K3Sm4(CuTe2)5 crystallizes in the orthorhombic Pmn2_1 space group. There are three inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to one Te(1), two equivalent Te(10), two equivalent Te(6), and two equivalent Te(8) atoms. In the second K site, K(2) is bonded in a 9-coordinate geometry to two equivalent Cu(5), one Te(2), two equivalent Te(5), two equivalent Te(7), and two equivalent Te(9) atoms. In the third K site, K(3) is bonded in a 6-coordinate geometry to two equivalent Te(6), two equivalent Te(7), and two equivalent Te(8) atoms. There are four inequivalent Sm sites. In the first Sm site, Sm(1) is bonded in a 7-coordinate geometry to one Cu(1), one Te(4), one Te(9), two equivalent Te(2), and two equivalent Te(6) atoms. In the second Sm site, Sm(2) is bonded in a 11-coordinate geometry to one Cu(2), two equivalent Cu(4), two equivalent Cu(5), one Te(10), one Te(3), two equivalent Te(1), and two equivalent Te(5) atoms. In the third Sm site, Sm(3) is bonded in a 7-coordinate geometry to one Cu(5), one Te(2), one Te(9), two equivalent Te(3), and two equivalent Te(7) atoms. In the fourth Sm site, Sm(4) is bonded to two equivalent Cu(2), one Te(1), one Te(10), two equivalent Te(4), and two equivalent Te(8) atoms to form SmCu2Te6 octahedra that share corners with two equivalent Te(1)KSm3Cu2 pentagonal pyramids,  an edgeedge with one Te(1)KSm3Cu2 pentagonal pyramid, edges with two equivalent Cu(4)Sm2Te4 tetrahedra, and faces with two equivalent Sm(4)Cu2Te6 octahedra. There are five inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 6-coordinate geometry to one Sm(1), one Cu(2), one Te(3), one Te(4), and two equivalent Te(2) atoms. In the second Cu site, Cu(2) is bonded in a 8-coordinate geometry to one Sm(2), two equivalent Sm(4), one Cu(1), one Te(3), one Te(4), and two equivalent Te(1) atoms. In the third Cu site, Cu(3) is bonded to one Te(6), one Te(7), and two equivalent Te(9) atoms to form distorted corner-sharing CuTe4 tetrahedra. In the fourth Cu site, Cu(4) is bonded to two equivalent Sm(2), one Te(5), one Te(8), and two equivalent Te(10) atoms to form distorted CuSm2Te4 tetrahedra that share corners with two equivalent Te(1)KSm3Cu2 pentagonal pyramids, edges with two equivalent Sm(4)Cu2Te6 octahedra,  an edgeedge with one Te(1)KSm3Cu2 pentagonal pyramid, and edges with two equivalent Cu(4)Sm2Te4 tetrahedra. In the fifth Cu site, Cu(5) is bonded in a 9-coordinate geometry to two equivalent K(2), one Sm(3), two equivalent Sm(2), one Te(5), one Te(9), and two equivalent Te(3) atoms. There are ten inequivalent Te sites. In the first Te site, Te(1) is bonded to one K(1), one Sm(4), two equivalent Sm(2), and two equivalent Cu(2) atoms to form distorted TeKSm3Cu2 pentagonal pyramids that share corners with two equivalent Sm(4)Cu2Te6 octahedra, corners with two equivalent Cu(4)Sm2Te4 tetrahedra,  an edgeedge with one Sm(4)Cu2Te6 octahedra, edges with two equivalent Te(1)KSm3Cu2 pentagonal pyramids, and  an edgeedge with one Cu(4)Sm2Te4 tetrahedra. The corner-sharing octahedral tilt angles are 66°. In the second Te site, Te(2) is bonded to one K(2), one Sm(3), two equivalent Sm(1), and two equivalent Cu(1) atoms to form distorted TeKSm3Cu2 pentagonal pyramids that share  a cornercorner with one Te(9)K2Sm2Cu3 pentagonal bipyramid, edges with two equivalent Te(9)K2Sm2Cu3 pentagonal bipyramids, and edges with two equivalent Te(2)KSm3Cu2 pentagonal pyramids. In the third Te site, Te(3) is bonded in a 7-coordinate geometry to one Sm(2), two equivalent Sm(3), one Cu(1), one Cu(2), and two equivalent Cu(5) atoms. In the fourth Te site, Te(4) is bonded in a 5-coordinate geometry to one Sm(1), two equivalent Sm(4), one Cu(1), and one Cu(2) atom. In the fifth Te site, Te(5) is bonded in a 6-coordinate geometry to two equivalent K(2), two equivalent Sm(2), one Cu(4), and one Cu(5) atom. In the sixth Te site, Te(6) is bonded in a 7-coordinate geometry to two equivalent K(1), two equivalent K(3), two equivalent Sm(1), and one Cu(3) atom. In the seventh Te site, Te(7) is bonded in a 7-coordinate geometry to two equivalent K(2), two equivalent K(3), two equivalent Sm(3), and one Cu(3) atom. In the eighth Te site, Te(8) is bonded in a 7-coordinate geometry to two equivalent K(1), two equivalent K(3), two equivalent Sm(4), and one Cu(4) atom. In the ninth Te site, Te(9) is bonded to two equivalent K(2), one Sm(1), one Sm(3), one Cu(5), and two equivalent Cu(3) atoms to form distorted TeK2Sm2Cu3 pentagonal bipyramids that share  a cornercorner with one Te(2)KSm3Cu2 pentagonal pyramid, edges with two equivalent Te(9)K2Sm2Cu3 pentagonal bipyramids, and edges with two equivalent Te(2)KSm3Cu2 pentagonal pyramids. In the tenth Te site, Te(10) is bonded in a 6-coordinate geometry to two equivalent K(1), one Sm(2), one Sm(4), and two equivalent Cu(4) atoms.
K3Sm4(CuTe2)5 crystallizes in the orthorhombic Pmn2_1 space group. There are three inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to one Te(1), two equivalent Te(10), two equivalent Te(6), and two equivalent Te(8) atoms. The K(1)-Te(1) bond length is 3.56 Å. Both K(1)-Te(10) bond lengths are 3.54 Å. Both K(1)-Te(6) bond lengths are 3.68 Å. Both K(1)-Te(8) bond lengths are 3.86 Å. In the second K site, K(2) is bonded in a 9-coordinate geometry to two equivalent Cu(5), one Te(2), two equivalent Te(5), two equivalent Te(7), and two equivalent Te(9) atoms. Both K(2)-Cu(5) bond lengths are 3.76 Å. The K(2)-Te(2) bond length is 3.48 Å. Both K(2)-Te(5) bond lengths are 3.56 Å. Both K(2)-Te(7) bond lengths are 3.70 Å. Both K(2)-Te(9) bond lengths are 3.52 Å. In the third K site, K(3) is bonded in a 6-coordinate geometry to two equivalent Te(6), two equivalent Te(7), and two equivalent Te(8) atoms. Both K(3)-Te(6) bond lengths are 3.86 Å. Both K(3)-Te(7) bond lengths are 3.56 Å. Both K(3)-Te(8) bond lengths are 3.53 Å. There are four inequivalent Sm sites. In the first Sm site, Sm(1) is bonded in a 7-coordinate geometry to one Cu(1), one Te(4), one Te(9), two equivalent Te(2), and two equivalent Te(6) atoms. The Sm(1)-Cu(1) bond length is 3.14 Å. The Sm(1)-Te(4) bond length is 3.21 Å. The Sm(1)-Te(9) bond length is 3.12 Å. Both Sm(1)-Te(2) bond lengths are 3.19 Å. Both Sm(1)-Te(6) bond lengths are 3.06 Å. In the second Sm site, Sm(2) is bonded in a 11-coordinate geometry to one Cu(2), two equivalent Cu(4), two equivalent Cu(5), one Te(10), one Te(3), two equivalent Te(1), and two equivalent Te(5) atoms. The Sm(2)-Cu(2) bond length is 3.14 Å. Both Sm(2)-Cu(4) bond lengths are 3.56 Å. Both Sm(2)-Cu(5) bond lengths are 3.49 Å. The Sm(2)-Te(10) bond length is 2.99 Å. The Sm(2)-Te(3) bond length is 3.16 Å. Both Sm(2)-Te(1) bond lengths are 3.18 Å. Both Sm(2)-Te(5) bond lengths are 3.10 Å. In the third Sm site, Sm(3) is bonded in a 7-coordinate geometry to one Cu(5), one Te(2), one Te(9), two equivalent Te(3), and two equivalent Te(7) atoms. The Sm(3)-Cu(5) bond length is 3.19 Å. The Sm(3)-Te(2) bond length is 3.08 Å. The Sm(3)-Te(9) bond length is 3.05 Å. Both Sm(3)-Te(3) bond lengths are 3.24 Å. Both Sm(3)-Te(7) bond lengths are 3.05 Å. In the fourth Sm site, Sm(4) is bonded to two equivalent Cu(2), one Te(1), one Te(10), two equivalent Te(4), and two equivalent Te(8) atoms to form SmCu2Te6 octahedra that share corners with two equivalent Te(1)KSm3Cu2 pentagonal pyramids,  an edgeedge with one Te(1)KSm3Cu2 pentagonal pyramid, edges with two equivalent Cu(4)Sm2Te4 tetrahedra, and faces with two equivalent Sm(4)Cu2Te6 octahedra. Both Sm(4)-Cu(2) bond lengths are 3.68 Å. The Sm(4)-Te(1) bond length is 3.12 Å. The Sm(4)-Te(10) bond length is 3.06 Å. Both Sm(4)-Te(4) bond lengths are 3.16 Å. Both Sm(4)-Te(8) bond lengths are 3.11 Å. There are five inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 6-coordinate geometry to one Sm(1), one Cu(2), one Te(3), one Te(4), and two equivalent Te(2) atoms. The Cu(1)-Cu(2) bond length is 2.55 Å. The Cu(1)-Te(3) bond length is 2.64 Å. The Cu(1)-Te(4) bond length is 2.67 Å. Both Cu(1)-Te(2) bond lengths are 2.67 Å. In the second Cu site, Cu(2) is bonded in a 8-coordinate geometry to one Sm(2), two equivalent Sm(4), one Cu(1), one Te(3), one Te(4), and two equivalent Te(1) atoms. The Cu(2)-Te(3) bond length is 2.75 Å. The Cu(2)-Te(4) bond length is 2.60 Å. Both Cu(2)-Te(1) bond lengths are 2.66 Å. In the third Cu site, Cu(3) is bonded to one Te(6), one Te(7), and two equivalent Te(9) atoms to form distorted corner-sharing CuTe4 tetrahedra. The Cu(3)-Te(6) bond length is 2.66 Å. The Cu(3)-Te(7) bond length is 2.67 Å. Both Cu(3)-Te(9) bond lengths are 2.72 Å. In the fourth Cu site, Cu(4) is bonded to two equivalent Sm(2), one Te(5), one Te(8), and two equivalent Te(10) atoms to form distorted CuSm2Te4 tetrahedra that share corners with two equivalent Te(1)KSm3Cu2 pentagonal pyramids, edges with two equivalent Sm(4)Cu2Te6 octahedra,  an edgeedge with one Te(1)KSm3Cu2 pentagonal pyramid, and edges with two equivalent Cu(4)Sm2Te4 tetrahedra. The Cu(4)-Te(5) bond length is 2.83 Å. The Cu(4)-Te(8) bond length is 2.63 Å. Both Cu(4)-Te(10) bond lengths are 2.68 Å. In the fifth Cu site, Cu(5) is bonded in a 9-coordinate geometry to two equivalent K(2), one Sm(3), two equivalent Sm(2), one Te(5), one Te(9), and two equivalent Te(3) atoms. The Cu(5)-Te(5) bond length is 2.64 Å. The Cu(5)-Te(9) bond length is 2.83 Å. Both Cu(5)-Te(3) bond lengths are 2.69 Å. There are ten inequivalent Te sites. In the first Te site, Te(1) is bonded to one K(1), one Sm(4), two equivalent Sm(2), and two equivalent Cu(2) atoms to form distorted TeKSm3Cu2 pentagonal pyramids that share corners with two equivalent Sm(4)Cu2Te6 octahedra, corners with two equivalent Cu(4)Sm2Te4 tetrahedra,  an edgeedge with one Sm(4)Cu2Te6 octahedra, edges with two equivalent Te(1)KSm3Cu2 pentagonal pyramids, and  an edgeedge with one Cu(4)Sm2Te4 tetrahedra. The corner-sharing octahedral tilt angles are 66°. In the second Te site, Te(2) is bonded to one K(2), one Sm(3), two equivalent Sm(1), and two equivalent Cu(1) atoms to form distorted TeKSm3Cu2 pentagonal pyramids that share  a cornercorner with one Te(9)K2Sm2Cu3 pentagonal bipyramid, edges with two equivalent Te(9)K2Sm2Cu3 pentagonal bipyramids, and edges with two equivalent Te(2)KSm3Cu2 pentagonal pyramids. In the third Te site, Te(3) is bonded in a 7-coordinate geometry to one Sm(2), two equivalent Sm(3), one Cu(1), one Cu(2), and two equivalent Cu(5) atoms. In the fourth Te site, Te(4) is bonded in a 5-coordinate geometry to one Sm(1), two equivalent Sm(4), one Cu(1), and one Cu(2) atom. In the fifth Te site, Te(5) is bonded in a 6-coordinate geometry to two equivalent K(2), two equivalent Sm(2), one Cu(4), and one Cu(5) atom. In the sixth Te site, Te(6) is bonded in a 7-coordinate geometry to two equivalent K(1), two equivalent K(3), two equivalent Sm(1), and one Cu(3) atom. In the seventh Te site, Te(7) is bonded in a 7-coordinate geometry to two equivalent K(2), two equivalent K(3), two equivalent Sm(3), and one Cu(3) atom. In the eighth Te site, Te(8) is bonded in a 7-coordinate geometry to two equivalent K(1), two equivalent K(3), two equivalent Sm(4), and one Cu(4) atom. In the ninth Te site, Te(9) is bonded to two equivalent K(2), one Sm(1), one Sm(3), one Cu(5), and two equivalent Cu(3) atoms to form distorted TeK2Sm2Cu3 pentagonal bipyramids that share  a cornercorner with one Te(2)KSm3Cu2 pentagonal pyramid, edges with two equivalent Te(9)K2Sm2Cu3 pentagonal bipyramids, and edges with two equivalent Te(2)KSm3Cu2 pentagonal pyramids. In the tenth Te site, Te(10) is bonded in a 6-coordinate geometry to two equivalent K(1), one Sm(2), one Sm(4), and two equivalent Cu(4) atoms.