Tm5(Co2Si7)2 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Tm sites. In the first Tm site, Tm(1) is bonded in a 18-coordinate geometry to two equivalent Co(2), four equivalent Co(1), two equivalent Si(2), two equivalent Si(3), two equivalent Si(4), two equivalent Si(5), and four equivalent Si(1) atoms. In the second Tm site, Tm(2) is bonded to two equivalent Co(2), one Si(3), one Si(5), two equivalent Si(4), three equivalent Si(6), and three equivalent Si(7) atoms to form a mixture of distorted face, corner, and edge-sharing TmCo2Si10 cuboctahedra. In the third Tm site, Tm(3) is bonded to two equivalent Co(2), one Si(3), one Si(5), two equivalent Si(2), three equivalent Si(6), and three equivalent Si(7) atoms to form a mixture of distorted face, corner, and edge-sharing TmCo2Si10 cuboctahedra. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded in a 10-coordinate geometry to two equivalent Tm(1), one Co(1), one Si(2), one Si(3), one Si(4), one Si(5), and three equivalent Si(1) atoms. In the second Co site, Co(2) is bonded in a 10-coordinate geometry to one Tm(1), two equivalent Tm(2), two equivalent Tm(3), one Si(2), one Si(3), one Si(4), one Si(5), and one Si(7) atom. There are seven inequivalent Si sites. In the first Si site, Si(5) is bonded in a 8-coordinate geometry to one Tm(1), one Tm(2), one Tm(3), one Co(1), one Co(2), one Si(1), one Si(2), and one Si(4) atom. In the second Si site, Si(6) is bonded in a 8-coordinate geometry to three equivalent Tm(2), three equivalent Tm(3), one Si(6), and one Si(7) atom. In the third Si site, Si(7) is bonded in a 9-coordinate geometry to three equivalent Tm(2), three equivalent Tm(3), one Co(2), one Si(6), and one Si(7) atom. In the fourth Si site, Si(1) is bonded in a 9-coordinate geometry to two equivalent Tm(1), three equivalent Co(1), one Si(2), one Si(3), one Si(4), and one Si(5) atom. In the fifth Si site, Si(2) is bonded in a 8-coordinate geometry to one Tm(1), two equivalent Tm(3), one Co(1), one Co(2), one Si(1), one Si(3), and one Si(5) atom. In the sixth Si site, Si(3) is bonded in a 8-coordinate geometry to one Tm(1), one Tm(2), one Tm(3), one Co(1), one Co(2), one Si(1), one Si(2), and one Si(4) atom. In the seventh Si site, Si(4) is bonded in a 8-coordinate geometry to one Tm(1), two equivalent Tm(2), one Co(1), one Co(2), one Si(1), one Si(3), and one Si(5) atom.
Tm5(Co2Si7)2 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Tm sites. In the first Tm site, Tm(1) is bonded in a 18-coordinate geometry to two equivalent Co(2), four equivalent Co(1), two equivalent Si(2), two equivalent Si(3), two equivalent Si(4), two equivalent Si(5), and four equivalent Si(1) atoms. Both Tm(1)-Co(2) bond lengths are 3.04 Å. There are two shorter (3.04 Å) and two longer (3.07 Å) Tm(1)-Co(1) bond lengths. Both Tm(1)-Si(2) bond lengths are 3.05 Å. Both Tm(1)-Si(3) bond lengths are 3.03 Å. Both Tm(1)-Si(4) bond lengths are 3.04 Å. Both Tm(1)-Si(5) bond lengths are 3.04 Å. There are two shorter (2.88 Å) and two longer (2.90 Å) Tm(1)-Si(1) bond lengths. In the second Tm site, Tm(2) is bonded to two equivalent Co(2), one Si(3), one Si(5), two equivalent Si(4), three equivalent Si(6), and three equivalent Si(7) atoms to form a mixture of distorted face, corner, and edge-sharing TmCo2Si10 cuboctahedra. There is one shorter (3.07 Å) and one longer (3.08 Å) Tm(2)-Co(2) bond length. The Tm(2)-Si(3) bond length is 2.98 Å. The Tm(2)-Si(5) bond length is 3.01 Å. There is one shorter (2.97 Å) and one longer (3.00 Å) Tm(2)-Si(4) bond length. There are a spread of Tm(2)-Si(6) bond distances ranging from 2.88-3.06 Å. There are a spread of Tm(2)-Si(7) bond distances ranging from 2.88-3.08 Å. In the third Tm site, Tm(3) is bonded to two equivalent Co(2), one Si(3), one Si(5), two equivalent Si(2), three equivalent Si(6), and three equivalent Si(7) atoms to form a mixture of distorted face, corner, and edge-sharing TmCo2Si10 cuboctahedra. There is one shorter (3.07 Å) and one longer (3.09 Å) Tm(3)-Co(2) bond length. The Tm(3)-Si(3) bond length is 3.02 Å. The Tm(3)-Si(5) bond length is 2.97 Å. There is one shorter (2.96 Å) and one longer (3.01 Å) Tm(3)-Si(2) bond length. There are a spread of Tm(3)-Si(6) bond distances ranging from 2.87-3.07 Å. There are two shorter (2.89 Å) and one longer (3.06 Å) Tm(3)-Si(7) bond length. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded in a 10-coordinate geometry to two equivalent Tm(1), one Co(1), one Si(2), one Si(3), one Si(4), one Si(5), and three equivalent Si(1) atoms. The Co(1)-Co(1) bond length is 2.78 Å. The Co(1)-Si(2) bond length is 2.49 Å. The Co(1)-Si(3) bond length is 2.48 Å. The Co(1)-Si(4) bond length is 2.49 Å. The Co(1)-Si(5) bond length is 2.48 Å. There are a spread of Co(1)-Si(1) bond distances ranging from 2.27-2.30 Å. In the second Co site, Co(2) is bonded in a 10-coordinate geometry to one Tm(1), two equivalent Tm(2), two equivalent Tm(3), one Si(2), one Si(3), one Si(4), one Si(5), and one Si(7) atom. The Co(2)-Si(2) bond length is 2.31 Å. The Co(2)-Si(3) bond length is 2.29 Å. The Co(2)-Si(4) bond length is 2.31 Å. The Co(2)-Si(5) bond length is 2.29 Å. The Co(2)-Si(7) bond length is 2.32 Å. There are seven inequivalent Si sites. In the first Si site, Si(5) is bonded in a 8-coordinate geometry to one Tm(1), one Tm(2), one Tm(3), one Co(1), one Co(2), one Si(1), one Si(2), and one Si(4) atom. The Si(5)-Si(1) bond length is 2.59 Å. The Si(5)-Si(2) bond length is 2.41 Å. The Si(5)-Si(4) bond length is 2.54 Å. In the second Si site, Si(6) is bonded in a 8-coordinate geometry to three equivalent Tm(2), three equivalent Tm(3), one Si(6), and one Si(7) atom. The Si(6)-Si(6) bond length is 2.42 Å. The Si(6)-Si(7) bond length is 2.42 Å. In the third Si site, Si(7) is bonded in a 9-coordinate geometry to three equivalent Tm(2), three equivalent Tm(3), one Co(2), one Si(6), and one Si(7) atom. The Si(7)-Si(7) bond length is 2.40 Å. In the fourth Si site, Si(1) is bonded in a 9-coordinate geometry to two equivalent Tm(1), three equivalent Co(1), one Si(2), one Si(3), one Si(4), and one Si(5) atom. The Si(1)-Si(2) bond length is 2.59 Å. The Si(1)-Si(3) bond length is 2.59 Å. The Si(1)-Si(4) bond length is 2.58 Å. In the fifth Si site, Si(2) is bonded in a 8-coordinate geometry to one Tm(1), two equivalent Tm(3), one Co(1), one Co(2), one Si(1), one Si(3), and one Si(5) atom. The Si(2)-Si(3) bond length is 2.53 Å. In the sixth Si site, Si(3) is bonded in a 8-coordinate geometry to one Tm(1), one Tm(2), one Tm(3), one Co(1), one Co(2), one Si(1), one Si(2), and one Si(4) atom. The Si(3)-Si(4) bond length is 2.41 Å. In the seventh Si site, Si(4) is bonded in a 8-coordinate geometry to one Tm(1), two equivalent Tm(2), one Co(1), one Co(2), one Si(1), one Si(3), and one Si(5) atom.