CsHo2Cu3Se5 crystallizes in the triclinic P1 space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 10-coordinate geometry to two equivalent Cu(3), one Se(1), one Se(10), two equivalent Se(4), two equivalent Se(8), and two equivalent Se(9) atoms. In the second Cs site, Cs(2) is bonded in a 10-coordinate geometry to two equivalent Cu(2), one Se(2), one Se(5), two equivalent Se(3), two equivalent Se(6), and two equivalent Se(7) atoms. There are four inequivalent Ho sites. In the first Ho site, Ho(1) is bonded to one Se(10), one Se(3), two equivalent Se(5), and two equivalent Se(7) atoms to form HoSe6 octahedra that share  a cornercorner with one Ho(4)Se6 octahedra, corners with four equivalent Cu(4)Se4 tetrahedra, edges with two equivalent Ho(1)Se6 octahedra, edges with two equivalent Ho(3)Se6 octahedra,  an edgeedge with one Cu(4)Se4 tetrahedra, and edges with two equivalent Cu(6)Se4 tetrahedra. The corner-sharing octahedral tilt angles are 27°. In the second Ho site, Ho(2) is bonded to one Se(2), one Se(9), two equivalent Se(1), and two equivalent Se(4) atoms to form HoSe6 octahedra that share  a cornercorner with one Ho(3)Se6 octahedra, corners with four equivalent Cu(1)Se4 tetrahedra, edges with two equivalent Ho(2)Se6 octahedra, edges with two equivalent Ho(4)Se6 octahedra,  an edgeedge with one Cu(1)Se4 tetrahedra, and edges with two equivalent Cu(5)Se4 tetrahedra. The corner-sharing octahedral tilt angles are 27°. In the third Ho site, Ho(3) is bonded to one Se(5), one Se(9), two equivalent Se(10), and two equivalent Se(8) atoms to form HoSe6 octahedra that share  a cornercorner with one Ho(2)Se6 octahedra, corners with four equivalent Cu(6)Se4 tetrahedra, edges with two equivalent Ho(1)Se6 octahedra, edges with two equivalent Ho(3)Se6 octahedra,  an edgeedge with one Cu(6)Se4 tetrahedra, and edges with two equivalent Cu(4)Se4 tetrahedra. The corner-sharing octahedral tilt angles are 27°. In the fourth Ho site, Ho(4) is bonded to one Se(1), one Se(3), two equivalent Se(2), and two equivalent Se(6) atoms to form HoSe6 octahedra that share  a cornercorner with one Ho(1)Se6 octahedra, corners with four equivalent Cu(5)Se4 tetrahedra, edges with two equivalent Ho(2)Se6 octahedra, edges with two equivalent Ho(4)Se6 octahedra,  an edgeedge with one Cu(5)Se4 tetrahedra, and edges with two equivalent Cu(1)Se4 tetrahedra. The corner-sharing octahedral tilt angles are 27°. There are six inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one Se(4), one Se(6), and two equivalent Se(1) atoms to form CuSe4 tetrahedra that share corners with four equivalent Ho(2)Se6 octahedra, corners with two equivalent Cu(1)Se4 tetrahedra,  an edgeedge with one Ho(2)Se6 octahedra, edges with two equivalent Ho(4)Se6 octahedra, and  an edgeedge with one Cu(5)Se4 tetrahedra. The corner-sharing octahedral tilt angles range from 15-60°. In the second Cu site, Cu(2) is bonded in a 4-coordinate geometry to two equivalent Cs(2), one Se(6), one Se(7), and two equivalent Se(3) atoms. In the third Cu site, Cu(3) is bonded in a 4-coordinate geometry to two equivalent Cs(1), one Se(4), one Se(8), and two equivalent Se(9) atoms. In the fourth Cu site, Cu(4) is bonded to one Se(7), one Se(8), and two equivalent Se(5) atoms to form CuSe4 tetrahedra that share corners with four equivalent Ho(1)Se6 octahedra, corners with two equivalent Cu(4)Se4 tetrahedra,  an edgeedge with one Ho(1)Se6 octahedra, edges with two equivalent Ho(3)Se6 octahedra, and  an edgeedge with one Cu(6)Se4 tetrahedra. The corner-sharing octahedral tilt angles range from 16-61°. In the fifth Cu site, Cu(5) is bonded to one Se(4), one Se(6), and two equivalent Se(2) atoms to form CuSe4 tetrahedra that share corners with four equivalent Ho(4)Se6 octahedra, corners with two equivalent Cu(5)Se4 tetrahedra,  an edgeedge with one Ho(4)Se6 octahedra, edges with two equivalent Ho(2)Se6 octahedra, and  an edgeedge with one Cu(1)Se4 tetrahedra. The corner-sharing octahedral tilt angles range from 15-60°. In the sixth Cu site, Cu(6) is bonded to one Se(7), one Se(8), and two equivalent Se(10) atoms to form CuSe4 tetrahedra that share corners with four equivalent Ho(3)Se6 octahedra, corners with two equivalent Cu(6)Se4 tetrahedra,  an edgeedge with one Ho(3)Se6 octahedra, edges with two equivalent Ho(1)Se6 octahedra, and  an edgeedge with one Cu(4)Se4 tetrahedra. The corner-sharing octahedral tilt angles range from 15-60°. There are ten inequivalent Se sites. In the first Se site, Se(1) is bonded to one Cs(1), one Ho(4), two equivalent Ho(2), and two equivalent Cu(1) atoms to form a mixture of distorted edge and corner-sharing SeCsHo3Cu2 octahedra. The corner-sharing octahedral tilt angles are 54°. In the second Se site, Se(2) is bonded to one Cs(2), one Ho(2), two equivalent Ho(4), and two equivalent Cu(5) atoms to form a mixture of distorted edge and corner-sharing SeCsHo3Cu2 octahedra. The corner-sharing octahedral tilt angles are 55°. In the third Se site, Se(3) is bonded in a 6-coordinate geometry to two equivalent Cs(2), one Ho(1), one Ho(4), and two equivalent Cu(2) atoms. In the fourth Se site, Se(4) is bonded in a 7-coordinate geometry to two equivalent Cs(1), two equivalent Ho(2), one Cu(1), one Cu(3), and one Cu(5) atom. In the fifth Se site, Se(5) is bonded to one Cs(2), one Ho(3), two equivalent Ho(1), and two equivalent Cu(4) atoms to form a mixture of distorted edge and corner-sharing SeCsHo3Cu2 octahedra. The corner-sharing octahedral tilt angles are 55°. In the sixth Se site, Se(6) is bonded in a 7-coordinate geometry to two equivalent Cs(2), two equivalent Ho(4), one Cu(1), one Cu(2), and one Cu(5) atom. In the seventh Se site, Se(7) is bonded in a 7-coordinate geometry to two equivalent Cs(2), two equivalent Ho(1), one Cu(2), one Cu(4), and one Cu(6) atom. In the eighth Se site, Se(8) is bonded in a 7-coordinate geometry to two equivalent Cs(1), two equivalent Ho(3), one Cu(3), one Cu(4), and one Cu(6) atom. In the ninth Se site, Se(9) is bonded in a 6-coordinate geometry to two equivalent Cs(1), one Ho(2), one Ho(3), and two equivalent Cu(3) atoms. In the tenth Se site, Se(10) is bonded to one Cs(1), one Ho(1), two equivalent Ho(3), and two equivalent Cu(6) atoms to form a mixture of distorted edge and corner-sharing SeCsHo3Cu2 octahedra. The corner-sharing octahedral tilt angles are 54°.
CsHo2Cu3Se5 crystallizes in the triclinic P1 space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 10-coordinate geometry to two equivalent Cu(3), one Se(1), one Se(10), two equivalent Se(4), two equivalent Se(8), and two equivalent Se(9) atoms. There is one shorter (3.80 Å) and one longer (3.82 Å) Cs(1)-Cu(3) bond length. The Cs(1)-Se(1) bond length is 3.50 Å. The Cs(1)-Se(10) bond length is 3.51 Å. There is one shorter (3.63 Å) and one longer (3.66 Å) Cs(1)-Se(4) bond length. There is one shorter (3.65 Å) and one longer (3.67 Å) Cs(1)-Se(8) bond length. Both Cs(1)-Se(9) bond lengths are 3.62 Å. In the second Cs site, Cs(2) is bonded in a 10-coordinate geometry to two equivalent Cu(2), one Se(2), one Se(5), two equivalent Se(3), two equivalent Se(6), and two equivalent Se(7) atoms. There is one shorter (3.79 Å) and one longer (3.81 Å) Cs(2)-Cu(2) bond length. The Cs(2)-Se(2) bond length is 3.51 Å. The Cs(2)-Se(5) bond length is 3.51 Å. There is one shorter (3.63 Å) and one longer (3.65 Å) Cs(2)-Se(3) bond length. There is one shorter (3.64 Å) and one longer (3.67 Å) Cs(2)-Se(6) bond length. There is one shorter (3.62 Å) and one longer (3.64 Å) Cs(2)-Se(7) bond length. There are four inequivalent Ho sites. In the first Ho site, Ho(1) is bonded to one Se(10), one Se(3), two equivalent Se(5), and two equivalent Se(7) atoms to form HoSe6 octahedra that share  a cornercorner with one Ho(4)Se6 octahedra, corners with four equivalent Cu(4)Se4 tetrahedra, edges with two equivalent Ho(1)Se6 octahedra, edges with two equivalent Ho(3)Se6 octahedra,  an edgeedge with one Cu(4)Se4 tetrahedra, and edges with two equivalent Cu(6)Se4 tetrahedra. The corner-sharing octahedral tilt angles are 27°. The Ho(1)-Se(10) bond length is 2.82 Å. The Ho(1)-Se(3) bond length is 2.84 Å. There is one shorter (2.93 Å) and one longer (2.94 Å) Ho(1)-Se(5) bond length. There is one shorter (2.83 Å) and one longer (2.84 Å) Ho(1)-Se(7) bond length. In the second Ho site, Ho(2) is bonded to one Se(2), one Se(9), two equivalent Se(1), and two equivalent Se(4) atoms to form HoSe6 octahedra that share  a cornercorner with one Ho(3)Se6 octahedra, corners with four equivalent Cu(1)Se4 tetrahedra, edges with two equivalent Ho(2)Se6 octahedra, edges with two equivalent Ho(4)Se6 octahedra,  an edgeedge with one Cu(1)Se4 tetrahedra, and edges with two equivalent Cu(5)Se4 tetrahedra. The corner-sharing octahedral tilt angles are 27°. The Ho(2)-Se(2) bond length is 2.83 Å. The Ho(2)-Se(9) bond length is 2.84 Å. There is one shorter (2.93 Å) and one longer (2.94 Å) Ho(2)-Se(1) bond length. There is one shorter (2.83 Å) and one longer (2.84 Å) Ho(2)-Se(4) bond length. In the third Ho site, Ho(3) is bonded to one Se(5), one Se(9), two equivalent Se(10), and two equivalent Se(8) atoms to form HoSe6 octahedra that share  a cornercorner with one Ho(2)Se6 octahedra, corners with four equivalent Cu(6)Se4 tetrahedra, edges with two equivalent Ho(1)Se6 octahedra, edges with two equivalent Ho(3)Se6 octahedra,  an edgeedge with one Cu(6)Se4 tetrahedra, and edges with two equivalent Cu(4)Se4 tetrahedra. The corner-sharing octahedral tilt angles are 27°. The Ho(3)-Se(5) bond length is 2.82 Å. The Ho(3)-Se(9) bond length is 2.84 Å. Both Ho(3)-Se(10) bond lengths are 2.94 Å. Both Ho(3)-Se(8) bond lengths are 2.83 Å. In the fourth Ho site, Ho(4) is bonded to one Se(1), one Se(3), two equivalent Se(2), and two equivalent Se(6) atoms to form HoSe6 octahedra that share  a cornercorner with one Ho(1)Se6 octahedra, corners with four equivalent Cu(5)Se4 tetrahedra, edges with two equivalent Ho(2)Se6 octahedra, edges with two equivalent Ho(4)Se6 octahedra,  an edgeedge with one Cu(5)Se4 tetrahedra, and edges with two equivalent Cu(1)Se4 tetrahedra. The corner-sharing octahedral tilt angles are 27°. The Ho(4)-Se(1) bond length is 2.82 Å. The Ho(4)-Se(3) bond length is 2.84 Å. There is one shorter (2.92 Å) and one longer (2.93 Å) Ho(4)-Se(2) bond length. There is one shorter (2.83 Å) and one longer (2.84 Å) Ho(4)-Se(6) bond length. There are six inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one Se(4), one Se(6), and two equivalent Se(1) atoms to form CuSe4 tetrahedra that share corners with four equivalent Ho(2)Se6 octahedra, corners with two equivalent Cu(1)Se4 tetrahedra,  an edgeedge with one Ho(2)Se6 octahedra, edges with two equivalent Ho(4)Se6 octahedra, and  an edgeedge with one Cu(5)Se4 tetrahedra. The corner-sharing octahedral tilt angles range from 15-60°. The Cu(1)-Se(4) bond length is 2.53 Å. The Cu(1)-Se(6) bond length is 2.54 Å. There is one shorter (2.48 Å) and one longer (2.51 Å) Cu(1)-Se(1) bond length. In the second Cu site, Cu(2) is bonded in a 4-coordinate geometry to two equivalent Cs(2), one Se(6), one Se(7), and two equivalent Se(3) atoms. The Cu(2)-Se(6) bond length is 2.80 Å. The Cu(2)-Se(7) bond length is 2.78 Å. Both Cu(2)-Se(3) bond lengths are 2.37 Å. In the third Cu site, Cu(3) is bonded in a 4-coordinate geometry to two equivalent Cs(1), one Se(4), one Se(8), and two equivalent Se(9) atoms. The Cu(3)-Se(4) bond length is 2.80 Å. The Cu(3)-Se(8) bond length is 2.76 Å. There is one shorter (2.37 Å) and one longer (2.38 Å) Cu(3)-Se(9) bond length. In the fourth Cu site, Cu(4) is bonded to one Se(7), one Se(8), and two equivalent Se(5) atoms to form CuSe4 tetrahedra that share corners with four equivalent Ho(1)Se6 octahedra, corners with two equivalent Cu(4)Se4 tetrahedra,  an edgeedge with one Ho(1)Se6 octahedra, edges with two equivalent Ho(3)Se6 octahedra, and  an edgeedge with one Cu(6)Se4 tetrahedra. The corner-sharing octahedral tilt angles range from 16-61°. The Cu(4)-Se(7) bond length is 2.55 Å. The Cu(4)-Se(8) bond length is 2.52 Å. There is one shorter (2.48 Å) and one longer (2.51 Å) Cu(4)-Se(5) bond length. In the fifth Cu site, Cu(5) is bonded to one Se(4), one Se(6), and two equivalent Se(2) atoms to form CuSe4 tetrahedra that share corners with four equivalent Ho(4)Se6 octahedra, corners with two equivalent Cu(5)Se4 tetrahedra,  an edgeedge with one Ho(4)Se6 octahedra, edges with two equivalent Ho(2)Se6 octahedra, and  an edgeedge with one Cu(1)Se4 tetrahedra. The corner-sharing octahedral tilt angles range from 15-60°. The Cu(5)-Se(4) bond length is 2.53 Å. The Cu(5)-Se(6) bond length is 2.53 Å. There is one shorter (2.50 Å) and one longer (2.51 Å) Cu(5)-Se(2) bond length. In the sixth Cu site, Cu(6) is bonded to one Se(7), one Se(8), and two equivalent Se(10) atoms to form CuSe4 tetrahedra that share corners with four equivalent Ho(3)Se6 octahedra, corners with two equivalent Cu(6)Se4 tetrahedra,  an edgeedge with one Ho(3)Se6 octahedra, edges with two equivalent Ho(1)Se6 octahedra, and  an edgeedge with one Cu(4)Se4 tetrahedra. The corner-sharing octahedral tilt angles range from 15-60°. The Cu(6)-Se(7) bond length is 2.52 Å. The Cu(6)-Se(8) bond length is 2.54 Å. Both Cu(6)-Se(10) bond lengths are 2.50 Å. There are ten inequivalent Se sites. In the first Se site, Se(1) is bonded to one Cs(1), one Ho(4), two equivalent Ho(2), and two equivalent Cu(1) atoms to form a mixture of distorted edge and corner-sharing SeCsHo3Cu2 octahedra. The corner-sharing octahedral tilt angles are 54°. In the second Se site, Se(2) is bonded to one Cs(2), one Ho(2), two equivalent Ho(4), and two equivalent Cu(5) atoms to form a mixture of distorted edge and corner-sharing SeCsHo3Cu2 octahedra. The corner-sharing octahedral tilt angles are 55°. In the third Se site, Se(3) is bonded in a 6-coordinate geometry to two equivalent Cs(2), one Ho(1), one Ho(4), and two equivalent Cu(2) atoms. In the fourth Se site, Se(4) is bonded in a 7-coordinate geometry to two equivalent Cs(1), two equivalent Ho(2), one Cu(1), one Cu(3), and one Cu(5) atom. In the fifth Se site, Se(5) is bonded to one Cs(2), one Ho(3), two equivalent Ho(1), and two equivalent Cu(4) atoms to form a mixture of distorted edge and corner-sharing SeCsHo3Cu2 octahedra. The corner-sharing octahedral tilt angles are 55°. In the sixth Se site, Se(6) is bonded in a 7-coordinate geometry to two equivalent Cs(2), two equivalent Ho(4), one Cu(1), one Cu(2), and one Cu(5) atom. In the seventh Se site, Se(7) is bonded in a 7-coordinate geometry to two equivalent Cs(2), two equivalent Ho(1), one Cu(2), one Cu(4), and one Cu(6) atom. In the eighth Se site, Se(8) is bonded in a 7-coordinate geometry to two equivalent Cs(1), two equivalent Ho(3), one Cu(3), one Cu(4), and one Cu(6) atom. In the ninth Se site, Se(9) is bonded in a 6-coordinate geometry to two equivalent Cs(1), one Ho(2), one Ho(3), and two equivalent Cu(3) atoms. In the tenth Se site, Se(10) is bonded to one Cs(1), one Ho(1), two equivalent Ho(3), and two equivalent Cu(6) atoms to form a mixture of distorted edge and corner-sharing SeCsHo3Cu2 octahedra. The corner-sharing octahedral tilt angles are 54°.