Cs3Tb7Te12 crystallizes in the orthorhombic Pmn2_1 space group. There are three inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 7-coordinate geometry to one Te(7), two equivalent Te(10), two equivalent Te(12), and two equivalent Te(6) atoms. In the second Cs site, Cs(2) is bonded in a 7-coordinate geometry to one Te(8), two equivalent Te(11), two equivalent Te(5), and two equivalent Te(9) atoms. In the third Cs site, Cs(3) is bonded in a 6-coordinate geometry to one Te(5), one Te(9), two equivalent Te(1), and two equivalent Te(2) atoms. There are seven inequivalent Tb sites. In the first Tb site, Tb(1) is bonded to one Te(1), one Te(11), two equivalent Te(3), and two equivalent Te(6) atoms to form a mixture of edge and corner-sharing TbTe6 octahedra. The corner-sharing octahedral tilt angles are 1°. In the second Tb site, Tb(2) is bonded to one Te(12), one Te(2), two equivalent Te(4), and two equivalent Te(5) atoms to form a mixture of edge and corner-sharing TbTe6 octahedra. The corner-sharing octahedral tilt angles are 1°. In the third Tb site, Tb(3) is bonded to one Te(7), one Te(8), two equivalent Te(10), and two equivalent Te(9) atoms to form a mixture of edge and corner-sharing TbTe6 octahedra. The corner-sharing octahedral tilt angles are 10°. In the fourth Tb site, Tb(4) is bonded to one Te(3), one Te(9), two equivalent Te(1), and two equivalent Te(7) atoms to form edge-sharing TbTe6 octahedra. In the fifth Tb site, Tb(5) is bonded to one Te(10), one Te(4), two equivalent Te(2), and two equivalent Te(8) atoms to form edge-sharing TbTe6 octahedra. In the sixth Tb site, Tb(6) is bonded to one Te(5), one Te(7), two equivalent Te(12), and two equivalent Te(3) atoms to form a mixture of edge and corner-sharing TbTe6 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. In the seventh Tb site, Tb(7) is bonded to one Te(6), one Te(8), two equivalent Te(11), and two equivalent Te(4) atoms to form a mixture of edge and corner-sharing TbTe6 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. There are twelve inequivalent Te sites. In the first Te site, Te(1) is bonded to two equivalent Cs(3), one Tb(1), and two equivalent Tb(4) atoms to form distorted TeCs2Tb3 trigonal bipyramids that share  a cornercorner with one Te(11)Cs2Tb3 trigonal bipyramid, corners with two equivalent Te(2)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(6)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(7)CsTb4 trigonal bipyramids, edges with two equivalent Te(3)Tb5 square pyramids,  an edgeedge with one Te(2)Cs2Tb3 trigonal bipyramid,  an edgeedge with one Te(7)CsTb4 trigonal bipyramid, and edges with two equivalent Te(1)Cs2Tb3 trigonal bipyramids. In the second Te site, Te(2) is bonded to two equivalent Cs(3), one Tb(2), and two equivalent Tb(5) atoms to form distorted TeCs2Tb3 trigonal bipyramids that share  a cornercorner with one Te(12)Cs2Tb3 trigonal bipyramid, corners with two equivalent Te(1)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(10)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(8)CsTb4 trigonal bipyramids, edges with two equivalent Te(4)Tb5 square pyramids,  an edgeedge with one Te(1)Cs2Tb3 trigonal bipyramid,  an edgeedge with one Te(8)CsTb4 trigonal bipyramid, and edges with two equivalent Te(2)Cs2Tb3 trigonal bipyramids. In the third Te site, Te(3) is bonded to one Tb(4), two equivalent Tb(1), and two equivalent Tb(6) atoms to form TeTb5 square pyramids that share corners with two equivalent Te(11)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(12)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(6)Cs2Tb3 trigonal bipyramids, edges with two equivalent Te(3)Tb5 square pyramids,  an edgeedge with one Te(12)Cs2Tb3 trigonal bipyramid,  an edgeedge with one Te(6)Cs2Tb3 trigonal bipyramid, edges with two equivalent Te(1)Cs2Tb3 trigonal bipyramids, and edges with two equivalent Te(7)CsTb4 trigonal bipyramids. In the fourth Te site, Te(4) is bonded to one Tb(5), two equivalent Tb(2), and two equivalent Tb(7) atoms to form TeTb5 square pyramids that share  a cornercorner with one Te(10)Cs2Tb3 trigonal bipyramid, corners with two equivalent Te(11)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(12)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(6)Cs2Tb3 trigonal bipyramids, edges with two equivalent Te(4)Tb5 square pyramids,  an edgeedge with one Te(11)Cs2Tb3 trigonal bipyramid, edges with two equivalent Te(2)Cs2Tb3 trigonal bipyramids, and edges with two equivalent Te(8)CsTb4 trigonal bipyramids. In the fifth Te site, Te(5) is bonded in a 6-coordinate geometry to one Cs(3), two equivalent Cs(2), one Tb(6), and two equivalent Tb(2) atoms. In the sixth Te site, Te(6) is bonded to two equivalent Cs(1), one Tb(7), and two equivalent Tb(1) atoms to form distorted TeCs2Tb3 trigonal bipyramids that share corners with two equivalent Te(3)Tb5 square pyramids, corners with two equivalent Te(4)Tb5 square pyramids,  a cornercorner with one Te(8)CsTb4 trigonal bipyramid, corners with two equivalent Te(1)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(10)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(12)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(7)CsTb4 trigonal bipyramids,  an edgeedge with one Te(3)Tb5 square pyramid,  an edgeedge with one Te(10)Cs2Tb3 trigonal bipyramid,  an edgeedge with one Te(12)Cs2Tb3 trigonal bipyramid, edges with two equivalent Te(11)Cs2Tb3 trigonal bipyramids, and edges with two equivalent Te(6)Cs2Tb3 trigonal bipyramids. In the seventh Te site, Te(7) is bonded to one Cs(1), one Tb(3), one Tb(6), and two equivalent Tb(4) atoms to form distorted TeCsTb4 trigonal bipyramids that share  a cornercorner with one Te(8)CsTb4 trigonal bipyramid, corners with two equivalent Te(1)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(6)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(7)CsTb4 trigonal bipyramids, edges with two equivalent Te(3)Tb5 square pyramids,  an edgeedge with one Te(1)Cs2Tb3 trigonal bipyramid, edges with two equivalent Te(10)Cs2Tb3 trigonal bipyramids, and edges with two equivalent Te(12)Cs2Tb3 trigonal bipyramids. In the eighth Te site, Te(8) is bonded to one Cs(2), one Tb(3), one Tb(7), and two equivalent Tb(5) atoms to form distorted TeCsTb4 trigonal bipyramids that share  a cornercorner with one Te(6)Cs2Tb3 trigonal bipyramid,  a cornercorner with one Te(7)CsTb4 trigonal bipyramid, corners with two equivalent Te(2)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(8)CsTb4 trigonal bipyramids, edges with two equivalent Te(4)Tb5 square pyramids,  an edgeedge with one Te(2)Cs2Tb3 trigonal bipyramid, edges with two equivalent Te(10)Cs2Tb3 trigonal bipyramids, and edges with two equivalent Te(11)Cs2Tb3 trigonal bipyramids. In the ninth Te site, Te(9) is bonded in a 6-coordinate geometry to one Cs(3), two equivalent Cs(2), one Tb(4), and two equivalent Tb(3) atoms. In the tenth Te site, Te(10) is bonded to two equivalent Cs(1), one Tb(5), and two equivalent Tb(3) atoms to form distorted TeCs2Tb3 trigonal bipyramids that share  a cornercorner with one Te(4)Tb5 square pyramid, corners with two equivalent Te(12)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(2)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(6)Cs2Tb3 trigonal bipyramids,  an edgeedge with one Te(12)Cs2Tb3 trigonal bipyramid,  an edgeedge with one Te(6)Cs2Tb3 trigonal bipyramid, edges with two equivalent Te(10)Cs2Tb3 trigonal bipyramids, edges with two equivalent Te(7)CsTb4 trigonal bipyramids, and edges with two equivalent Te(8)CsTb4 trigonal bipyramids. In the eleventh Te site, Te(11) is bonded to two equivalent Cs(2), one Tb(1), and two equivalent Tb(7) atoms to form distorted TeCs2Tb3 trigonal bipyramids that share corners with two equivalent Te(3)Tb5 square pyramids, corners with two equivalent Te(4)Tb5 square pyramids,  a cornercorner with one Te(1)Cs2Tb3 trigonal bipyramid,  an edgeedge with one Te(4)Tb5 square pyramid, edges with two equivalent Te(11)Cs2Tb3 trigonal bipyramids, edges with two equivalent Te(6)Cs2Tb3 trigonal bipyramids, and edges with two equivalent Te(8)CsTb4 trigonal bipyramids. In the twelfth Te site, Te(12) is bonded to two equivalent Cs(1), one Tb(2), and two equivalent Tb(6) atoms to form distorted TeCs2Tb3 trigonal bipyramids that share corners with two equivalent Te(3)Tb5 square pyramids, corners with two equivalent Te(4)Tb5 square pyramids,  a cornercorner with one Te(2)Cs2Tb3 trigonal bipyramid, corners with two equivalent Te(10)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(6)Cs2Tb3 trigonal bipyramids,  an edgeedge with one Te(3)Tb5 square pyramid,  an edgeedge with one Te(10)Cs2Tb3 trigonal bipyramid,  an edgeedge with one Te(6)Cs2Tb3 trigonal bipyramid, edges with two equivalent Te(12)Cs2Tb3 trigonal bipyramids, and edges with two equivalent Te(7)CsTb4 trigonal bipyramids.
Cs3Tb7Te12 crystallizes in the orthorhombic Pmn2_1 space group. There are three inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 7-coordinate geometry to one Te(7), two equivalent Te(10), two equivalent Te(12), and two equivalent Te(6) atoms. The Cs(1)-Te(7) bond length is 3.98 Å. Both Cs(1)-Te(10) bond lengths are 3.96 Å. Both Cs(1)-Te(12) bond lengths are 3.90 Å. Both Cs(1)-Te(6) bond lengths are 3.91 Å. In the second Cs site, Cs(2) is bonded in a 7-coordinate geometry to one Te(8), two equivalent Te(11), two equivalent Te(5), and two equivalent Te(9) atoms. The Cs(2)-Te(8) bond length is 3.89 Å. Both Cs(2)-Te(11) bond lengths are 3.78 Å. Both Cs(2)-Te(5) bond lengths are 3.91 Å. Both Cs(2)-Te(9) bond lengths are 4.02 Å. In the third Cs site, Cs(3) is bonded in a 6-coordinate geometry to one Te(5), one Te(9), two equivalent Te(1), and two equivalent Te(2) atoms. The Cs(3)-Te(5) bond length is 4.42 Å. The Cs(3)-Te(9) bond length is 3.92 Å. Both Cs(3)-Te(1) bond lengths are 3.83 Å. Both Cs(3)-Te(2) bond lengths are 3.73 Å. There are seven inequivalent Tb sites. In the first Tb site, Tb(1) is bonded to one Te(1), one Te(11), two equivalent Te(3), and two equivalent Te(6) atoms to form a mixture of edge and corner-sharing TbTe6 octahedra. The corner-sharing octahedral tilt angles are 1°. The Tb(1)-Te(1) bond length is 3.05 Å. The Tb(1)-Te(11) bond length is 3.03 Å. Both Tb(1)-Te(3) bond lengths are 3.23 Å. Both Tb(1)-Te(6) bond lengths are 3.06 Å. In the second Tb site, Tb(2) is bonded to one Te(12), one Te(2), two equivalent Te(4), and two equivalent Te(5) atoms to form a mixture of edge and corner-sharing TbTe6 octahedra. The corner-sharing octahedral tilt angles are 1°. The Tb(2)-Te(12) bond length is 3.04 Å. The Tb(2)-Te(2) bond length is 3.06 Å. Both Tb(2)-Te(4) bond lengths are 3.20 Å. Both Tb(2)-Te(5) bond lengths are 3.07 Å. In the third Tb site, Tb(3) is bonded to one Te(7), one Te(8), two equivalent Te(10), and two equivalent Te(9) atoms to form a mixture of edge and corner-sharing TbTe6 octahedra. The corner-sharing octahedral tilt angles are 10°. The Tb(3)-Te(7) bond length is 3.07 Å. The Tb(3)-Te(8) bond length is 3.07 Å. Both Tb(3)-Te(10) bond lengths are 3.10 Å. Both Tb(3)-Te(9) bond lengths are 3.13 Å. In the fourth Tb site, Tb(4) is bonded to one Te(3), one Te(9), two equivalent Te(1), and two equivalent Te(7) atoms to form edge-sharing TbTe6 octahedra. The Tb(4)-Te(3) bond length is 3.20 Å. The Tb(4)-Te(9) bond length is 3.07 Å. Both Tb(4)-Te(1) bond lengths are 3.10 Å. Both Tb(4)-Te(7) bond lengths are 3.10 Å. In the fifth Tb site, Tb(5) is bonded to one Te(10), one Te(4), two equivalent Te(2), and two equivalent Te(8) atoms to form edge-sharing TbTe6 octahedra. The Tb(5)-Te(10) bond length is 3.03 Å. The Tb(5)-Te(4) bond length is 3.24 Å. Both Tb(5)-Te(2) bond lengths are 3.08 Å. Both Tb(5)-Te(8) bond lengths are 3.10 Å. In the sixth Tb site, Tb(6) is bonded to one Te(5), one Te(7), two equivalent Te(12), and two equivalent Te(3) atoms to form a mixture of edge and corner-sharing TbTe6 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. The Tb(6)-Te(5) bond length is 3.12 Å. The Tb(6)-Te(7) bond length is 3.08 Å. Both Tb(6)-Te(12) bond lengths are 3.04 Å. Both Tb(6)-Te(3) bond lengths are 3.19 Å. In the seventh Tb site, Tb(7) is bonded to one Te(6), one Te(8), two equivalent Te(11), and two equivalent Te(4) atoms to form a mixture of edge and corner-sharing TbTe6 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. The Tb(7)-Te(6) bond length is 3.08 Å. The Tb(7)-Te(8) bond length is 3.09 Å. Both Tb(7)-Te(11) bond lengths are 3.04 Å. Both Tb(7)-Te(4) bond lengths are 3.18 Å. There are twelve inequivalent Te sites. In the first Te site, Te(1) is bonded to two equivalent Cs(3), one Tb(1), and two equivalent Tb(4) atoms to form distorted TeCs2Tb3 trigonal bipyramids that share  a cornercorner with one Te(11)Cs2Tb3 trigonal bipyramid, corners with two equivalent Te(2)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(6)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(7)CsTb4 trigonal bipyramids, edges with two equivalent Te(3)Tb5 square pyramids,  an edgeedge with one Te(2)Cs2Tb3 trigonal bipyramid,  an edgeedge with one Te(7)CsTb4 trigonal bipyramid, and edges with two equivalent Te(1)Cs2Tb3 trigonal bipyramids. In the second Te site, Te(2) is bonded to two equivalent Cs(3), one Tb(2), and two equivalent Tb(5) atoms to form distorted TeCs2Tb3 trigonal bipyramids that share  a cornercorner with one Te(12)Cs2Tb3 trigonal bipyramid, corners with two equivalent Te(1)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(10)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(8)CsTb4 trigonal bipyramids, edges with two equivalent Te(4)Tb5 square pyramids,  an edgeedge with one Te(1)Cs2Tb3 trigonal bipyramid,  an edgeedge with one Te(8)CsTb4 trigonal bipyramid, and edges with two equivalent Te(2)Cs2Tb3 trigonal bipyramids. In the third Te site, Te(3) is bonded to one Tb(4), two equivalent Tb(1), and two equivalent Tb(6) atoms to form TeTb5 square pyramids that share corners with two equivalent Te(11)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(12)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(6)Cs2Tb3 trigonal bipyramids, edges with two equivalent Te(3)Tb5 square pyramids,  an edgeedge with one Te(12)Cs2Tb3 trigonal bipyramid,  an edgeedge with one Te(6)Cs2Tb3 trigonal bipyramid, edges with two equivalent Te(1)Cs2Tb3 trigonal bipyramids, and edges with two equivalent Te(7)CsTb4 trigonal bipyramids. In the fourth Te site, Te(4) is bonded to one Tb(5), two equivalent Tb(2), and two equivalent Tb(7) atoms to form TeTb5 square pyramids that share  a cornercorner with one Te(10)Cs2Tb3 trigonal bipyramid, corners with two equivalent Te(11)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(12)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(6)Cs2Tb3 trigonal bipyramids, edges with two equivalent Te(4)Tb5 square pyramids,  an edgeedge with one Te(11)Cs2Tb3 trigonal bipyramid, edges with two equivalent Te(2)Cs2Tb3 trigonal bipyramids, and edges with two equivalent Te(8)CsTb4 trigonal bipyramids. In the fifth Te site, Te(5) is bonded in a 6-coordinate geometry to one Cs(3), two equivalent Cs(2), one Tb(6), and two equivalent Tb(2) atoms. In the sixth Te site, Te(6) is bonded to two equivalent Cs(1), one Tb(7), and two equivalent Tb(1) atoms to form distorted TeCs2Tb3 trigonal bipyramids that share corners with two equivalent Te(3)Tb5 square pyramids, corners with two equivalent Te(4)Tb5 square pyramids,  a cornercorner with one Te(8)CsTb4 trigonal bipyramid, corners with two equivalent Te(1)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(10)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(12)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(7)CsTb4 trigonal bipyramids,  an edgeedge with one Te(3)Tb5 square pyramid,  an edgeedge with one Te(10)Cs2Tb3 trigonal bipyramid,  an edgeedge with one Te(12)Cs2Tb3 trigonal bipyramid, edges with two equivalent Te(11)Cs2Tb3 trigonal bipyramids, and edges with two equivalent Te(6)Cs2Tb3 trigonal bipyramids. In the seventh Te site, Te(7) is bonded to one Cs(1), one Tb(3), one Tb(6), and two equivalent Tb(4) atoms to form distorted TeCsTb4 trigonal bipyramids that share  a cornercorner with one Te(8)CsTb4 trigonal bipyramid, corners with two equivalent Te(1)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(6)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(7)CsTb4 trigonal bipyramids, edges with two equivalent Te(3)Tb5 square pyramids,  an edgeedge with one Te(1)Cs2Tb3 trigonal bipyramid, edges with two equivalent Te(10)Cs2Tb3 trigonal bipyramids, and edges with two equivalent Te(12)Cs2Tb3 trigonal bipyramids. In the eighth Te site, Te(8) is bonded to one Cs(2), one Tb(3), one Tb(7), and two equivalent Tb(5) atoms to form distorted TeCsTb4 trigonal bipyramids that share  a cornercorner with one Te(6)Cs2Tb3 trigonal bipyramid,  a cornercorner with one Te(7)CsTb4 trigonal bipyramid, corners with two equivalent Te(2)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(8)CsTb4 trigonal bipyramids, edges with two equivalent Te(4)Tb5 square pyramids,  an edgeedge with one Te(2)Cs2Tb3 trigonal bipyramid, edges with two equivalent Te(10)Cs2Tb3 trigonal bipyramids, and edges with two equivalent Te(11)Cs2Tb3 trigonal bipyramids. In the ninth Te site, Te(9) is bonded in a 6-coordinate geometry to one Cs(3), two equivalent Cs(2), one Tb(4), and two equivalent Tb(3) atoms. In the tenth Te site, Te(10) is bonded to two equivalent Cs(1), one Tb(5), and two equivalent Tb(3) atoms to form distorted TeCs2Tb3 trigonal bipyramids that share  a cornercorner with one Te(4)Tb5 square pyramid, corners with two equivalent Te(12)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(2)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(6)Cs2Tb3 trigonal bipyramids,  an edgeedge with one Te(12)Cs2Tb3 trigonal bipyramid,  an edgeedge with one Te(6)Cs2Tb3 trigonal bipyramid, edges with two equivalent Te(10)Cs2Tb3 trigonal bipyramids, edges with two equivalent Te(7)CsTb4 trigonal bipyramids, and edges with two equivalent Te(8)CsTb4 trigonal bipyramids. In the eleventh Te site, Te(11) is bonded to two equivalent Cs(2), one Tb(1), and two equivalent Tb(7) atoms to form distorted TeCs2Tb3 trigonal bipyramids that share corners with two equivalent Te(3)Tb5 square pyramids, corners with two equivalent Te(4)Tb5 square pyramids,  a cornercorner with one Te(1)Cs2Tb3 trigonal bipyramid,  an edgeedge with one Te(4)Tb5 square pyramid, edges with two equivalent Te(11)Cs2Tb3 trigonal bipyramids, edges with two equivalent Te(6)Cs2Tb3 trigonal bipyramids, and edges with two equivalent Te(8)CsTb4 trigonal bipyramids. In the twelfth Te site, Te(12) is bonded to two equivalent Cs(1), one Tb(2), and two equivalent Tb(6) atoms to form distorted TeCs2Tb3 trigonal bipyramids that share corners with two equivalent Te(3)Tb5 square pyramids, corners with two equivalent Te(4)Tb5 square pyramids,  a cornercorner with one Te(2)Cs2Tb3 trigonal bipyramid, corners with two equivalent Te(10)Cs2Tb3 trigonal bipyramids, corners with two equivalent Te(6)Cs2Tb3 trigonal bipyramids,  an edgeedge with one Te(3)Tb5 square pyramid,  an edgeedge with one Te(10)Cs2Tb3 trigonal bipyramid,  an edgeedge with one Te(6)Cs2Tb3 trigonal bipyramid, edges with two equivalent Te(12)Cs2Tb3 trigonal bipyramids, and edges with two equivalent Te(7)CsTb4 trigonal bipyramids.