MnCu4Cd(GeSe4)2 is Clathrate-derived structured and crystallizes in the monoclinic Pm space group. Mn(1) is bonded to one Se(4), one Se(6), and two equivalent Se(1) atoms to form MnSe4 tetrahedra that share corners with two equivalent Ge(1)Se4 tetrahedra, corners with two equivalent Ge(2)Se4 tetrahedra, corners with four equivalent Cu(1)Se4 tetrahedra, and corners with four equivalent Cu(2)Se4 tetrahedra. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one Se(1), one Se(2), one Se(4), and one Se(5) atom to form CuSe4 tetrahedra that share corners with two equivalent Mn(1)Se4 tetrahedra, corners with two equivalent Cu(1)Se4 tetrahedra, corners with two equivalent Cu(2)Se4 tetrahedra, corners with two equivalent Cd(1)Se4 tetrahedra, corners with two equivalent Ge(1)Se4 tetrahedra, and corners with two equivalent Ge(2)Se4 tetrahedra. In the second Cu site, Cu(2) is bonded to one Se(1), one Se(2), one Se(3), and one Se(6) atom to form CuSe4 tetrahedra that share corners with two equivalent Mn(1)Se4 tetrahedra, corners with two equivalent Cu(1)Se4 tetrahedra, corners with two equivalent Cu(2)Se4 tetrahedra, corners with two equivalent Cd(1)Se4 tetrahedra, corners with two equivalent Ge(1)Se4 tetrahedra, and corners with two equivalent Ge(2)Se4 tetrahedra. Cd(1) is bonded to one Se(3), one Se(5), and two equivalent Se(2) atoms to form CdSe4 tetrahedra that share corners with two equivalent Ge(1)Se4 tetrahedra, corners with two equivalent Ge(2)Se4 tetrahedra, corners with four equivalent Cu(1)Se4 tetrahedra, and corners with four equivalent Cu(2)Se4 tetrahedra. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one Se(3), one Se(5), and two equivalent Se(1) atoms to form GeSe4 tetrahedra that share corners with two equivalent Mn(1)Se4 tetrahedra, corners with two equivalent Cd(1)Se4 tetrahedra, corners with four equivalent Cu(1)Se4 tetrahedra, and corners with four equivalent Cu(2)Se4 tetrahedra. In the second Ge site, Ge(2) is bonded to one Se(4), one Se(6), and two equivalent Se(2) atoms to form GeSe4 tetrahedra that share corners with two equivalent Mn(1)Se4 tetrahedra, corners with two equivalent Cd(1)Se4 tetrahedra, corners with four equivalent Cu(1)Se4 tetrahedra, and corners with four equivalent Cu(2)Se4 tetrahedra. There are six inequivalent Se sites. In the first Se site, Se(1) is bonded to one Mn(1), one Cu(1), one Cu(2), and one Ge(1) atom to form SeMnCu2Ge tetrahedra that share corners with two equivalent Se(2)CdCu2Ge tetrahedra, corners with two equivalent Se(3)CdCu2Ge tetrahedra, corners with two equivalent Se(5)CdCu2Ge tetrahedra, corners with two equivalent Se(1)MnCu2Ge tetrahedra, corners with two equivalent Se(4)MnCu2Ge tetrahedra, and corners with two equivalent Se(6)MnCu2Ge tetrahedra. In the second Se site, Se(2) is bonded to one Cu(1), one Cu(2), one Cd(1), and one Ge(2) atom to form SeCdCu2Ge tetrahedra that share corners with two equivalent Se(2)CdCu2Ge tetrahedra, corners with two equivalent Se(3)CdCu2Ge tetrahedra, corners with two equivalent Se(5)CdCu2Ge tetrahedra, corners with two equivalent Se(1)MnCu2Ge tetrahedra, corners with two equivalent Se(4)MnCu2Ge tetrahedra, and corners with two equivalent Se(6)MnCu2Ge tetrahedra. In the third Se site, Se(3) is bonded to two equivalent Cu(2), one Cd(1), and one Ge(1) atom to form SeCdCu2Ge tetrahedra that share corners with two equivalent Se(5)CdCu2Ge tetrahedra, corners with two equivalent Se(6)MnCu2Ge tetrahedra, corners with four equivalent Se(2)CdCu2Ge tetrahedra, and corners with four equivalent Se(1)MnCu2Ge tetrahedra. In the fourth Se site, Se(4) is bonded to one Mn(1), two equivalent Cu(1), and one Ge(2) atom to form SeMnCu2Ge tetrahedra that share corners with two equivalent Se(5)CdCu2Ge tetrahedra, corners with two equivalent Se(6)MnCu2Ge tetrahedra, corners with four equivalent Se(2)CdCu2Ge tetrahedra, and corners with four equivalent Se(1)MnCu2Ge tetrahedra. In the fifth Se site, Se(5) is bonded to two equivalent Cu(1), one Cd(1), and one Ge(1) atom to form SeCdCu2Ge tetrahedra that share corners with two equivalent Se(3)CdCu2Ge tetrahedra, corners with two equivalent Se(4)MnCu2Ge tetrahedra, corners with four equivalent Se(2)CdCu2Ge tetrahedra, and corners with four equivalent Se(1)MnCu2Ge tetrahedra. In the sixth Se site, Se(6) is bonded to one Mn(1), two equivalent Cu(2), and one Ge(2) atom to form SeMnCu2Ge tetrahedra that share corners with two equivalent Se(3)CdCu2Ge tetrahedra, corners with two equivalent Se(4)MnCu2Ge tetrahedra, corners with four equivalent Se(2)CdCu2Ge tetrahedra, and corners with four equivalent Se(1)MnCu2Ge tetrahedra.
MnCu4Cd(GeSe4)2 is Clathrate-derived structured and crystallizes in the monoclinic Pm space group. Mn(1) is bonded to one Se(4), one Se(6), and two equivalent Se(1) atoms to form MnSe4 tetrahedra that share corners with two equivalent Ge(1)Se4 tetrahedra, corners with two equivalent Ge(2)Se4 tetrahedra, corners with four equivalent Cu(1)Se4 tetrahedra, and corners with four equivalent Cu(2)Se4 tetrahedra. The Mn(1)-Se(4) bond length is 2.53 Å. The Mn(1)-Se(6) bond length is 2.54 Å. Both Mn(1)-Se(1) bond lengths are 2.59 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one Se(1), one Se(2), one Se(4), and one Se(5) atom to form CuSe4 tetrahedra that share corners with two equivalent Mn(1)Se4 tetrahedra, corners with two equivalent Cu(1)Se4 tetrahedra, corners with two equivalent Cu(2)Se4 tetrahedra, corners with two equivalent Cd(1)Se4 tetrahedra, corners with two equivalent Ge(1)Se4 tetrahedra, and corners with two equivalent Ge(2)Se4 tetrahedra. The Cu(1)-Se(1) bond length is 2.46 Å. The Cu(1)-Se(2) bond length is 2.43 Å. The Cu(1)-Se(4) bond length is 2.41 Å. The Cu(1)-Se(5) bond length is 2.42 Å. In the second Cu site, Cu(2) is bonded to one Se(1), one Se(2), one Se(3), and one Se(6) atom to form CuSe4 tetrahedra that share corners with two equivalent Mn(1)Se4 tetrahedra, corners with two equivalent Cu(1)Se4 tetrahedra, corners with two equivalent Cu(2)Se4 tetrahedra, corners with two equivalent Cd(1)Se4 tetrahedra, corners with two equivalent Ge(1)Se4 tetrahedra, and corners with two equivalent Ge(2)Se4 tetrahedra. The Cu(2)-Se(1) bond length is 2.43 Å. The Cu(2)-Se(2) bond length is 2.44 Å. The Cu(2)-Se(3) bond length is 2.40 Å. The Cu(2)-Se(6) bond length is 2.44 Å. Cd(1) is bonded to one Se(3), one Se(5), and two equivalent Se(2) atoms to form CdSe4 tetrahedra that share corners with two equivalent Ge(1)Se4 tetrahedra, corners with two equivalent Ge(2)Se4 tetrahedra, corners with four equivalent Cu(1)Se4 tetrahedra, and corners with four equivalent Cu(2)Se4 tetrahedra. The Cd(1)-Se(3) bond length is 2.67 Å. The Cd(1)-Se(5) bond length is 2.67 Å. Both Cd(1)-Se(2) bond lengths are 2.69 Å. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one Se(3), one Se(5), and two equivalent Se(1) atoms to form GeSe4 tetrahedra that share corners with two equivalent Mn(1)Se4 tetrahedra, corners with two equivalent Cd(1)Se4 tetrahedra, corners with four equivalent Cu(1)Se4 tetrahedra, and corners with four equivalent Cu(2)Se4 tetrahedra. The Ge(1)-Se(3) bond length is 2.44 Å. The Ge(1)-Se(5) bond length is 2.43 Å. Both Ge(1)-Se(1) bond lengths are 2.45 Å. In the second Ge site, Ge(2) is bonded to one Se(4), one Se(6), and two equivalent Se(2) atoms to form GeSe4 tetrahedra that share corners with two equivalent Mn(1)Se4 tetrahedra, corners with two equivalent Cd(1)Se4 tetrahedra, corners with four equivalent Cu(1)Se4 tetrahedra, and corners with four equivalent Cu(2)Se4 tetrahedra. The Ge(2)-Se(4) bond length is 2.45 Å. The Ge(2)-Se(6) bond length is 2.43 Å. Both Ge(2)-Se(2) bond lengths are 2.43 Å. There are six inequivalent Se sites. In the first Se site, Se(1) is bonded to one Mn(1), one Cu(1), one Cu(2), and one Ge(1) atom to form SeMnCu2Ge tetrahedra that share corners with two equivalent Se(2)CdCu2Ge tetrahedra, corners with two equivalent Se(3)CdCu2Ge tetrahedra, corners with two equivalent Se(5)CdCu2Ge tetrahedra, corners with two equivalent Se(1)MnCu2Ge tetrahedra, corners with two equivalent Se(4)MnCu2Ge tetrahedra, and corners with two equivalent Se(6)MnCu2Ge tetrahedra. In the second Se site, Se(2) is bonded to one Cu(1), one Cu(2), one Cd(1), and one Ge(2) atom to form SeCdCu2Ge tetrahedra that share corners with two equivalent Se(2)CdCu2Ge tetrahedra, corners with two equivalent Se(3)CdCu2Ge tetrahedra, corners with two equivalent Se(5)CdCu2Ge tetrahedra, corners with two equivalent Se(1)MnCu2Ge tetrahedra, corners with two equivalent Se(4)MnCu2Ge tetrahedra, and corners with two equivalent Se(6)MnCu2Ge tetrahedra. In the third Se site, Se(3) is bonded to two equivalent Cu(2), one Cd(1), and one Ge(1) atom to form SeCdCu2Ge tetrahedra that share corners with two equivalent Se(5)CdCu2Ge tetrahedra, corners with two equivalent Se(6)MnCu2Ge tetrahedra, corners with four equivalent Se(2)CdCu2Ge tetrahedra, and corners with four equivalent Se(1)MnCu2Ge tetrahedra. In the fourth Se site, Se(4) is bonded to one Mn(1), two equivalent Cu(1), and one Ge(2) atom to form SeMnCu2Ge tetrahedra that share corners with two equivalent Se(5)CdCu2Ge tetrahedra, corners with two equivalent Se(6)MnCu2Ge tetrahedra, corners with four equivalent Se(2)CdCu2Ge tetrahedra, and corners with four equivalent Se(1)MnCu2Ge tetrahedra. In the fifth Se site, Se(5) is bonded to two equivalent Cu(1), one Cd(1), and one Ge(1) atom to form SeCdCu2Ge tetrahedra that share corners with two equivalent Se(3)CdCu2Ge tetrahedra, corners with two equivalent Se(4)MnCu2Ge tetrahedra, corners with four equivalent Se(2)CdCu2Ge tetrahedra, and corners with four equivalent Se(1)MnCu2Ge tetrahedra. In the sixth Se site, Se(6) is bonded to one Mn(1), two equivalent Cu(2), and one Ge(2) atom to form SeMnCu2Ge tetrahedra that share corners with two equivalent Se(3)CdCu2Ge tetrahedra, corners with two equivalent Se(4)MnCu2Ge tetrahedra, corners with four equivalent Se(2)CdCu2Ge tetrahedra, and corners with four equivalent Se(1)MnCu2Ge tetrahedra.