Tm4Zn5Ge6 crystallizes in the orthorhombic Cmc2_1 space group. There are four inequivalent Tm sites. In the first Tm site, Tm(1) is bonded in a 11-coordinate geometry to one Zn(2), two equivalent Zn(1), two equivalent Zn(5), two equivalent Ge(2), two equivalent Ge(4), and two equivalent Ge(5) atoms. In the second Tm site, Tm(2) is bonded to one Ge(3), one Ge(6), two equivalent Ge(1), and two equivalent Ge(4) atoms to form distorted TmGe6 octahedra that share  a cornercorner with one Tm(3)Ge6 octahedra,  a cornercorner with one Zn(4)Ge4 tetrahedra, edges with two equivalent Tm(2)Ge6 octahedra, edges with two equivalent Tm(3)Ge6 octahedra, and edges with two equivalent Zn(4)Ge4 tetrahedra. The corner-sharing octahedral tilt angles are 43°. In the third Tm site, Tm(3) is bonded to one Ge(1), one Ge(6), two equivalent Ge(2), and two equivalent Ge(3) atoms to form distorted TmGe6 octahedra that share  a cornercorner with one Tm(2)Ge6 octahedra,  a cornercorner with one Zn(4)Ge4 tetrahedra, edges with two equivalent Tm(2)Ge6 octahedra, edges with two equivalent Tm(3)Ge6 octahedra, and edges with two equivalent Zn(4)Ge4 tetrahedra. The corner-sharing octahedral tilt angles are 43°. In the fourth Tm site, Tm(4) is bonded in a 10-coordinate geometry to one Zn(2), two equivalent Zn(3), one Ge(6), two equivalent Ge(2), two equivalent Ge(4), and two equivalent Ge(5) atoms. There are five inequivalent Zn sites. In the first Zn site, Zn(1) is bonded in a 4-coordinate geometry to two equivalent Tm(1), one Ge(4), one Ge(5), and two equivalent Ge(6) atoms. In the second Zn site, Zn(2) is bonded in a 4-coordinate geometry to one Tm(1), one Tm(4), one Ge(1), one Ge(3), and two equivalent Ge(5) atoms. In the third Zn site, Zn(3) is bonded in a 4-coordinate geometry to two equivalent Tm(4), one Ge(4), one Ge(5), and two equivalent Ge(3) atoms. In the fourth Zn site, Zn(4) is bonded to one Ge(1), one Ge(3), and two equivalent Ge(6) atoms to form distorted ZnGe4 tetrahedra that share  a cornercorner with one Tm(2)Ge6 octahedra,  a cornercorner with one Tm(3)Ge6 octahedra, corners with two equivalent Zn(4)Ge4 tetrahedra, edges with two equivalent Tm(2)Ge6 octahedra, and edges with two equivalent Tm(3)Ge6 octahedra. The corner-sharing octahedral tilt angles range from 12-14°. In the fifth Zn site, Zn(5) is bonded in a 4-coordinate geometry to two equivalent Tm(1), one Ge(2), one Ge(5), and two equivalent Ge(1) atoms. There are six inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one Tm(3), two equivalent Tm(2), one Zn(2), one Zn(4), and two equivalent Zn(5) atoms to form distorted edge-sharing GeTm3Zn4 pentagonal bipyramids. In the second Ge site, Ge(2) is bonded in a 8-coordinate geometry to two equivalent Tm(1), two equivalent Tm(3), two equivalent Tm(4), one Zn(5), and one Ge(4) atom. In the third Ge site, Ge(3) is bonded to one Tm(2), two equivalent Tm(3), one Zn(2), one Zn(4), and two equivalent Zn(3) atoms to form distorted edge-sharing GeTm3Zn4 pentagonal bipyramids. In the fourth Ge site, Ge(4) is bonded in a 9-coordinate geometry to two equivalent Tm(1), two equivalent Tm(2), two equivalent Tm(4), one Zn(1), one Zn(3), and one Ge(2) atom. In the fifth Ge site, Ge(5) is bonded in a 9-coordinate geometry to two equivalent Tm(1), two equivalent Tm(4), one Zn(1), one Zn(3), one Zn(5), and two equivalent Zn(2) atoms. In the sixth Ge site, Ge(6) is bonded in a 7-coordinate geometry to one Tm(2), one Tm(3), one Tm(4), two equivalent Zn(1), and two equivalent Zn(4) atoms.
Tm4Zn5Ge6 crystallizes in the orthorhombic Cmc2_1 space group. There are four inequivalent Tm sites. In the first Tm site, Tm(1) is bonded in a 11-coordinate geometry to one Zn(2), two equivalent Zn(1), two equivalent Zn(5), two equivalent Ge(2), two equivalent Ge(4), and two equivalent Ge(5) atoms. The Tm(1)-Zn(2) bond length is 3.00 Å. Both Tm(1)-Zn(1) bond lengths are 2.98 Å. Both Tm(1)-Zn(5) bond lengths are 3.07 Å. Both Tm(1)-Ge(2) bond lengths are 3.08 Å. Both Tm(1)-Ge(4) bond lengths are 3.02 Å. Both Tm(1)-Ge(5) bond lengths are 2.97 Å. In the second Tm site, Tm(2) is bonded to one Ge(3), one Ge(6), two equivalent Ge(1), and two equivalent Ge(4) atoms to form distorted TmGe6 octahedra that share  a cornercorner with one Tm(3)Ge6 octahedra,  a cornercorner with one Zn(4)Ge4 tetrahedra, edges with two equivalent Tm(2)Ge6 octahedra, edges with two equivalent Tm(3)Ge6 octahedra, and edges with two equivalent Zn(4)Ge4 tetrahedra. The corner-sharing octahedral tilt angles are 43°. The Tm(2)-Ge(3) bond length is 2.93 Å. The Tm(2)-Ge(6) bond length is 2.98 Å. Both Tm(2)-Ge(1) bond lengths are 2.88 Å. Both Tm(2)-Ge(4) bond lengths are 2.97 Å. In the third Tm site, Tm(3) is bonded to one Ge(1), one Ge(6), two equivalent Ge(2), and two equivalent Ge(3) atoms to form distorted TmGe6 octahedra that share  a cornercorner with one Tm(2)Ge6 octahedra,  a cornercorner with one Zn(4)Ge4 tetrahedra, edges with two equivalent Tm(2)Ge6 octahedra, edges with two equivalent Tm(3)Ge6 octahedra, and edges with two equivalent Zn(4)Ge4 tetrahedra. The corner-sharing octahedral tilt angles are 43°. The Tm(3)-Ge(1) bond length is 2.87 Å. The Tm(3)-Ge(6) bond length is 2.85 Å. Both Tm(3)-Ge(2) bond lengths are 2.91 Å. Both Tm(3)-Ge(3) bond lengths are 2.86 Å. In the fourth Tm site, Tm(4) is bonded in a 10-coordinate geometry to one Zn(2), two equivalent Zn(3), one Ge(6), two equivalent Ge(2), two equivalent Ge(4), and two equivalent Ge(5) atoms. The Tm(4)-Zn(2) bond length is 3.12 Å. Both Tm(4)-Zn(3) bond lengths are 3.22 Å. The Tm(4)-Ge(6) bond length is 2.97 Å. Both Tm(4)-Ge(2) bond lengths are 2.97 Å. Both Tm(4)-Ge(4) bond lengths are 3.14 Å. Both Tm(4)-Ge(5) bond lengths are 2.99 Å. There are five inequivalent Zn sites. In the first Zn site, Zn(1) is bonded in a 4-coordinate geometry to two equivalent Tm(1), one Ge(4), one Ge(5), and two equivalent Ge(6) atoms. The Zn(1)-Ge(4) bond length is 2.56 Å. The Zn(1)-Ge(5) bond length is 2.56 Å. Both Zn(1)-Ge(6) bond lengths are 2.48 Å. In the second Zn site, Zn(2) is bonded in a 4-coordinate geometry to one Tm(1), one Tm(4), one Ge(1), one Ge(3), and two equivalent Ge(5) atoms. The Zn(2)-Ge(1) bond length is 2.52 Å. The Zn(2)-Ge(3) bond length is 2.50 Å. Both Zn(2)-Ge(5) bond lengths are 2.60 Å. In the third Zn site, Zn(3) is bonded in a 4-coordinate geometry to two equivalent Tm(4), one Ge(4), one Ge(5), and two equivalent Ge(3) atoms. The Zn(3)-Ge(4) bond length is 2.53 Å. The Zn(3)-Ge(5) bond length is 2.70 Å. Both Zn(3)-Ge(3) bond lengths are 2.48 Å. In the fourth Zn site, Zn(4) is bonded to one Ge(1), one Ge(3), and two equivalent Ge(6) atoms to form distorted ZnGe4 tetrahedra that share  a cornercorner with one Tm(2)Ge6 octahedra,  a cornercorner with one Tm(3)Ge6 octahedra, corners with two equivalent Zn(4)Ge4 tetrahedra, edges with two equivalent Tm(2)Ge6 octahedra, and edges with two equivalent Tm(3)Ge6 octahedra. The corner-sharing octahedral tilt angles range from 12-14°. The Zn(4)-Ge(1) bond length is 2.51 Å. The Zn(4)-Ge(3) bond length is 2.53 Å. Both Zn(4)-Ge(6) bond lengths are 2.62 Å. In the fifth Zn site, Zn(5) is bonded in a 4-coordinate geometry to two equivalent Tm(1), one Ge(2), one Ge(5), and two equivalent Ge(1) atoms. The Zn(5)-Ge(2) bond length is 2.56 Å. The Zn(5)-Ge(5) bond length is 2.70 Å. Both Zn(5)-Ge(1) bond lengths are 2.48 Å. There are six inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one Tm(3), two equivalent Tm(2), one Zn(2), one Zn(4), and two equivalent Zn(5) atoms to form distorted edge-sharing GeTm3Zn4 pentagonal bipyramids. In the second Ge site, Ge(2) is bonded in a 8-coordinate geometry to two equivalent Tm(1), two equivalent Tm(3), two equivalent Tm(4), one Zn(5), and one Ge(4) atom. The Ge(2)-Ge(4) bond length is 2.49 Å. In the third Ge site, Ge(3) is bonded to one Tm(2), two equivalent Tm(3), one Zn(2), one Zn(4), and two equivalent Zn(3) atoms to form distorted edge-sharing GeTm3Zn4 pentagonal bipyramids. In the fourth Ge site, Ge(4) is bonded in a 9-coordinate geometry to two equivalent Tm(1), two equivalent Tm(2), two equivalent Tm(4), one Zn(1), one Zn(3), and one Ge(2) atom. In the fifth Ge site, Ge(5) is bonded in a 9-coordinate geometry to two equivalent Tm(1), two equivalent Tm(4), one Zn(1), one Zn(3), one Zn(5), and two equivalent Zn(2) atoms. In the sixth Ge site, Ge(6) is bonded in a 7-coordinate geometry to one Tm(2), one Tm(3), one Tm(4), two equivalent Zn(1), and two equivalent Zn(4) atoms.