MnZn4Se5 is Chalcopyrite-like structured and crystallizes in the monoclinic Cm space group. Mn(1) is bonded to one Se(3), one Se(5), and two equivalent Se(2) atoms to form MnSe4 tetrahedra that share corners with two equivalent Mn(1)Se4 tetrahedra, corners with two equivalent Zn(1)Se4 tetrahedra, corners with two equivalent Zn(4)Se4 tetrahedra, corners with three equivalent Zn(2)Se4 tetrahedra, and corners with three equivalent Zn(3)Se4 tetrahedra. There are four inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one Se(1), one Se(4), and two equivalent Se(3) atoms to form ZnSe4 tetrahedra that share corners with two equivalent Mn(1)Se4 tetrahedra, corners with two equivalent Zn(1)Se4 tetrahedra, corners with two equivalent Zn(2)Se4 tetrahedra, corners with three equivalent Zn(3)Se4 tetrahedra, and corners with three equivalent Zn(4)Se4 tetrahedra. In the second Zn site, Zn(2) is bonded to one Se(2), one Se(5), and two equivalent Se(4) atoms to form ZnSe4 tetrahedra that share corners with two equivalent Zn(1)Se4 tetrahedra, corners with two equivalent Zn(2)Se4 tetrahedra, corners with two equivalent Zn(3)Se4 tetrahedra, corners with three equivalent Mn(1)Se4 tetrahedra, and corners with three equivalent Zn(4)Se4 tetrahedra. In the third Zn site, Zn(3) is bonded to one Se(1), one Se(3), and two equivalent Se(5) atoms to form ZnSe4 tetrahedra that share corners with two equivalent Zn(2)Se4 tetrahedra, corners with two equivalent Zn(3)Se4 tetrahedra, corners with two equivalent Zn(4)Se4 tetrahedra, corners with three equivalent Mn(1)Se4 tetrahedra, and corners with three equivalent Zn(1)Se4 tetrahedra. In the fourth Zn site, Zn(4) is bonded to one Se(2), one Se(4), and two equivalent Se(1) atoms to form ZnSe4 tetrahedra that share corners with two equivalent Mn(1)Se4 tetrahedra, corners with two equivalent Zn(3)Se4 tetrahedra, corners with two equivalent Zn(4)Se4 tetrahedra, corners with three equivalent Zn(1)Se4 tetrahedra, and corners with three equivalent Zn(2)Se4 tetrahedra. There are five inequivalent Se sites. In the first Se site, Se(1) is bonded to one Zn(1), one Zn(3), and two equivalent Zn(4) atoms to form SeZn4 tetrahedra that share corners with two equivalent Se(2)Mn2Zn2 tetrahedra, corners with two equivalent Se(5)MnZn3 tetrahedra, corners with two equivalent Se(1)Zn4 tetrahedra, corners with three equivalent Se(3)MnZn3 tetrahedra, and corners with three equivalent Se(4)Zn4 tetrahedra. In the second Se site, Se(2) is bonded to two equivalent Mn(1), one Zn(2), and one Zn(4) atom to form SeMn2Zn2 tetrahedra that share corners with two equivalent Se(2)Mn2Zn2 tetrahedra, corners with two equivalent Se(3)MnZn3 tetrahedra, corners with two equivalent Se(1)Zn4 tetrahedra, corners with three equivalent Se(5)MnZn3 tetrahedra, and corners with three equivalent Se(4)Zn4 tetrahedra. In the third Se site, Se(3) is bonded to one Mn(1), one Zn(3), and two equivalent Zn(1) atoms to form SeMnZn3 tetrahedra that share corners with two equivalent Se(2)Mn2Zn2 tetrahedra, corners with two equivalent Se(3)MnZn3 tetrahedra, corners with two equivalent Se(4)Zn4 tetrahedra, corners with three equivalent Se(5)MnZn3 tetrahedra, and corners with three equivalent Se(1)Zn4 tetrahedra. In the fourth Se site, Se(4) is bonded to one Zn(1), one Zn(4), and two equivalent Zn(2) atoms to form SeZn4 tetrahedra that share corners with two equivalent Se(3)MnZn3 tetrahedra, corners with two equivalent Se(5)MnZn3 tetrahedra, corners with two equivalent Se(4)Zn4 tetrahedra, corners with three equivalent Se(2)Mn2Zn2 tetrahedra, and corners with three equivalent Se(1)Zn4 tetrahedra. In the fifth Se site, Se(5) is bonded to one Mn(1), one Zn(2), and two equivalent Zn(3) atoms to form SeMnZn3 tetrahedra that share corners with two equivalent Se(5)MnZn3 tetrahedra, corners with two equivalent Se(1)Zn4 tetrahedra, corners with two equivalent Se(4)Zn4 tetrahedra, corners with three equivalent Se(2)Mn2Zn2 tetrahedra, and corners with three equivalent Se(3)MnZn3 tetrahedra.
MnZn4Se5 is Chalcopyrite-like structured and crystallizes in the monoclinic Cm space group. Mn(1) is bonded to one Se(3), one Se(5), and two equivalent Se(2) atoms to form MnSe4 tetrahedra that share corners with two equivalent Mn(1)Se4 tetrahedra, corners with two equivalent Zn(1)Se4 tetrahedra, corners with two equivalent Zn(4)Se4 tetrahedra, corners with three equivalent Zn(2)Se4 tetrahedra, and corners with three equivalent Zn(3)Se4 tetrahedra. The Mn(1)-Se(3) bond length is 2.53 Å. The Mn(1)-Se(5) bond length is 2.53 Å. Both Mn(1)-Se(2) bond lengths are 2.53 Å. There are four inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one Se(1), one Se(4), and two equivalent Se(3) atoms to form ZnSe4 tetrahedra that share corners with two equivalent Mn(1)Se4 tetrahedra, corners with two equivalent Zn(1)Se4 tetrahedra, corners with two equivalent Zn(2)Se4 tetrahedra, corners with three equivalent Zn(3)Se4 tetrahedra, and corners with three equivalent Zn(4)Se4 tetrahedra. The Zn(1)-Se(1) bond length is 2.46 Å. The Zn(1)-Se(4) bond length is 2.45 Å. Both Zn(1)-Se(3) bond lengths are 2.46 Å. In the second Zn site, Zn(2) is bonded to one Se(2), one Se(5), and two equivalent Se(4) atoms to form ZnSe4 tetrahedra that share corners with two equivalent Zn(1)Se4 tetrahedra, corners with two equivalent Zn(2)Se4 tetrahedra, corners with two equivalent Zn(3)Se4 tetrahedra, corners with three equivalent Mn(1)Se4 tetrahedra, and corners with three equivalent Zn(4)Se4 tetrahedra. The Zn(2)-Se(2) bond length is 2.45 Å. The Zn(2)-Se(5) bond length is 2.46 Å. Both Zn(2)-Se(4) bond lengths are 2.46 Å. In the third Zn site, Zn(3) is bonded to one Se(1), one Se(3), and two equivalent Se(5) atoms to form ZnSe4 tetrahedra that share corners with two equivalent Zn(2)Se4 tetrahedra, corners with two equivalent Zn(3)Se4 tetrahedra, corners with two equivalent Zn(4)Se4 tetrahedra, corners with three equivalent Mn(1)Se4 tetrahedra, and corners with three equivalent Zn(1)Se4 tetrahedra. The Zn(3)-Se(1) bond length is 2.46 Å. The Zn(3)-Se(3) bond length is 2.45 Å. Both Zn(3)-Se(5) bond lengths are 2.46 Å. In the fourth Zn site, Zn(4) is bonded to one Se(2), one Se(4), and two equivalent Se(1) atoms to form ZnSe4 tetrahedra that share corners with two equivalent Mn(1)Se4 tetrahedra, corners with two equivalent Zn(3)Se4 tetrahedra, corners with two equivalent Zn(4)Se4 tetrahedra, corners with three equivalent Zn(1)Se4 tetrahedra, and corners with three equivalent Zn(2)Se4 tetrahedra. The Zn(4)-Se(2) bond length is 2.45 Å. The Zn(4)-Se(4) bond length is 2.46 Å. Both Zn(4)-Se(1) bond lengths are 2.46 Å. There are five inequivalent Se sites. In the first Se site, Se(1) is bonded to one Zn(1), one Zn(3), and two equivalent Zn(4) atoms to form SeZn4 tetrahedra that share corners with two equivalent Se(2)Mn2Zn2 tetrahedra, corners with two equivalent Se(5)MnZn3 tetrahedra, corners with two equivalent Se(1)Zn4 tetrahedra, corners with three equivalent Se(3)MnZn3 tetrahedra, and corners with three equivalent Se(4)Zn4 tetrahedra. In the second Se site, Se(2) is bonded to two equivalent Mn(1), one Zn(2), and one Zn(4) atom to form SeMn2Zn2 tetrahedra that share corners with two equivalent Se(2)Mn2Zn2 tetrahedra, corners with two equivalent Se(3)MnZn3 tetrahedra, corners with two equivalent Se(1)Zn4 tetrahedra, corners with three equivalent Se(5)MnZn3 tetrahedra, and corners with three equivalent Se(4)Zn4 tetrahedra. In the third Se site, Se(3) is bonded to one Mn(1), one Zn(3), and two equivalent Zn(1) atoms to form SeMnZn3 tetrahedra that share corners with two equivalent Se(2)Mn2Zn2 tetrahedra, corners with two equivalent Se(3)MnZn3 tetrahedra, corners with two equivalent Se(4)Zn4 tetrahedra, corners with three equivalent Se(5)MnZn3 tetrahedra, and corners with three equivalent Se(1)Zn4 tetrahedra. In the fourth Se site, Se(4) is bonded to one Zn(1), one Zn(4), and two equivalent Zn(2) atoms to form SeZn4 tetrahedra that share corners with two equivalent Se(3)MnZn3 tetrahedra, corners with two equivalent Se(5)MnZn3 tetrahedra, corners with two equivalent Se(4)Zn4 tetrahedra, corners with three equivalent Se(2)Mn2Zn2 tetrahedra, and corners with three equivalent Se(1)Zn4 tetrahedra. In the fifth Se site, Se(5) is bonded to one Mn(1), one Zn(2), and two equivalent Zn(3) atoms to form SeMnZn3 tetrahedra that share corners with two equivalent Se(5)MnZn3 tetrahedra, corners with two equivalent Se(1)Zn4 tetrahedra, corners with two equivalent Se(4)Zn4 tetrahedra, corners with three equivalent Se(2)Mn2Zn2 tetrahedra, and corners with three equivalent Se(3)MnZn3 tetrahedra.