CsBi4Te6 crystallizes in the triclinic P1 space group. There are four inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 9-coordinate geometry to one Te(18), one Te(8), one Te(9), two equivalent Te(21), two equivalent Te(3), and two equivalent Te(7) atoms. In the second Cs site, Cs(2) is bonded in a 10-coordinate geometry to one Te(21), one Te(5), two equivalent Te(11), two equivalent Te(18), two equivalent Te(20), and two equivalent Te(24) atoms. In the third Cs site, Cs(3) is bonded in a 10-coordinate geometry to one Te(13), one Te(6), two equivalent Te(14), two equivalent Te(15), two equivalent Te(20), and two equivalent Te(24) atoms. In the fourth Cs site, Cs(4) is bonded in a 9-coordinate geometry to one Te(1), one Te(15), one Te(3), two equivalent Te(23), two equivalent Te(6), and two equivalent Te(9) atoms. There are sixteen inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one Te(10), one Te(22), two equivalent Te(17), and two equivalent Te(8) atoms to form BiTe6 octahedra that share  a cornercorner with one Bi(11)BiTe5 octahedra,  a cornercorner with one Bi(16)Te6 octahedra, corners with two equivalent Bi(9)Te6 octahedra,  an edgeedge with one Bi(9)Te6 octahedra, edges with two equivalent Bi(1)Te6 octahedra, edges with two equivalent Bi(13)Te6 octahedra, edges with two equivalent Bi(14)Te6 octahedra, edges with two equivalent Bi(2)Te6 octahedra, and edges with two equivalent Bi(6)Te6 octahedra. The corner-sharing octahedral tilt angles are 7°. In the second Bi site, Bi(2) is bonded to one Te(16), one Te(17), two equivalent Te(22), and two equivalent Te(7) atoms to form a mixture of corner and edge-sharing BiTe6 octahedra. The corner-sharing octahedral tilt angles range from 2-7°. In the third Bi site, Bi(3) is bonded to one Te(12), one Te(19), two equivalent Te(13), and two equivalent Te(4) atoms to form BiTe6 octahedra that share  a cornercorner with one Bi(16)Te6 octahedra, corners with two equivalent Bi(15)Te6 octahedra,  an edgeedge with one Bi(15)Te6 octahedra, edges with two equivalent Bi(12)BiTe5 octahedra, edges with two equivalent Bi(4)BiTe5 octahedra, edges with two equivalent Bi(3)Te6 octahedra, edges with two equivalent Bi(5)Te6 octahedra, and edges with two equivalent Bi(8)Te6 octahedra. The corner-sharing octahedral tilt angles range from 2-6°. In the fourth Bi site, Bi(4) is bonded to one Bi(7), one Te(4), two equivalent Te(14), and two equivalent Te(19) atoms to form distorted BiBiTe5 octahedra that share  a cornercorner with one Bi(8)Te6 octahedra, corners with two equivalent Bi(12)BiTe5 octahedra, corners with two equivalent Te(20)Cs4Bi2 pentagonal pyramids, corners with two equivalent Te(2)Bi5 square pyramids,  a cornercorner with one Te(5)CsBi4 trigonal bipyramid,  an edgeedge with one Bi(12)BiTe5 octahedra, edges with two equivalent Bi(4)BiTe5 octahedra, edges with two equivalent Bi(15)Te6 octahedra, and edges with two equivalent Bi(3)Te6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. In the fifth Bi site, Bi(5) is bonded to one Te(13), one Te(23), two equivalent Te(12), and two equivalent Te(15) atoms to form BiTe6 octahedra that share  a cornercorner with one Bi(12)BiTe5 octahedra,  a cornercorner with one Bi(13)Te6 octahedra, corners with two equivalent Bi(8)Te6 octahedra,  an edgeedge with one Bi(8)Te6 octahedra, edges with two equivalent Bi(16)Te6 octahedra, edges with two equivalent Bi(3)Te6 octahedra, and edges with two equivalent Bi(5)Te6 octahedra. The corner-sharing octahedral tilt angles range from 7-10°. In the sixth Bi site, Bi(6) is bonded to one Te(17), one Te(2), two equivalent Te(10), and two equivalent Te(5) atoms to form BiTe6 octahedra that share  a cornercorner with one Bi(2)Te6 octahedra, corners with two equivalent Bi(14)Te6 octahedra,  an edgeedge with one Bi(14)Te6 octahedra, edges with two equivalent Bi(11)BiTe5 octahedra, edges with two equivalent Bi(7)BiTe5 octahedra, edges with two equivalent Bi(1)Te6 octahedra, edges with two equivalent Bi(6)Te6 octahedra, and edges with two equivalent Bi(9)Te6 octahedra. The corner-sharing octahedral tilt angles range from 2-7°. In the seventh Bi site, Bi(7) is bonded to one Bi(4), one Te(5), two equivalent Te(2), and two equivalent Te(20) atoms to form distorted BiBiTe5 octahedra that share  a cornercorner with one Bi(9)Te6 octahedra,  a cornercorner with one Te(4)Bi6 octahedra, corners with two equivalent Bi(11)BiTe5 octahedra, corners with two equivalent Te(19)Bi5 square pyramids, corners with two equivalent Te(14)Cs2Bi3 square pyramids,  an edgeedge with one Bi(11)BiTe5 octahedra, edges with two equivalent Bi(7)BiTe5 octahedra, and edges with two equivalent Bi(6)Te6 octahedra. The corner-sharing octahedral tilt angles range from 9-10°. In the eighth Bi site, Bi(8) is bonded to one Te(16), one Te(4), two equivalent Te(1), and two equivalent Te(12) atoms to form BiTe6 octahedra that share  a cornercorner with one Bi(4)BiTe5 octahedra,  a cornercorner with one Bi(2)Te6 octahedra, corners with two equivalent Bi(5)Te6 octahedra,  an edgeedge with one Bi(5)Te6 octahedra, edges with two equivalent Bi(10)Te6 octahedra, edges with two equivalent Bi(15)Te6 octahedra, edges with two equivalent Bi(16)Te6 octahedra, edges with two equivalent Bi(3)Te6 octahedra, and edges with two equivalent Bi(8)Te6 octahedra. The corner-sharing octahedral tilt angles range from 6-7°. In the ninth Bi site, Bi(9) is bonded to one Te(5), one Te(7), two equivalent Te(17), and two equivalent Te(18) atoms to form BiTe6 octahedra that share  a cornercorner with one Bi(7)BiTe5 octahedra,  a cornercorner with one Bi(10)Te6 octahedra, corners with two equivalent Bi(1)Te6 octahedra,  an edgeedge with one Bi(1)Te6 octahedra, edges with two equivalent Bi(2)Te6 octahedra, edges with two equivalent Bi(6)Te6 octahedra, and edges with two equivalent Bi(9)Te6 octahedra. The corner-sharing octahedral tilt angles range from 7-9°. In the tenth Bi site, Bi(10) is bonded to one Te(1), one Te(7), two equivalent Te(16), and two equivalent Te(9) atoms to form a mixture of corner and edge-sharing BiTe6 octahedra. The corner-sharing octahedral tilt angles range from 4-14°. In the eleventh Bi site, Bi(11) is bonded to one Bi(12), one Te(10), two equivalent Te(11), and two equivalent Te(2) atoms to form distorted BiBiTe5 octahedra that share  a cornercorner with one Bi(1)Te6 octahedra, corners with two equivalent Bi(7)BiTe5 octahedra, corners with two equivalent Te(24)Cs4Bi2 pentagonal pyramids, corners with two equivalent Te(19)Bi5 square pyramids,  a cornercorner with one Te(13)CsBi4 trigonal bipyramid,  an edgeedge with one Bi(7)BiTe5 octahedra, edges with two equivalent Bi(11)BiTe5 octahedra, edges with two equivalent Bi(14)Te6 octahedra, and edges with two equivalent Bi(6)Te6 octahedra. The corner-sharing octahedral tilt angles range from 7-10°. In the twelfth Bi site, Bi(12) is bonded to one Bi(11), one Te(13), two equivalent Te(19), and two equivalent Te(24) atoms to form distorted BiBiTe5 octahedra that share  a cornercorner with one Bi(5)Te6 octahedra,  a cornercorner with one Te(10)Bi6 octahedra, corners with two equivalent Bi(4)BiTe5 octahedra, corners with two equivalent Te(2)Bi5 square pyramids, corners with two equivalent Te(11)Cs2Bi3 square pyramids,  an edgeedge with one Bi(4)BiTe5 octahedra, edges with two equivalent Bi(12)BiTe5 octahedra, and edges with two equivalent Bi(3)Te6 octahedra. The corner-sharing octahedral tilt angles are 10°. In the thirteenth Bi site, Bi(13) is bonded to one Te(23), one Te(8), two equivalent Te(22), and two equivalent Te(3) atoms to form a mixture of corner and edge-sharing BiTe6 octahedra. The corner-sharing octahedral tilt angles range from 4-14°. In the fourteenth Bi site, Bi(14) is bonded to one Te(11), one Te(8), two equivalent Te(10), and two equivalent Te(21) atoms to form BiTe6 octahedra that share  a cornercorner with one Bi(13)Te6 octahedra, corners with two equivalent Bi(6)Te6 octahedra,  an edgeedge with one Bi(6)Te6 octahedra, edges with two equivalent Bi(11)BiTe5 octahedra, edges with two equivalent Bi(1)Te6 octahedra, and edges with two equivalent Bi(14)Te6 octahedra. The corner-sharing octahedral tilt angles range from 7-14°. In the fifteenth Bi site, Bi(15) is bonded to one Te(1), one Te(14), two equivalent Te(4), and two equivalent Te(6) atoms to form BiTe6 octahedra that share  a cornercorner with one Bi(10)Te6 octahedra, corners with two equivalent Bi(3)Te6 octahedra,  an edgeedge with one Bi(3)Te6 octahedra, edges with two equivalent Bi(4)BiTe5 octahedra, edges with two equivalent Bi(15)Te6 octahedra, and edges with two equivalent Bi(8)Te6 octahedra. The corner-sharing octahedral tilt angles range from 6-14°. In the sixteenth Bi site, Bi(16) is bonded to one Te(12), one Te(22), two equivalent Te(16), and two equivalent Te(23) atoms to form a mixture of corner and edge-sharing BiTe6 octahedra. The corner-sharing octahedral tilt angles range from 2-7°. There are twenty-four inequivalent Te sites. In the first Te site, Te(1) is bonded to one Cs(4), one Bi(10), one Bi(15), and two equivalent Bi(8) atoms to form TeCsBi4 trigonal bipyramids that share  a cornercorner with one Te(7)Cs2Bi4 octahedra, corners with two equivalent Te(12)Bi6 octahedra, corners with two equivalent Te(23)Cs2Bi4 octahedra,  a cornercorner with one Te(14)Cs2Bi3 square pyramid,  a cornercorner with one Te(3)Cs3Bi2 trigonal bipyramid, corners with two equivalent Te(1)CsBi4 trigonal bipyramids,  an edgeedge with one Te(12)Bi6 octahedra, edges with two equivalent Te(16)Bi6 octahedra, edges with two equivalent Te(4)Bi6 octahedra, and edges with two equivalent Te(9)Cs3Bi2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 5-34°. In the second Te site, Te(2) is bonded to one Bi(6), two equivalent Bi(11), and two equivalent Bi(7) atoms to form TeBi5 square pyramids that share  a cornercorner with one Te(17)Bi6 octahedra, corners with two equivalent Bi(12)BiTe5 octahedra, corners with two equivalent Bi(4)BiTe5 octahedra, corners with two equivalent Te(20)Cs4Bi2 pentagonal pyramids, corners with two equivalent Te(11)Cs2Bi3 square pyramids, edges with two equivalent Te(10)Bi6 octahedra,  an edgeedge with one Te(20)Cs4Bi2 pentagonal pyramid,  an edgeedge with one Te(11)Cs2Bi3 square pyramid, edges with two equivalent Te(2)Bi5 square pyramids, and edges with two equivalent Te(5)CsBi4 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 5-96°. In the third Te site, Te(3) is bonded to one Cs(4), two equivalent Cs(1), and two equivalent Bi(13) atoms to form distorted TeCs3Bi2 trigonal bipyramids that share corners with two equivalent Te(22)Bi6 octahedra, corners with two equivalent Te(7)Cs2Bi4 octahedra,  a cornercorner with one Te(1)CsBi4 trigonal bipyramid,  an edgeedge with one Te(22)Bi6 octahedra,  an edgeedge with one Te(7)Cs2Bi4 octahedra, edges with two equivalent Te(23)Cs2Bi4 octahedra, edges with two equivalent Te(3)Cs3Bi2 trigonal bipyramids, edges with two equivalent Te(9)Cs3Bi2 trigonal bipyramids, and edges with two equivalent Te(8)CsBi4 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 8-53°. In the fourth Te site, Te(4) is bonded to one Bi(4), one Bi(8), two equivalent Bi(15), and two equivalent Bi(3) atoms to form distorted TeBi6 octahedra that share  a cornercorner with one Bi(7)BiTe5 octahedra,  a cornercorner with one Te(16)Bi6 octahedra, corners with two equivalent Te(13)CsBi4 trigonal bipyramids, edges with two equivalent Te(12)Bi6 octahedra, edges with two equivalent Te(4)Bi6 octahedra, edges with two equivalent Te(19)Bi5 square pyramids, edges with two equivalent Te(14)Cs2Bi3 square pyramids,  an edgeedge with one Te(13)CsBi4 trigonal bipyramid, and edges with two equivalent Te(1)CsBi4 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 2-10°. In the fifth Te site, Te(5) is bonded to one Cs(2), one Bi(7), one Bi(9), and two equivalent Bi(6) atoms to form TeCsBi4 trigonal bipyramids that share  a cornercorner with one Bi(4)BiTe5 octahedra,  a cornercorner with one Te(7)Cs2Bi4 octahedra, corners with two equivalent Te(10)Bi6 octahedra, corners with two equivalent Te(24)Cs4Bi2 pentagonal pyramids, corners with two equivalent Te(11)Cs2Bi3 square pyramids, corners with two equivalent Te(5)CsBi4 trigonal bipyramids,  an edgeedge with one Te(10)Bi6 octahedra, edges with two equivalent Te(17)Bi6 octahedra, edges with two equivalent Te(20)Cs4Bi2 pentagonal pyramids, and edges with two equivalent Te(2)Bi5 square pyramids. The corner-sharing octahedral tilt angles range from 7-18°. In the sixth Te site, Te(6) is bonded in a 5-coordinate geometry to one Cs(3), two equivalent Cs(4), and two equivalent Bi(15) atoms. In the seventh Te site, Te(7) is bonded to two equivalent Cs(1), one Bi(10), one Bi(9), and two equivalent Bi(2) atoms to form TeCs2Bi4 octahedra that share corners with two equivalent Te(22)Bi6 octahedra,  a cornercorner with one Te(1)CsBi4 trigonal bipyramid,  a cornercorner with one Te(5)CsBi4 trigonal bipyramid, corners with two equivalent Te(3)Cs3Bi2 trigonal bipyramids, corners with two equivalent Te(8)CsBi4 trigonal bipyramids,  an edgeedge with one Te(22)Bi6 octahedra, edges with two equivalent Te(16)Bi6 octahedra, edges with two equivalent Te(17)Bi6 octahedra, edges with two equivalent Te(7)Cs2Bi4 octahedra,  an edgeedge with one Te(3)Cs3Bi2 trigonal bipyramid, and edges with two equivalent Te(9)Cs3Bi2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 2-3°. In the eighth Te site, Te(8) is bonded to one Cs(1), one Bi(13), one Bi(14), and two equivalent Bi(1) atoms to form TeCsBi4 trigonal bipyramids that share  a cornercorner with one Te(23)Cs2Bi4 octahedra, corners with two equivalent Te(17)Bi6 octahedra, corners with two equivalent Te(7)Cs2Bi4 octahedra,  a cornercorner with one Te(11)Cs2Bi3 square pyramid,  a cornercorner with one Te(9)Cs3Bi2 trigonal bipyramid, corners with two equivalent Te(8)CsBi4 trigonal bipyramids,  an edgeedge with one Te(17)Bi6 octahedra, edges with two equivalent Te(10)Bi6 octahedra, edges with two equivalent Te(22)Bi6 octahedra, and edges with two equivalent Te(3)Cs3Bi2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 5-33°. In the ninth Te site, Te(9) is bonded to one Cs(1), two equivalent Cs(4), and two equivalent Bi(10) atoms to form distorted TeCs3Bi2 trigonal bipyramids that share corners with two equivalent Te(16)Bi6 octahedra, corners with two equivalent Te(23)Cs2Bi4 octahedra,  a cornercorner with one Te(8)CsBi4 trigonal bipyramid,  an edgeedge with one Te(16)Bi6 octahedra,  an edgeedge with one Te(23)Cs2Bi4 octahedra, edges with two equivalent Te(7)Cs2Bi4 octahedra, edges with two equivalent Te(3)Cs3Bi2 trigonal bipyramids, edges with two equivalent Te(9)Cs3Bi2 trigonal bipyramids, and edges with two equivalent Te(1)CsBi4 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 9-53°. In the tenth Te site, Te(10) is bonded to one Bi(1), one Bi(11), two equivalent Bi(14), and two equivalent Bi(6) atoms to form distorted TeBi6 octahedra that share  a cornercorner with one Bi(12)BiTe5 octahedra,  a cornercorner with one Te(22)Bi6 octahedra, corners with two equivalent Te(5)CsBi4 trigonal bipyramids, edges with two equivalent Te(10)Bi6 octahedra, edges with two equivalent Te(17)Bi6 octahedra, edges with two equivalent Te(2)Bi5 square pyramids, edges with two equivalent Te(11)Cs2Bi3 square pyramids,  an edgeedge with one Te(5)CsBi4 trigonal bipyramid, and edges with two equivalent Te(8)CsBi4 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 2-10°. In the eleventh Te site, Te(11) is bonded to two equivalent Cs(2), one Bi(14), and two equivalent Bi(11) atoms to form distorted TeCs2Bi3 square pyramids that share corners with two equivalent Bi(12)BiTe5 octahedra, corners with two equivalent Te(20)Cs4Bi2 pentagonal pyramids, corners with two equivalent Te(24)Cs4Bi2 pentagonal pyramids, corners with two equivalent Te(2)Bi5 square pyramids,  a cornercorner with one Te(8)CsBi4 trigonal bipyramid, corners with two equivalent Te(5)CsBi4 trigonal bipyramids, edges with two equivalent Te(10)Bi6 octahedra,  an edgeedge with one Te(20)Cs4Bi2 pentagonal pyramid,  an edgeedge with one Te(24)Cs4Bi2 pentagonal pyramid,  an edgeedge with one Te(2)Bi5 square pyramid, and edges with two equivalent Te(11)Cs2Bi3 square pyramids. The corner-sharing octahedral tilt angles are 93°. In the twelfth Te site, Te(12) is bonded to one Bi(16), one Bi(3), two equivalent Bi(5), and two equivalent Bi(8) atoms to form TeBi6 octahedra that share  a cornercorner with one Te(22)Bi6 octahedra,  a cornercorner with one Te(19)Bi5 square pyramid, corners with two equivalent Te(1)CsBi4 trigonal bipyramids, edges with two equivalent Te(12)Bi6 octahedra, edges with two equivalent Te(16)Bi6 octahedra, edges with two equivalent Te(4)Bi6 octahedra, edges with two equivalent Te(23)Cs2Bi4 octahedra,  an edgeedge with one Te(1)CsBi4 trigonal bipyramid, and edges with two equivalent Te(13)CsBi4 trigonal bipyramids. The corner-sharing octahedral tilt angles are 8°. In the thirteenth Te site, Te(13) is bonded to one Cs(3), one Bi(12), one Bi(5), and two equivalent Bi(3) atoms to form TeCsBi4 trigonal bipyramids that share  a cornercorner with one Bi(11)BiTe5 octahedra,  a cornercorner with one Te(23)Cs2Bi4 octahedra, corners with two equivalent Te(4)Bi6 octahedra, corners with two equivalent Te(20)Cs4Bi2 pentagonal pyramids, corners with two equivalent Te(14)Cs2Bi3 square pyramids, corners with two equivalent Te(13)CsBi4 trigonal bipyramids,  an edgeedge with one Te(4)Bi6 octahedra, edges with two equivalent Te(12)Bi6 octahedra, edges with two equivalent Te(24)Cs4Bi2 pentagonal pyramids, and edges with two equivalent Te(19)Bi5 square pyramids. The corner-sharing octahedral tilt angles range from 7-18°. In the fourteenth Te site, Te(14) is bonded to two equivalent Cs(3), one Bi(15), and two equivalent Bi(4) atoms to form distorted TeCs2Bi3 square pyramids that share corners with two equivalent Bi(7)BiTe5 octahedra, corners with two equivalent Te(20)Cs4Bi2 pentagonal pyramids, corners with two equivalent Te(24)Cs4Bi2 pentagonal pyramids, corners with two equivalent Te(19)Bi5 square pyramids,  a cornercorner with one Te(1)CsBi4 trigonal bipyramid, corners with two equivalent Te(13)CsBi4 trigonal bipyramids, edges with two equivalent Te(4)Bi6 octahedra,  an edgeedge with one Te(20)Cs4Bi2 pentagonal pyramid,  an edgeedge with one Te(24)Cs4Bi2 pentagonal pyramid,  an edgeedge with one Te(19)Bi5 square pyramid, and edges with two equivalent Te(14)Cs2Bi3 square pyramids. The corner-sharing octahedral tilt angles are 93°. In the fifteenth Te site, Te(15) is bonded in a 5-coordinate geometry to one Cs(4), two equivalent Cs(3), and two equivalent Bi(5) atoms. In the sixteenth Te site, Te(16) is bonded to one Bi(2), one Bi(8), two equivalent Bi(10), and two equivalent Bi(16) atoms to form TeBi6 octahedra that share  a cornercorner with one Te(17)Bi6 octahedra,  a cornercorner with one Te(4)Bi6 octahedra, corners with two equivalent Te(23)Cs2Bi4 octahedra, corners with two equivalent Te(9)Cs3Bi2 trigonal bipyramids,  an edgeedge with one Te(23)Cs2Bi4 octahedra, edges with two equivalent Te(12)Bi6 octahedra, edges with two equivalent Te(16)Bi6 octahedra, edges with two equivalent Te(22)Bi6 octahedra, edges with two equivalent Te(7)Cs2Bi4 octahedra,  an edgeedge with one Te(9)Cs3Bi2 trigonal bipyramid, and edges with two equivalent Te(1)CsBi4 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 2-8°. In the seventeenth Te site, Te(17) is bonded to one Bi(2), one Bi(6), two equivalent Bi(1), and two equivalent Bi(9) atoms to form TeBi6 octahedra that share  a cornercorner with one Te(16)Bi6 octahedra,  a cornercorner with one Te(2)Bi5 square pyramid, corners with two equivalent Te(8)CsBi4 trigonal bipyramids, edges with two equivalent Te(10)Bi6 octahedra, edges with two equivalent Te(17)Bi6 octahedra, edges with two equivalent Te(22)Bi6 octahedra, edges with two equivalent Te(7)Cs2Bi4 octahedra,  an edgeedge with one Te(8)CsBi4 trigonal bipyramid, and edges with two equivalent Te(5)CsBi4 trigonal bipyramids. The corner-sharing octahedral tilt angles are 8°. In the eighteenth Te site, Te(18) is bonded in a 5-coordinate geometry to one Cs(1), two equivalent Cs(2), and two equivalent Bi(9) atoms. In the nineteenth Te site, Te(19) is bonded to one Bi(3), two equivalent Bi(12), and two equivalent Bi(4) atoms to form TeBi5 square pyramids that share  a cornercorner with one Te(12)Bi6 octahedra, corners with two equivalent Bi(11)BiTe5 octahedra, corners with two equivalent Bi(7)BiTe5 octahedra, corners with two equivalent Te(24)Cs4Bi2 pentagonal pyramids, corners with two equivalent Te(14)Cs2Bi3 square pyramids, edges with two equivalent Te(4)Bi6 octahedra,  an edgeedge with one Te(24)Cs4Bi2 pentagonal pyramid,  an edgeedge with one Te(14)Cs2Bi3 square pyramid, edges with two equivalent Te(19)Bi5 square pyramids, and edges with two equivalent Te(13)CsBi4 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 5-96°. In the twentieth Te site, Te(20) is bonded to two equivalent Cs(2), two equivalent Cs(3), and two equivalent Bi(7) atoms to form distorted TeCs4Bi2 pentagonal pyramids that share corners with two equivalent Bi(4)BiTe5 octahedra, corners with two equivalent Te(2)Bi5 square pyramids, corners with two equivalent Te(11)Cs2Bi3 square pyramids, corners with two equivalent Te(14)Cs2Bi3 square pyramids, corners with two equivalent Te(13)CsBi4 trigonal bipyramids, edges with two equivalent Te(24)Cs4Bi2 pentagonal pyramids,  an edgeedge with one Te(2)Bi5 square pyramid,  an edgeedge with one Te(11)Cs2Bi3 square pyramid,  an edgeedge with one Te(14)Cs2Bi3 square pyramid, edges with two equivalent Te(5)CsBi4 trigonal bipyramids,  a faceface with one Te(24)Cs4Bi2 pentagonal pyramid, and faces with two equivalent Te(20)Cs4Bi2 pentagonal pyramids. The corner-sharing octahedral tilt angles are 77°. In the twenty-first Te site, Te(21) is bonded in a 5-coordinate geometry to one Cs(2), two equivalent Cs(1), and two equivalent Bi(14) atoms. In the twenty-second Te site, Te(22) is bonded to one Bi(1), one Bi(16), two equivalent Bi(13), and two equivalent Bi(2) atoms to form TeBi6 octahedra that share  a cornercorner with one Te(10)Bi6 octahedra,  a cornercorner with one Te(12)Bi6 octahedra, corners with two equivalent Te(7)Cs2Bi4 octahedra, corners with two equivalent Te(3)Cs3Bi2 trigonal bipyramids,  an edgeedge with one Te(7)Cs2Bi4 octahedra, edges with two equivalent Te(16)Bi6 octahedra, edges with two equivalent Te(17)Bi6 octahedra, edges with two equivalent Te(22)Bi6 octahedra, edges with two equivalent Te(23)Cs2Bi4 octahedra,  an edgeedge with one Te(3)Cs3Bi2 trigonal bipyramid, and edges with two equivalent Te(8)CsBi4 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 2-8°. In the twenty-third Te site, Te(23) is bonded to two equivalent Cs(4), one Bi(13), one Bi(5), and two equivalent Bi(16) atoms to form TeCs2Bi4 octahedra that share corners with two equivalent Te(16)Bi6 octahedra,  a cornercorner with one Te(13)CsBi4 trigonal bipyramid,  a cornercorner with one Te(8)CsBi4 trigonal bipyramid, corners with two equivalent Te(9)Cs3Bi2 trigonal bipyramids, corners with two equivalent Te(1)CsBi4 trigonal bipyramids,  an edgeedge with one Te(16)Bi6 octahedra, edges with two equivalent Te(12)Bi6 octahedra, edges with two equivalent Te(22)Bi6 octahedra, edges with two equivalent Te(23)Cs2Bi4 octahedra,  an edgeedge with one Te(9)Cs3Bi2 trigonal bipyramid, and edges with two equivalent Te(3)Cs3Bi2 trigonal bipyramids. The corner-sharing octahedral tilt angles are 3°. In the twenty-fourth Te site, Te(24) is bonded to two equivalent Cs(2), two equivalent Cs(3), and two equivalent Bi(12) atoms to form distorted TeCs4Bi2 pentagonal pyramids that share corners with two equivalent Bi(11)BiTe5 octahedra, corners with two equivalent Te(19)Bi5 square pyramids, corners with two equivalent Te(11)Cs2Bi3 square pyramids, corners with two equivalent Te(14)Cs2Bi3 square pyramids, corners with two equivalent Te(5)CsBi4 trigonal bipyramids, edges with two equivalent Te(20)Cs4Bi2 pentagonal pyramids,  an edgeedge with one Te(19)Bi5 square pyramid,  an edgeedge with one Te(11)Cs2Bi3 square pyramid,  an edgeedge with one Te(14)Cs2Bi3 square pyramid, edges with two equivalent Te(13)CsBi4 trigonal bipyramids,  a faceface with one Te(20)Cs4Bi2 pentagonal pyramid, and faces with two equivalent Te(24)Cs4Bi2 pentagonal pyramids. The corner-sharing octahedral tilt angles are 77°.
CsBi4Te6 crystallizes in the triclinic P1 space group. There are four inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 9-coordinate geometry to one Te(18), one Te(8), one Te(9), two equivalent Te(21), two equivalent Te(3), and two equivalent Te(7) atoms. The Cs(1)-Te(18) bond length is 3.88 Å. The Cs(1)-Te(8) bond length is 3.95 Å. The Cs(1)-Te(9) bond length is 3.81 Å. There is one shorter (4.04 Å) and one longer (4.05 Å) Cs(1)-Te(21) bond length. There is one shorter (4.13 Å) and one longer (4.14 Å) Cs(1)-Te(3) bond length. There is one shorter (4.13 Å) and one longer (4.16 Å) Cs(1)-Te(7) bond length. In the second Cs site, Cs(2) is bonded in a 10-coordinate geometry to one Te(21), one Te(5), two equivalent Te(11), two equivalent Te(18), two equivalent Te(20), and two equivalent Te(24) atoms. The Cs(2)-Te(21) bond length is 4.11 Å. The Cs(2)-Te(5) bond length is 4.01 Å. There is one shorter (4.08 Å) and one longer (4.09 Å) Cs(2)-Te(11) bond length. There is one shorter (4.22 Å) and one longer (4.28 Å) Cs(2)-Te(18) bond length. There is one shorter (4.08 Å) and one longer (4.12 Å) Cs(2)-Te(20) bond length. There is one shorter (4.21 Å) and one longer (4.23 Å) Cs(2)-Te(24) bond length. In the third Cs site, Cs(3) is bonded in a 10-coordinate geometry to one Te(13), one Te(6), two equivalent Te(14), two equivalent Te(15), two equivalent Te(20), and two equivalent Te(24) atoms. The Cs(3)-Te(13) bond length is 4.07 Å. The Cs(3)-Te(6) bond length is 4.13 Å. There is one shorter (4.05 Å) and one longer (4.06 Å) Cs(3)-Te(14) bond length. There is one shorter (4.28 Å) and one longer (4.30 Å) Cs(3)-Te(15) bond length. There is one shorter (4.18 Å) and one longer (4.19 Å) Cs(3)-Te(20) bond length. There is one shorter (4.10 Å) and one longer (4.13 Å) Cs(3)-Te(24) bond length. In the fourth Cs site, Cs(4) is bonded in a 9-coordinate geometry to one Te(1), one Te(15), one Te(3), two equivalent Te(23), two equivalent Te(6), and two equivalent Te(9) atoms. The Cs(4)-Te(1) bond length is 3.96 Å. The Cs(4)-Te(15) bond length is 3.88 Å. The Cs(4)-Te(3) bond length is 3.81 Å. There is one shorter (4.11 Å) and one longer (4.14 Å) Cs(4)-Te(23) bond length. There is one shorter (4.02 Å) and one longer (4.06 Å) Cs(4)-Te(6) bond length. There is one shorter (4.12 Å) and one longer (4.16 Å) Cs(4)-Te(9) bond length. There are sixteen inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one Te(10), one Te(22), two equivalent Te(17), and two equivalent Te(8) atoms to form BiTe6 octahedra that share  a cornercorner with one Bi(11)BiTe5 octahedra,  a cornercorner with one Bi(16)Te6 octahedra, corners with two equivalent Bi(9)Te6 octahedra,  an edgeedge with one Bi(9)Te6 octahedra, edges with two equivalent Bi(1)Te6 octahedra, edges with two equivalent Bi(13)Te6 octahedra, edges with two equivalent Bi(14)Te6 octahedra, edges with two equivalent Bi(2)Te6 octahedra, and edges with two equivalent Bi(6)Te6 octahedra. The corner-sharing octahedral tilt angles are 7°. The Bi(1)-Te(10) bond length is 3.09 Å. The Bi(1)-Te(22) bond length is 3.31 Å. There is one shorter (3.23 Å) and one longer (3.24 Å) Bi(1)-Te(17) bond length. There is one shorter (3.10 Å) and one longer (3.11 Å) Bi(1)-Te(8) bond length. In the second Bi site, Bi(2) is bonded to one Te(16), one Te(17), two equivalent Te(22), and two equivalent Te(7) atoms to form a mixture of corner and edge-sharing BiTe6 octahedra. The corner-sharing octahedral tilt angles range from 2-7°. The Bi(2)-Te(16) bond length is 3.26 Å. The Bi(2)-Te(17) bond length is 3.14 Å. There is one shorter (3.23 Å) and one longer (3.27 Å) Bi(2)-Te(22) bond length. There is one shorter (3.12 Å) and one longer (3.13 Å) Bi(2)-Te(7) bond length. In the third Bi site, Bi(3) is bonded to one Te(12), one Te(19), two equivalent Te(13), and two equivalent Te(4) atoms to form BiTe6 octahedra that share  a cornercorner with one Bi(16)Te6 octahedra, corners with two equivalent Bi(15)Te6 octahedra,  an edgeedge with one Bi(15)Te6 octahedra, edges with two equivalent Bi(12)BiTe5 octahedra, edges with two equivalent Bi(4)BiTe5 octahedra, edges with two equivalent Bi(3)Te6 octahedra, edges with two equivalent Bi(5)Te6 octahedra, and edges with two equivalent Bi(8)Te6 octahedra. The corner-sharing octahedral tilt angles range from 2-6°. The Bi(3)-Te(12) bond length is 3.44 Å. The Bi(3)-Te(19) bond length is 3.04 Å. Both Bi(3)-Te(13) bond lengths are 3.11 Å. There is one shorter (3.24 Å) and one longer (3.25 Å) Bi(3)-Te(4) bond length. In the fourth Bi site, Bi(4) is bonded to one Bi(7), one Te(4), two equivalent Te(14), and two equivalent Te(19) atoms to form distorted BiBiTe5 octahedra that share  a cornercorner with one Bi(8)Te6 octahedra, corners with two equivalent Bi(12)BiTe5 octahedra, corners with two equivalent Te(20)Cs4Bi2 pentagonal pyramids, corners with two equivalent Te(2)Bi5 square pyramids,  a cornercorner with one Te(5)CsBi4 trigonal bipyramid,  an edgeedge with one Bi(12)BiTe5 octahedra, edges with two equivalent Bi(4)BiTe5 octahedra, edges with two equivalent Bi(15)Te6 octahedra, and edges with two equivalent Bi(3)Te6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. The Bi(4)-Bi(7) bond length is 3.27 Å. The Bi(4)-Te(4) bond length is 3.54 Å. There is one shorter (3.06 Å) and one longer (3.07 Å) Bi(4)-Te(14) bond length. There is one shorter (3.35 Å) and one longer (3.36 Å) Bi(4)-Te(19) bond length. In the fifth Bi site, Bi(5) is bonded to one Te(13), one Te(23), two equivalent Te(12), and two equivalent Te(15) atoms to form BiTe6 octahedra that share  a cornercorner with one Bi(12)BiTe5 octahedra,  a cornercorner with one Bi(13)Te6 octahedra, corners with two equivalent Bi(8)Te6 octahedra,  an edgeedge with one Bi(8)Te6 octahedra, edges with two equivalent Bi(16)Te6 octahedra, edges with two equivalent Bi(3)Te6 octahedra, and edges with two equivalent Bi(5)Te6 octahedra. The corner-sharing octahedral tilt angles range from 7-10°. The Bi(5)-Te(13) bond length is 3.07 Å. The Bi(5)-Te(23) bond length is 3.46 Å. Both Bi(5)-Te(12) bond lengths are 3.43 Å. There is one shorter (3.01 Å) and one longer (3.02 Å) Bi(5)-Te(15) bond length. In the sixth Bi site, Bi(6) is bonded to one Te(17), one Te(2), two equivalent Te(10), and two equivalent Te(5) atoms to form BiTe6 octahedra that share  a cornercorner with one Bi(2)Te6 octahedra, corners with two equivalent Bi(14)Te6 octahedra,  an edgeedge with one Bi(14)Te6 octahedra, edges with two equivalent Bi(11)BiTe5 octahedra, edges with two equivalent Bi(7)BiTe5 octahedra, edges with two equivalent Bi(1)Te6 octahedra, edges with two equivalent Bi(6)Te6 octahedra, and edges with two equivalent Bi(9)Te6 octahedra. The corner-sharing octahedral tilt angles range from 2-7°. The Bi(6)-Te(17) bond length is 3.45 Å. The Bi(6)-Te(2) bond length is 3.04 Å. There is one shorter (3.23 Å) and one longer (3.26 Å) Bi(6)-Te(10) bond length. There is one shorter (3.10 Å) and one longer (3.11 Å) Bi(6)-Te(5) bond length. In the seventh Bi site, Bi(7) is bonded to one Bi(4), one Te(5), two equivalent Te(2), and two equivalent Te(20) atoms to form distorted BiBiTe5 octahedra that share  a cornercorner with one Bi(9)Te6 octahedra,  a cornercorner with one Te(4)Bi6 octahedra, corners with two equivalent Bi(11)BiTe5 octahedra, corners with two equivalent Te(19)Bi5 square pyramids, corners with two equivalent Te(14)Cs2Bi3 square pyramids,  an edgeedge with one Bi(11)BiTe5 octahedra, edges with two equivalent Bi(7)BiTe5 octahedra, and edges with two equivalent Bi(6)Te6 octahedra. The corner-sharing octahedral tilt angles range from 9-10°. The Bi(7)-Te(5) bond length is 3.48 Å. Both Bi(7)-Te(2) bond lengths are 3.36 Å. There is one shorter (3.05 Å) and one longer (3.06 Å) Bi(7)-Te(20) bond length. In the eighth Bi site, Bi(8) is bonded to one Te(16), one Te(4), two equivalent Te(1), and two equivalent Te(12) atoms to form BiTe6 octahedra that share  a cornercorner with one Bi(4)BiTe5 octahedra,  a cornercorner with one Bi(2)Te6 octahedra, corners with two equivalent Bi(5)Te6 octahedra,  an edgeedge with one Bi(5)Te6 octahedra, edges with two equivalent Bi(10)Te6 octahedra, edges with two equivalent Bi(15)Te6 octahedra, edges with two equivalent Bi(16)Te6 octahedra, edges with two equivalent Bi(3)Te6 octahedra, and edges with two equivalent Bi(8)Te6 octahedra. The corner-sharing octahedral tilt angles range from 6-7°. The Bi(8)-Te(16) bond length is 3.31 Å. The Bi(8)-Te(4) bond length is 3.09 Å. Both Bi(8)-Te(1) bond lengths are 3.10 Å. There is one shorter (3.23 Å) and one longer (3.24 Å) Bi(8)-Te(12) bond length. In the ninth Bi site, Bi(9) is bonded to one Te(5), one Te(7), two equivalent Te(17), and two equivalent Te(18) atoms to form BiTe6 octahedra that share  a cornercorner with one Bi(7)BiTe5 octahedra,  a cornercorner with one Bi(10)Te6 octahedra, corners with two equivalent Bi(1)Te6 octahedra,  an edgeedge with one Bi(1)Te6 octahedra, edges with two equivalent Bi(2)Te6 octahedra, edges with two equivalent Bi(6)Te6 octahedra, and edges with two equivalent Bi(9)Te6 octahedra. The corner-sharing octahedral tilt angles range from 7-9°. The Bi(9)-Te(5) bond length is 3.07 Å. The Bi(9)-Te(7) bond length is 3.48 Å. Both Bi(9)-Te(17) bond lengths are 3.43 Å. There is one shorter (3.01 Å) and one longer (3.02 Å) Bi(9)-Te(18) bond length. In the tenth Bi site, Bi(10) is bonded to one Te(1), one Te(7), two equivalent Te(16), and two equivalent Te(9) atoms to form a mixture of corner and edge-sharing BiTe6 octahedra. The corner-sharing octahedral tilt angles range from 4-14°. The Bi(10)-Te(1) bond length is 3.10 Å. The Bi(10)-Te(7) bond length is 3.32 Å. There is one shorter (3.46 Å) and one longer (3.47 Å) Bi(10)-Te(16) bond length. Both Bi(10)-Te(9) bond lengths are 3.02 Å. In the eleventh Bi site, Bi(11) is bonded to one Bi(12), one Te(10), two equivalent Te(11), and two equivalent Te(2) atoms to form distorted BiBiTe5 octahedra that share  a cornercorner with one Bi(1)Te6 octahedra, corners with two equivalent Bi(7)BiTe5 octahedra, corners with two equivalent Te(24)Cs4Bi2 pentagonal pyramids, corners with two equivalent Te(19)Bi5 square pyramids,  a cornercorner with one Te(13)CsBi4 trigonal bipyramid,  an edgeedge with one Bi(7)BiTe5 octahedra, edges with two equivalent Bi(11)BiTe5 octahedra, edges with two equivalent Bi(14)Te6 octahedra, and edges with two equivalent Bi(6)Te6 octahedra. The corner-sharing octahedral tilt angles range from 7-10°. The Bi(11)-Bi(12) bond length is 3.26 Å. The Bi(11)-Te(10) bond length is 3.58 Å. There is one shorter (3.06 Å) and one longer (3.07 Å) Bi(11)-Te(11) bond length. There is one shorter (3.36 Å) and one longer (3.38 Å) Bi(11)-Te(2) bond length. In the twelfth Bi site, Bi(12) is bonded to one Bi(11), one Te(13), two equivalent Te(19), and two equivalent Te(24) atoms to form distorted BiBiTe5 octahedra that share  a cornercorner with one Bi(5)Te6 octahedra,  a cornercorner with one Te(10)Bi6 octahedra, corners with two equivalent Bi(4)BiTe5 octahedra, corners with two equivalent Te(2)Bi5 square pyramids, corners with two equivalent Te(11)Cs2Bi3 square pyramids,  an edgeedge with one Bi(4)BiTe5 octahedra, edges with two equivalent Bi(12)BiTe5 octahedra, and edges with two equivalent Bi(3)Te6 octahedra. The corner-sharing octahedral tilt angles are 10°. The Bi(12)-Te(13) bond length is 3.49 Å. There is one shorter (3.35 Å) and one longer (3.39 Å) Bi(12)-Te(19) bond length. There is one shorter (3.04 Å) and one longer (3.06 Å) Bi(12)-Te(24) bond length. In the thirteenth Bi site, Bi(13) is bonded to one Te(23), one Te(8), two equivalent Te(22), and two equivalent Te(3) atoms to form a mixture of corner and edge-sharing BiTe6 octahedra. The corner-sharing octahedral tilt angles range from 4-14°. The Bi(13)-Te(23) bond length is 3.32 Å. The Bi(13)-Te(8) bond length is 3.10 Å. Both Bi(13)-Te(22) bond lengths are 3.45 Å. Both Bi(13)-Te(3) bond lengths are 3.02 Å. In the fourteenth Bi site, Bi(14) is bonded to one Te(11), one Te(8), two equivalent Te(10), and two equivalent Te(21) atoms to form BiTe6 octahedra that share  a cornercorner with one Bi(13)Te6 octahedra, corners with two equivalent Bi(6)Te6 octahedra,  an edgeedge with one Bi(6)Te6 octahedra, edges with two equivalent Bi(11)BiTe5 octahedra, edges with two equivalent Bi(1)Te6 octahedra, and edges with two equivalent Bi(14)Te6 octahedra. The corner-sharing octahedral tilt angles range from 7-14°. The Bi(14)-Te(11) bond length is 3.01 Å. The Bi(14)-Te(8) bond length is 3.35 Å. Both Bi(14)-Te(10) bond lengths are 3.39 Å. There is one shorter (3.02 Å) and one longer (3.03 Å) Bi(14)-Te(21) bond length. In the fifteenth Bi site, Bi(15) is bonded to one Te(1), one Te(14), two equivalent Te(4), and two equivalent Te(6) atoms to form BiTe6 octahedra that share  a cornercorner with one Bi(10)Te6 octahedra, corners with two equivalent Bi(3)Te6 octahedra,  an edgeedge with one Bi(3)Te6 octahedra, edges with two equivalent Bi(4)BiTe5 octahedra, edges with two equivalent Bi(15)Te6 octahedra, and edges with two equivalent Bi(8)Te6 octahedra. The corner-sharing octahedral tilt angles range from 6-14°. The Bi(15)-Te(1) bond length is 3.34 Å. The Bi(15)-Te(14) bond length is 3.01 Å. There is one shorter (3.38 Å) and one longer (3.40 Å) Bi(15)-Te(4) bond length. Both Bi(15)-Te(6) bond lengths are 3.02 Å. In the sixteenth Bi site, Bi(16) is bonded to one Te(12), one Te(22), two equivalent Te(16), and two equivalent Te(23) atoms to form a mixture of corner and edge-sharing BiTe6 octahedra. The corner-sharing octahedral tilt angles range from 2-7°. The Bi(16)-Te(12) bond length is 3.15 Å. The Bi(16)-Te(22) bond length is 3.25 Å. Both Bi(16)-Te(16) bond lengths are 3.25 Å. There is one shorter (3.12 Å) and one longer (3.13 Å) Bi(16)-Te(23) bond length. There are twenty-four inequivalent Te sites. In the first Te site, Te(1) is bonded to one Cs(4), one Bi(10), one Bi(15), and two equivalent Bi(8) atoms to form TeCsBi4 trigonal bipyramids that share  a cornercorner with one Te(7)Cs2Bi4 octahedra, corners with two equivalent Te(12)Bi6 octahedra, corners with two equivalent Te(23)Cs2Bi4 octahedra,  a cornercorner with one Te(14)Cs2Bi3 square pyramid,  a cornercorner with one Te(3)Cs3Bi2 trigonal bipyramid, corners with two equivalent Te(1)CsBi4 trigonal bipyramids,  an edgeedge with one Te(12)Bi6 octahedra, edges with two equivalent Te(16)Bi6 octahedra, edges with two equivalent Te(4)Bi6 octahedra, and edges with two equivalent Te(9)Cs3Bi2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 5-34°. In the second Te site, Te(2) is bonded to one Bi(6), two equivalent Bi(11), and two equivalent Bi(7) atoms to form TeBi5 square pyramids that share  a cornercorner with one Te(17)Bi6 octahedra, corners with two equivalent Bi(12)BiTe5 octahedra, corners with two equivalent Bi(4)BiTe5 octahedra, corners with two equivalent Te(20)Cs4Bi2 pentagonal pyramids, corners with two equivalent Te(11)Cs2Bi3 square pyramids, edges with two equivalent Te(10)Bi6 octahedra,  an edgeedge with one Te(20)Cs4Bi2 pentagonal pyramid,  an edgeedge with one Te(11)Cs2Bi3 square pyramid, edges with two equivalent Te(2)Bi5 square pyramids, and edges with two equivalent Te(5)CsBi4 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 5-96°. In the third Te site, Te(3) is bonded to one Cs(4), two equivalent Cs(1), and two equivalent Bi(13) atoms to form distorted TeCs3Bi2 trigonal bipyramids that share corners with two equivalent Te(22)Bi6 octahedra, corners with two equivalent Te(7)Cs2Bi4 octahedra,  a cornercorner with one Te(1)CsBi4 trigonal bipyramid,  an edgeedge with one Te(22)Bi6 octahedra,  an edgeedge with one Te(7)Cs2Bi4 octahedra, edges with two equivalent Te(23)Cs2Bi4 octahedra, edges with two equivalent Te(3)Cs3Bi2 trigonal bipyramids, edges with two equivalent Te(9)Cs3Bi2 trigonal bipyramids, and edges with two equivalent Te(8)CsBi4 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 8-53°. In the fourth Te site, Te(4) is bonded to one Bi(4), one Bi(8), two equivalent Bi(15), and two equivalent Bi(3) atoms to form distorted TeBi6 octahedra that share  a cornercorner with one Bi(7)BiTe5 octahedra,  a cornercorner with one Te(16)Bi6 octahedra, corners with two equivalent Te(13)CsBi4 trigonal bipyramids, edges with two equivalent Te(12)Bi6 octahedra, edges with two equivalent Te(4)Bi6 octahedra, edges with two equivalent Te(19)Bi5 square pyramids, edges with two equivalent Te(14)Cs2Bi3 square pyramids,  an edgeedge with one Te(13)CsBi4 trigonal bipyramid, and edges with two equivalent Te(1)CsBi4 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 2-10°. In the fifth Te site, Te(5) is bonded to one Cs(2), one Bi(7), one Bi(9), and two equivalent Bi(6) atoms to form TeCsBi4 trigonal bipyramids that share  a cornercorner with one Bi(4)BiTe5 octahedra,  a cornercorner with one Te(7)Cs2Bi4 octahedra, corners with two equivalent Te(10)Bi6 octahedra, corners with two equivalent Te(24)Cs4Bi2 pentagonal pyramids, corners with two equivalent Te(11)Cs2Bi3 square pyramids, corners with two equivalent Te(5)CsBi4 trigonal bipyramids,  an edgeedge with one Te(10)Bi6 octahedra, edges with two equivalent Te(17)Bi6 octahedra, edges with two equivalent Te(20)Cs4Bi2 pentagonal pyramids, and edges with two equivalent Te(2)Bi5 square pyramids. The corner-sharing octahedral tilt angles range from 7-18°. In the sixth Te site, Te(6) is bonded in a 5-coordinate geometry to one Cs(3), two equivalent Cs(4), and two equivalent Bi(15) atoms. In the seventh Te site, Te(7) is bonded to two equivalent Cs(1), one Bi(10), one Bi(9), and two equivalent Bi(2) atoms to form TeCs2Bi4 octahedra that share corners with two equivalent Te(22)Bi6 octahedra,  a cornercorner with one Te(1)CsBi4 trigonal bipyramid,  a cornercorner with one Te(5)CsBi4 trigonal bipyramid, corners with two equivalent Te(3)Cs3Bi2 trigonal bipyramids, corners with two equivalent Te(8)CsBi4 trigonal bipyramids,  an edgeedge with one Te(22)Bi6 octahedra, edges with two equivalent Te(16)Bi6 octahedra, edges with two equivalent Te(17)Bi6 octahedra, edges with two equivalent Te(7)Cs2Bi4 octahedra,  an edgeedge with one Te(3)Cs3Bi2 trigonal bipyramid, and edges with two equivalent Te(9)Cs3Bi2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 2-3°. In the eighth Te site, Te(8) is bonded to one Cs(1), one Bi(13), one Bi(14), and two equivalent Bi(1) atoms to form TeCsBi4 trigonal bipyramids that share  a cornercorner with one Te(23)Cs2Bi4 octahedra, corners with two equivalent Te(17)Bi6 octahedra, corners with two equivalent Te(7)Cs2Bi4 octahedra,  a cornercorner with one Te(11)Cs2Bi3 square pyramid,  a cornercorner with one Te(9)Cs3Bi2 trigonal bipyramid, corners with two equivalent Te(8)CsBi4 trigonal bipyramids,  an edgeedge with one Te(17)Bi6 octahedra, edges with two equivalent Te(10)Bi6 octahedra, edges with two equivalent Te(22)Bi6 octahedra, and edges with two equivalent Te(3)Cs3Bi2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 5-33°. In the ninth Te site, Te(9) is bonded to one Cs(1), two equivalent Cs(4), and two equivalent Bi(10) atoms to form distorted TeCs3Bi2 trigonal bipyramids that share corners with two equivalent Te(16)Bi6 octahedra, corners with two equivalent Te(23)Cs2Bi4 octahedra,  a cornercorner with one Te(8)CsBi4 trigonal bipyramid,  an edgeedge with one Te(16)Bi6 octahedra,  an edgeedge with one Te(23)Cs2Bi4 octahedra, edges with two equivalent Te(7)Cs2Bi4 octahedra, edges with two equivalent Te(3)Cs3Bi2 trigonal bipyramids, edges with two equivalent Te(9)Cs3Bi2 trigonal bipyramids, and edges with two equivalent Te(1)CsBi4 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 9-53°. In the tenth Te site, Te(10) is bonded to one Bi(1), one Bi(11), two equivalent Bi(14), and two equivalent Bi(6) atoms to form distorted TeBi6 octahedra that share  a cornercorner with one Bi(12)BiTe5 octahedra,  a cornercorner with one Te(22)Bi6 octahedra, corners with two equivalent Te(5)CsBi4 trigonal bipyramids, edges with two equivalent Te(10)Bi6 octahedra, edges with two equivalent Te(17)Bi6 octahedra, edges with two equivalent Te(2)Bi5 square pyramids, edges with two equivalent Te(11)Cs2Bi3 square pyramids,  an edgeedge with one Te(5)CsBi4 trigonal bipyramid, and edges with two equivalent Te(8)CsBi4 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 2-10°. In the eleventh Te site, Te(11) is bonded to two equivalent Cs(2), one Bi(14), and two equivalent Bi(11) atoms to form distorted TeCs2Bi3 square pyramids that share corners with two equivalent Bi(12)BiTe5 octahedra, corners with two equivalent Te(20)Cs4Bi2 pentagonal pyramids, corners with two equivalent Te(24)Cs4Bi2 pentagonal pyramids, corners with two equivalent Te(2)Bi5 square pyramids,  a cornercorner with one Te(8)CsBi4 trigonal bipyramid, corners with two equivalent Te(5)CsBi4 trigonal bipyramids, edges with two equivalent Te(10)Bi6 octahedra,  an edgeedge with one Te(20)Cs4Bi2 pentagonal pyramid,  an edgeedge with one Te(24)Cs4Bi2 pentagonal pyramid,  an edgeedge with one Te(2)Bi5 square pyramid, and edges with two equivalent Te(11)Cs2Bi3 square pyramids. The corner-sharing octahedral tilt angles are 93°. In the twelfth Te site, Te(12) is bonded to one Bi(16), one Bi(3), two equivalent Bi(5), and two equivalent Bi(8) atoms to form TeBi6 octahedra that share  a cornercorner with one Te(22)Bi6 octahedra,  a cornercorner with one Te(19)Bi5 square pyramid, corners with two equivalent Te(1)CsBi4 trigonal bipyramids, edges with two equivalent Te(12)Bi6 octahedra, edges with two equivalent Te(16)Bi6 octahedra, edges with two equivalent Te(4)Bi6 octahedra, edges with two equivalent Te(23)Cs2Bi4 octahedra,  an edgeedge with one Te(1)CsBi4 trigonal bipyramid, and edges with two equivalent Te(13)CsBi4 trigonal bipyramids. The corner-sharing octahedral tilt angles are 8°. In the thirteenth Te site, Te(13) is bonded to one Cs(3), one Bi(12), one Bi(5), and two equivalent Bi(3) atoms to form TeCsBi4 trigonal bipyramids that share  a cornercorner with one Bi(11)BiTe5 octahedra,  a cornercorner with one Te(23)Cs2Bi4 octahedra, corners with two equivalent Te(4)Bi6 octahedra, corners with two equivalent Te(20)Cs4Bi2 pentagonal pyramids, corners with two equivalent Te(14)Cs2Bi3 square pyramids, corners with two equivalent Te(13)CsBi4 trigonal bipyramids,  an edgeedge with one Te(4)Bi6 octahedra, edges with two equivalent Te(12)Bi6 octahedra, edges with two equivalent Te(24)Cs4Bi2 pentagonal pyramids, and edges with two equivalent Te(19)Bi5 square pyramids. The corner-sharing octahedral tilt angles range from 7-18°. In the fourteenth Te site, Te(14) is bonded to two equivalent Cs(3), one Bi(15), and two equivalent Bi(4) atoms to form distorted TeCs2Bi3 square pyramids that share corners with two equivalent Bi(7)BiTe5 octahedra, corners with two equivalent Te(20)Cs4Bi2 pentagonal pyramids, corners with two equivalent Te(24)Cs4Bi2 pentagonal pyramids, corners with two equivalent Te(19)Bi5 square pyramids,  a cornercorner with one Te(1)CsBi4 trigonal bipyramid, corners with two equivalent Te(13)CsBi4 trigonal bipyramids, edges with two equivalent Te(4)Bi6 octahedra,  an edgeedge with one Te(20)Cs4Bi2 pentagonal pyramid,  an edgeedge with one Te(24)Cs4Bi2 pentagonal pyramid,  an edgeedge with one Te(19)Bi5 square pyramid, and edges with two equivalent Te(14)Cs2Bi3 square pyramids. The corner-sharing octahedral tilt angles are 93°. In the fifteenth Te site, Te(15) is bonded in a 5-coordinate geometry to one Cs(4), two equivalent Cs(3), and two equivalent Bi(5) atoms. In the sixteenth Te site, Te(16) is bonded to one Bi(2), one Bi(8), two equivalent Bi(10), and two equivalent Bi(16) atoms to form TeBi6 octahedra that share  a cornercorner with one Te(17)Bi6 octahedra,  a cornercorner with one Te(4)Bi6 octahedra, corners with two equivalent Te(23)Cs2Bi4 octahedra, corners with two equivalent Te(9)Cs3Bi2 trigonal bipyramids,  an edgeedge with one Te(23)Cs2Bi4 octahedra, edges with two equivalent Te(12)Bi6 octahedra, edges with two equivalent Te(16)Bi6 octahedra, edges with two equivalent Te(22)Bi6 octahedra, edges with two equivalent Te(7)Cs2Bi4 octahedra,  an edgeedge with one Te(9)Cs3Bi2 trigonal bipyramid, and edges with two equivalent Te(1)CsBi4 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 2-8°. In the seventeenth Te site, Te(17) is bonded to one Bi(2), one Bi(6), two equivalent Bi(1), and two equivalent Bi(9) atoms to form TeBi6 octahedra that share  a cornercorner with one Te(16)Bi6 octahedra,  a cornercorner with one Te(2)Bi5 square pyramid, corners with two equivalent Te(8)CsBi4 trigonal bipyramids, edges with two equivalent Te(10)Bi6 octahedra, edges with two equivalent Te(17)Bi6 octahedra, edges with two equivalent Te(22)Bi6 octahedra, edges with two equivalent Te(7)Cs2Bi4 octahedra,  an edgeedge with one Te(8)CsBi4 trigonal bipyramid, and edges with two equivalent Te(5)CsBi4 trigonal bipyramids. The corner-sharing octahedral tilt angles are 8°. In the eighteenth Te site, Te(18) is bonded in a 5-coordinate geometry to one Cs(1), two equivalent Cs(2), and two equivalent Bi(9) atoms. In the nineteenth Te site, Te(19) is bonded to one Bi(3), two equivalent Bi(12), and two equivalent Bi(4) atoms to form TeBi5 square pyramids that share  a cornercorner with one Te(12)Bi6 octahedra, corners with two equivalent Bi(11)BiTe5 octahedra, corners with two equivalent Bi(7)BiTe5 octahedra, corners with two equivalent Te(24)Cs4Bi2 pentagonal pyramids, corners with two equivalent Te(14)Cs2Bi3 square pyramids, edges with two equivalent Te(4)Bi6 octahedra,  an edgeedge with one Te(24)Cs4Bi2 pentagonal pyramid,  an edgeedge with one Te(14)Cs2Bi3 square pyramid, edges with two equivalent Te(19)Bi5 square pyramids, and edges with two equivalent Te(13)CsBi4 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 5-96°. In the twentieth Te site, Te(20) is bonded to two equivalent Cs(2), two equivalent Cs(3), and two equivalent Bi(7) atoms to form distorted TeCs4Bi2 pentagonal pyramids that share corners with two equivalent Bi(4)BiTe5 octahedra, corners with two equivalent Te(2)Bi5 square pyramids, corners with two equivalent Te(11)Cs2Bi3 square pyramids, corners with two equivalent Te(14)Cs2Bi3 square pyramids, corners with two equivalent Te(13)CsBi4 trigonal bipyramids, edges with two equivalent Te(24)Cs4Bi2 pentagonal pyramids,  an edgeedge with one Te(2)Bi5 square pyramid,  an edgeedge with one Te(11)Cs2Bi3 square pyramid,  an edgeedge with one Te(14)Cs2Bi3 square pyramid, edges with two equivalent Te(5)CsBi4 trigonal bipyramids,  a faceface with one Te(24)Cs4Bi2 pentagonal pyramid, and faces with two equivalent Te(20)Cs4Bi2 pentagonal pyramids. The corner-sharing octahedral tilt angles are 77°. In the twenty-first Te site, Te(21) is bonded in a 5-coordinate geometry to one Cs(2), two equivalent Cs(1), and two equivalent Bi(14) atoms. In the twenty-second Te site, Te(22) is bonded to one Bi(1), one Bi(16), two equivalent Bi(13), and two equivalent Bi(2) atoms to form TeBi6 octahedra that share  a cornercorner with one Te(10)Bi6 octahedra,  a cornercorner with one Te(12)Bi6 octahedra, corners with two equivalent Te(7)Cs2Bi4 octahedra, corners with two equivalent Te(3)Cs3Bi2 trigonal bipyramids,  an edgeedge with one Te(7)Cs2Bi4 octahedra, edges with two equivalent Te(16)Bi6 octahedra, edges with two equivalent Te(17)Bi6 octahedra, edges with two equivalent Te(22)Bi6 octahedra, edges with two equivalent Te(23)Cs2Bi4 octahedra,  an edgeedge with one Te(3)Cs3Bi2 trigonal bipyramid, and edges with two equivalent Te(8)CsBi4 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 2-8°. In the twenty-third Te site, Te(23) is bonded to two equivalent Cs(4), one Bi(13), one Bi(5), and two equivalent Bi(16) atoms to form TeCs2Bi4 octahedra that share corners with two equivalent Te(16)Bi6 octahedra,  a cornercorner with one Te(13)CsBi4 trigonal bipyramid,  a cornercorner with one Te(8)CsBi4 trigonal bipyramid, corners with two equivalent Te(9)Cs3Bi2 trigonal bipyramids, corners with two equivalent Te(1)CsBi4 trigonal bipyramids,  an edgeedge with one Te(16)Bi6 octahedra, edges with two equivalent Te(12)Bi6 octahedra, edges with two equivalent Te(22)Bi6 octahedra, edges with two equivalent Te(23)Cs2Bi4 octahedra,  an edgeedge with one Te(9)Cs3Bi2 trigonal bipyramid, and edges with two equivalent Te(3)Cs3Bi2 trigonal bipyramids. The corner-sharing octahedral tilt angles are 3°. In the twenty-fourth Te site, Te(24) is bonded to two equivalent Cs(2), two equivalent Cs(3), and two equivalent Bi(12) atoms to form distorted TeCs4Bi2 pentagonal pyramids that share corners with two equivalent Bi(11)BiTe5 octahedra, corners with two equivalent Te(19)Bi5 square pyramids, corners with two equivalent Te(11)Cs2Bi3 square pyramids, corners with two equivalent Te(14)Cs2Bi3 square pyramids, corners with two equivalent Te(5)CsBi4 trigonal bipyramids, edges with two equivalent Te(20)Cs4Bi2 pentagonal pyramids,  an edgeedge with one Te(19)Bi5 square pyramid,  an edgeedge with one Te(11)Cs2Bi3 square pyramid,  an edgeedge with one Te(14)Cs2Bi3 square pyramid, edges with two equivalent Te(13)CsBi4 trigonal bipyramids,  a faceface with one Te(20)Cs4Bi2 pentagonal pyramid, and faces with two equivalent Te(24)Cs4Bi2 pentagonal pyramids. The corner-sharing octahedral tilt angles are 77°.