ni(6) bond length is 2.77 Å. The Ni(4)-Ni(8) bond length is 2.74 Å. In the fifth Ni site, Ni(5) is bonded in a 12-coordinate geometry to one Zr(12), one Zr(13), one Zr(15), one Zr(2), one Zr(3), one Zr(5), one Zr(7), one Zr(8), one Zr(9), one Ni(1), one Ni(3), and one Ni(7) atom. The Ni(5)-Ni(7) bond length is 2.76 Å. In the sixth Ni site, Ni(6) is bonded in a 12-coordinate geometry to one Zr(11), one Zr(12), one Zr(13), one Zr(14), one Zr(15), one Zr(4), one Zr(5), one Zr(7), one Zr(8), one Ni(2), one Ni(4), and one Ni(8) atom. The Ni(6)-Ni(8) bond length is 2.76 Å. In the seventh Ni site, Ni(7) is bonded in a 12-coordinate geometry to one Zr(1), one Zr(10), one Zr(11), one Zr(12), one Zr(14), one Zr(2), one Zr(4), one Zr(5), one Zr(8), one Ni(1), one Ni(3), and one Ni(5) atom. In the eighth Ni site, Ni(8) is bonded in a 12-coordinate geometry to one Zr(1), one Zr(10), one Zr(13), one Zr(14), one Zr(2), one Zr(3), one Zr(5), one Zr(8), one Zr(9), one Ni(2), one Ni(4), and one Ni(6) atom. There are four inequivalent Al sites. In the first Al site, Al(1) is bonded to one Zr(10), one Zr(15), one Zr(3), one Zr(4), one Zr(5), and one Zr(6) atom to form distorted corner-sharing AlZr6 octahedra. The corner-sharing octahedral tilt angles range from 59-62°. In the second Al site, Al(2) is bonded to one Zr(10), one Zr(11), one Zr(15), one Zr(16), one Zr(8), and one Zr(9) atom to form distorted corner-sharing AlZr6 octahedra. The corner-sharing octahedral tilt angles range from 59-61°. In the third Al site, Al(3) is bonded to one Zr(1), one Zr(16), one Zr(3), one Zr(4), one Zr(7), and one Zr(8) atom to form distorted corner-sharing AlZr6 octahedra. The corner-sharing octahedral tilt angles range from 58-62°. In the fourth Al site, Al(4) is bonded to one Zr(1), one Zr(11), one Zr(5), one Zr(6), one Zr(7), and one Zr(9) atom to form distorted corner-sharing AlZr6 octahedra. The corner-sharing octahedral tilt angles range from 58-61°.