Tm4Ni13C4 crystallizes in the orthorhombic Cmmm space group. There are two inequivalent Tm sites. In the first Tm site, Tm(1) is bonded in a 14-coordinate geometry to two equivalent Ni(1), two equivalent Ni(2), two equivalent Ni(5), four equivalent Ni(3), and four equivalent Ni(4) atoms. In the second Tm site, Tm(2) is bonded in a 15-coordinate geometry to one Ni(5), two equivalent Ni(1), four equivalent Ni(3), four equivalent Ni(4), and four equivalent C(1) atoms. There are five inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a linear geometry to two equivalent Tm(1), two equivalent Tm(2), and two equivalent C(2) atoms. In the second Ni site, Ni(2) is bonded to four equivalent Tm(1), four equivalent Ni(4), and four equivalent Ni(5) atoms to form NiTm4Ni8 cuboctahedra that share corners with four equivalent C(2)Ni6 octahedra and faces with two equivalent Ni(2)Tm4Ni8 cuboctahedra. The corner-sharing octahedral tilt angles are 34°. In the third Ni site, Ni(3) is bonded in a distorted bent 150 degrees geometry to two equivalent Tm(1), two equivalent Tm(2), one C(1), and one C(2) atom. In the fourth Ni site, Ni(4) is bonded in a single-bond geometry to two equivalent Tm(1), two equivalent Tm(2), one Ni(2), two equivalent Ni(5), and one C(2) atom. In the fifth Ni site, Ni(5) is bonded in a 9-coordinate geometry to one Tm(2), two equivalent Tm(1), two equivalent Ni(2), and four equivalent Ni(4) atoms. There are two inequivalent C sites. In the first C site, C(1) is bonded in a 7-coordinate geometry to four equivalent Tm(2), two equivalent Ni(3), and one C(1) atom. In the second C site, C(2) is bonded to two equivalent Ni(1), two equivalent Ni(3), and two equivalent Ni(4) atoms to form CNi6 octahedra that share corners with two equivalent Ni(2)Tm4Ni8 cuboctahedra and corners with two equivalent C(2)Ni6 octahedra. The corner-sharing octahedra are not tilted.
Tm4Ni13C4 crystallizes in the orthorhombic Cmmm space group. There are two inequivalent Tm sites. In the first Tm site, Tm(1) is bonded in a 14-coordinate geometry to two equivalent Ni(1), two equivalent Ni(2), two equivalent Ni(5), four equivalent Ni(3), and four equivalent Ni(4) atoms. Both Tm(1)-Ni(1) bond lengths are 3.01 Å. Both Tm(1)-Ni(2) bond lengths are 2.93 Å. Both Tm(1)-Ni(5) bond lengths are 2.65 Å. All Tm(1)-Ni(3) bond lengths are 2.80 Å. All Tm(1)-Ni(4) bond lengths are 3.01 Å. In the second Tm site, Tm(2) is bonded in a 15-coordinate geometry to one Ni(5), two equivalent Ni(1), four equivalent Ni(3), four equivalent Ni(4), and four equivalent C(1) atoms. The Tm(2)-Ni(5) bond length is 2.61 Å. Both Tm(2)-Ni(1) bond lengths are 3.19 Å. All Tm(2)-Ni(3) bond lengths are 2.89 Å. All Tm(2)-Ni(4) bond lengths are 3.00 Å. All Tm(2)-C(1) bond lengths are 2.69 Å. There are five inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a linear geometry to two equivalent Tm(1), two equivalent Tm(2), and two equivalent C(2) atoms. Both Ni(1)-C(2) bond lengths are 1.91 Å. In the second Ni site, Ni(2) is bonded to four equivalent Tm(1), four equivalent Ni(4), and four equivalent Ni(5) atoms to form NiTm4Ni8 cuboctahedra that share corners with four equivalent C(2)Ni6 octahedra and faces with two equivalent Ni(2)Tm4Ni8 cuboctahedra. The corner-sharing octahedral tilt angles are 34°. All Ni(2)-Ni(4) bond lengths are 2.49 Å. All Ni(2)-Ni(5) bond lengths are 2.40 Å. In the third Ni site, Ni(3) is bonded in a distorted bent 150 degrees geometry to two equivalent Tm(1), two equivalent Tm(2), one C(1), and one C(2) atom. The Ni(3)-C(1) bond length is 1.90 Å. The Ni(3)-C(2) bond length is 1.88 Å. In the fourth Ni site, Ni(4) is bonded in a single-bond geometry to two equivalent Tm(1), two equivalent Tm(2), one Ni(2), two equivalent Ni(5), and one C(2) atom. Both Ni(4)-Ni(5) bond lengths are 2.41 Å. The Ni(4)-C(2) bond length is 1.86 Å. In the fifth Ni site, Ni(5) is bonded in a 9-coordinate geometry to one Tm(2), two equivalent Tm(1), two equivalent Ni(2), and four equivalent Ni(4) atoms. There are two inequivalent C sites. In the first C site, C(1) is bonded in a 7-coordinate geometry to four equivalent Tm(2), two equivalent Ni(3), and one C(1) atom. The C(1)-C(1) bond length is 1.36 Å. In the second C site, C(2) is bonded to two equivalent Ni(1), two equivalent Ni(3), and two equivalent Ni(4) atoms to form CNi6 octahedra that share corners with two equivalent Ni(2)Tm4Ni8 cuboctahedra and corners with two equivalent C(2)Ni6 octahedra. The corner-sharing octahedra are not tilted.