Sm4Ni6Al23 crystallizes in the monoclinic C2/m space group. There are two inequivalent Sm sites. In the first Sm site, Sm(1) is bonded in a 15-coordinate geometry to two equivalent Ni(2), one Al(1), one Al(4), one Al(5), one Al(6), one Al(8), two equivalent Al(10), two equivalent Al(2), two equivalent Al(3), and two equivalent Al(9) atoms. In the second Sm site, Sm(2) is bonded in a 15-coordinate geometry to two equivalent Ni(3), one Al(1), one Al(9), two equivalent Al(12), two equivalent Al(2), two equivalent Al(5), two equivalent Al(8), and three equivalent Al(7) atoms. There are three inequivalent Ni sites. In the first Ni site, Ni(3) is bonded in a 7-coordinate geometry to two equivalent Sm(2), one Al(5), one Al(8), two equivalent Al(9), and three equivalent Al(7) atoms. In the second Ni site, Ni(1) is bonded in a 9-coordinate geometry to one Al(10), one Al(6), one Al(8), two equivalent Al(1), two equivalent Al(11), and two equivalent Al(3) atoms. In the third Ni site, Ni(2) is bonded in a 8-coordinate geometry to two equivalent Sm(1), one Al(10), one Al(11), one Al(3), two equivalent Al(6), and three equivalent Al(4) atoms. There are twelve inequivalent Al sites. In the first Al site, Al(1) is bonded to one Sm(1), one Sm(2), two equivalent Ni(1), one Al(11), one Al(3), two equivalent Al(10), two equivalent Al(2), and two equivalent Al(8) atoms to form distorted face-sharing AlSm2Al8Ni2 cuboctahedra. In the second Al site, Al(2) is bonded in a 10-coordinate geometry to two equivalent Sm(1), two equivalent Sm(2), one Al(10), one Al(8), two equivalent Al(1), and two equivalent Al(5) atoms. In the third Al site, Al(3) is bonded in a 3-coordinate geometry to two equivalent Sm(1), one Ni(2), two equivalent Ni(1), and one Al(1) atom. In the fourth Al site, Al(4) is bonded in a 3-coordinate geometry to one Sm(1) and three equivalent Ni(2) atoms. In the fifth Al site, Al(5) is bonded in a distorted single-bond geometry to one Sm(1), two equivalent Sm(2), one Ni(3), two equivalent Al(12), and two equivalent Al(2) atoms. In the sixth Al site, Al(6) is bonded in a distorted trigonal non-coplanar geometry to one Sm(1), one Ni(1), and two equivalent Ni(2) atoms. In the seventh Al site, Al(7) is bonded in a 3-coordinate geometry to three equivalent Sm(2) and three equivalent Ni(3) atoms. In the eighth Al site, Al(8) is bonded in a distorted bent 150 degrees geometry to one Sm(1), two equivalent Sm(2), one Ni(1), one Ni(3), one Al(2), and two equivalent Al(1) atoms. In the ninth Al site, Al(9) is bonded in a 2-coordinate geometry to one Sm(2), two equivalent Sm(1), and two equivalent Ni(3) atoms. In the tenth Al site, Al(10) is bonded in a distorted bent 150 degrees geometry to two equivalent Sm(1), one Ni(1), one Ni(2), one Al(2), and two equivalent Al(1) atoms. In the eleventh Al site, Al(11) is bonded in a distorted trigonal planar geometry to one Ni(2), two equivalent Ni(1), and one Al(1) atom. In the twelfth Al site, Al(12) is bonded in a 8-coordinate geometry to four equivalent Sm(2) and four equivalent Al(5) atoms.
Sm4Ni6Al23 crystallizes in the monoclinic C2/m space group. There are two inequivalent Sm sites. In the first Sm site, Sm(1) is bonded in a 15-coordinate geometry to two equivalent Ni(2), one Al(1), one Al(4), one Al(5), one Al(6), one Al(8), two equivalent Al(10), two equivalent Al(2), two equivalent Al(3), and two equivalent Al(9) atoms. Both Sm(1)-Ni(2) bond lengths are 3.25 Å. The Sm(1)-Al(1) bond length is 3.24 Å. The Sm(1)-Al(4) bond length is 3.08 Å. The Sm(1)-Al(5) bond length is 3.16 Å. The Sm(1)-Al(6) bond length is 3.24 Å. The Sm(1)-Al(8) bond length is 3.36 Å. Both Sm(1)-Al(10) bond lengths are 3.13 Å. Both Sm(1)-Al(2) bond lengths are 3.13 Å. Both Sm(1)-Al(3) bond lengths are 3.07 Å. Both Sm(1)-Al(9) bond lengths are 3.06 Å. In the second Sm site, Sm(2) is bonded in a 15-coordinate geometry to two equivalent Ni(3), one Al(1), one Al(9), two equivalent Al(12), two equivalent Al(2), two equivalent Al(5), two equivalent Al(8), and three equivalent Al(7) atoms. Both Sm(2)-Ni(3) bond lengths are 3.26 Å. The Sm(2)-Al(1) bond length is 3.18 Å. The Sm(2)-Al(9) bond length is 3.31 Å. Both Sm(2)-Al(12) bond lengths are 3.13 Å. Both Sm(2)-Al(2) bond lengths are 3.11 Å. There is one shorter (3.09 Å) and one longer (3.21 Å) Sm(2)-Al(5) bond length. Both Sm(2)-Al(8) bond lengths are 3.20 Å. There are two shorter (3.08 Å) and one longer (3.31 Å) Sm(2)-Al(7) bond length. There are three inequivalent Ni sites. In the first Ni site, Ni(3) is bonded in a 7-coordinate geometry to two equivalent Sm(2), one Al(5), one Al(8), two equivalent Al(9), and three equivalent Al(7) atoms. The Ni(3)-Al(5) bond length is 2.32 Å. The Ni(3)-Al(8) bond length is 2.40 Å. Both Ni(3)-Al(9) bond lengths are 2.43 Å. There is one shorter (2.41 Å) and two longer (2.50 Å) Ni(3)-Al(7) bond lengths. In the second Ni site, Ni(1) is bonded in a 9-coordinate geometry to one Al(10), one Al(6), one Al(8), two equivalent Al(1), two equivalent Al(11), and two equivalent Al(3) atoms. The Ni(1)-Al(10) bond length is 2.46 Å. The Ni(1)-Al(6) bond length is 2.40 Å. The Ni(1)-Al(8) bond length is 2.43 Å. Both Ni(1)-Al(1) bond lengths are 2.75 Å. Both Ni(1)-Al(11) bond lengths are 2.48 Å. Both Ni(1)-Al(3) bond lengths are 2.52 Å. In the third Ni site, Ni(2) is bonded in a 8-coordinate geometry to two equivalent Sm(1), one Al(10), one Al(11), one Al(3), two equivalent Al(6), and three equivalent Al(4) atoms. The Ni(2)-Al(10) bond length is 2.46 Å. The Ni(2)-Al(11) bond length is 2.36 Å. The Ni(2)-Al(3) bond length is 2.51 Å. Both Ni(2)-Al(6) bond lengths are 2.52 Å. There are two shorter (2.39 Å) and one longer (2.53 Å) Ni(2)-Al(4) bond length. There are twelve inequivalent Al sites. In the first Al site, Al(1) is bonded to one Sm(1), one Sm(2), two equivalent Ni(1), one Al(11), one Al(3), two equivalent Al(10), two equivalent Al(2), and two equivalent Al(8) atoms to form distorted face-sharing AlSm2Al8Ni2 cuboctahedra. The Al(1)-Al(11) bond length is 2.68 Å. The Al(1)-Al(3) bond length is 2.79 Å. Both Al(1)-Al(10) bond lengths are 2.71 Å. Both Al(1)-Al(2) bond lengths are 2.97 Å. Both Al(1)-Al(8) bond lengths are 2.74 Å. In the second Al site, Al(2) is bonded in a 10-coordinate geometry to two equivalent Sm(1), two equivalent Sm(2), one Al(10), one Al(8), two equivalent Al(1), and two equivalent Al(5) atoms. The Al(2)-Al(10) bond length is 2.88 Å. The Al(2)-Al(8) bond length is 3.03 Å. Both Al(2)-Al(5) bond lengths are 2.89 Å. In the third Al site, Al(3) is bonded in a 3-coordinate geometry to two equivalent Sm(1), one Ni(2), two equivalent Ni(1), and one Al(1) atom. In the fourth Al site, Al(4) is bonded in a 3-coordinate geometry to one Sm(1) and three equivalent Ni(2) atoms. In the fifth Al site, Al(5) is bonded in a distorted single-bond geometry to one Sm(1), two equivalent Sm(2), one Ni(3), two equivalent Al(12), and two equivalent Al(2) atoms. Both Al(5)-Al(12) bond lengths are 2.90 Å. In the sixth Al site, Al(6) is bonded in a distorted trigonal non-coplanar geometry to one Sm(1), one Ni(1), and two equivalent Ni(2) atoms. In the seventh Al site, Al(7) is bonded in a 3-coordinate geometry to three equivalent Sm(2) and three equivalent Ni(3) atoms. In the eighth Al site, Al(8) is bonded in a distorted bent 150 degrees geometry to one Sm(1), two equivalent Sm(2), one Ni(1), one Ni(3), one Al(2), and two equivalent Al(1) atoms. In the ninth Al site, Al(9) is bonded in a 2-coordinate geometry to one Sm(2), two equivalent Sm(1), and two equivalent Ni(3) atoms. In the tenth Al site, Al(10) is bonded in a distorted bent 150 degrees geometry to two equivalent Sm(1), one Ni(1), one Ni(2), one Al(2), and two equivalent Al(1) atoms. In the eleventh Al site, Al(11) is bonded in a distorted trigonal planar geometry to one Ni(2), two equivalent Ni(1), and one Al(1) atom. In the twelfth Al site, Al(12) is bonded in a 8-coordinate geometry to four equivalent Sm(2) and four equivalent Al(5) atoms.