FeCu4Zn(GeS4)2 is Stannite-derived structured and crystallizes in the orthorhombic Amm2 space group. Fe(1) is bonded to two equivalent S(1) and two equivalent S(3) atoms to form FeS4 tetrahedra that share corners with two equivalent Ge(1)S4 tetrahedra, corners with two equivalent Ge(2)S4 tetrahedra, and corners with eight equivalent Cu(1)S4 tetrahedra. Cu(1) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form CuS4 tetrahedra that share corners with two equivalent Fe(1)S4 tetrahedra, corners with two equivalent Zn(1)S4 tetrahedra, corners with two equivalent Ge(1)S4 tetrahedra, corners with two equivalent Ge(2)S4 tetrahedra, and corners with four equivalent Cu(1)S4 tetrahedra. Zn(1) is bonded to two equivalent S(2) and two equivalent S(4) atoms to form ZnS4 tetrahedra that share corners with two equivalent Ge(1)S4 tetrahedra, corners with two equivalent Ge(2)S4 tetrahedra, and corners with eight equivalent Cu(1)S4 tetrahedra. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to two equivalent S(1) and two equivalent S(4) atoms to form GeS4 tetrahedra that share corners with two equivalent Fe(1)S4 tetrahedra, corners with two equivalent Zn(1)S4 tetrahedra, and corners with eight equivalent Cu(1)S4 tetrahedra. In the second Ge site, Ge(2) is bonded to two equivalent S(2) and two equivalent S(3) atoms to form GeS4 tetrahedra that share corners with two equivalent Fe(1)S4 tetrahedra, corners with two equivalent Zn(1)S4 tetrahedra, and corners with eight equivalent Cu(1)S4 tetrahedra. There are four inequivalent S sites. In the first S site, S(1) is bonded to one Fe(1), two equivalent Cu(1), and one Ge(1) atom to form SFeCu2Ge tetrahedra that share corners with two equivalent S(1)FeCu2Ge tetrahedra, corners with two equivalent S(2)ZnCu2Ge tetrahedra, corners with four equivalent S(3)FeCu2Ge tetrahedra, and corners with four equivalent S(4)ZnCu2Ge tetrahedra. In the second S site, S(2) is bonded to two equivalent Cu(1), one Zn(1), and one Ge(2) atom to form SZnCu2Ge tetrahedra that share corners with two equivalent S(1)FeCu2Ge tetrahedra, corners with two equivalent S(2)ZnCu2Ge tetrahedra, corners with four equivalent S(3)FeCu2Ge tetrahedra, and corners with four equivalent S(4)ZnCu2Ge tetrahedra. In the third S site, S(3) is bonded to one Fe(1), two equivalent Cu(1), and one Ge(2) atom to form SFeCu2Ge tetrahedra that share corners with two equivalent S(3)FeCu2Ge tetrahedra, corners with two equivalent S(4)ZnCu2Ge tetrahedra, corners with four equivalent S(1)FeCu2Ge tetrahedra, and corners with four equivalent S(2)ZnCu2Ge tetrahedra. In the fourth S site, S(4) is bonded to two equivalent Cu(1), one Zn(1), and one Ge(1) atom to form SZnCu2Ge tetrahedra that share corners with two equivalent S(3)FeCu2Ge tetrahedra, corners with two equivalent S(4)ZnCu2Ge tetrahedra, corners with four equivalent S(1)FeCu2Ge tetrahedra, and corners with four equivalent S(2)ZnCu2Ge tetrahedra.
FeCu4Zn(GeS4)2 is Stannite-derived structured and crystallizes in the orthorhombic Amm2 space group. Fe(1) is bonded to two equivalent S(1) and two equivalent S(3) atoms to form FeS4 tetrahedra that share corners with two equivalent Ge(1)S4 tetrahedra, corners with two equivalent Ge(2)S4 tetrahedra, and corners with eight equivalent Cu(1)S4 tetrahedra. Both Fe(1)-S(1) bond lengths are 2.31 Å. Both Fe(1)-S(3) bond lengths are 2.31 Å. Cu(1) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form CuS4 tetrahedra that share corners with two equivalent Fe(1)S4 tetrahedra, corners with two equivalent Zn(1)S4 tetrahedra, corners with two equivalent Ge(1)S4 tetrahedra, corners with two equivalent Ge(2)S4 tetrahedra, and corners with four equivalent Cu(1)S4 tetrahedra. The Cu(1)-S(1) bond length is 2.30 Å. The Cu(1)-S(2) bond length is 2.29 Å. The Cu(1)-S(3) bond length is 2.30 Å. The Cu(1)-S(4) bond length is 2.29 Å. Zn(1) is bonded to two equivalent S(2) and two equivalent S(4) atoms to form ZnS4 tetrahedra that share corners with two equivalent Ge(1)S4 tetrahedra, corners with two equivalent Ge(2)S4 tetrahedra, and corners with eight equivalent Cu(1)S4 tetrahedra. Both Zn(1)-S(2) bond lengths are 2.37 Å. Both Zn(1)-S(4) bond lengths are 2.37 Å. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to two equivalent S(1) and two equivalent S(4) atoms to form GeS4 tetrahedra that share corners with two equivalent Fe(1)S4 tetrahedra, corners with two equivalent Zn(1)S4 tetrahedra, and corners with eight equivalent Cu(1)S4 tetrahedra. Both Ge(1)-S(1) bond lengths are 2.31 Å. Both Ge(1)-S(4) bond lengths are 2.30 Å. In the second Ge site, Ge(2) is bonded to two equivalent S(2) and two equivalent S(3) atoms to form GeS4 tetrahedra that share corners with two equivalent Fe(1)S4 tetrahedra, corners with two equivalent Zn(1)S4 tetrahedra, and corners with eight equivalent Cu(1)S4 tetrahedra. Both Ge(2)-S(2) bond lengths are 2.29 Å. Both Ge(2)-S(3) bond lengths are 2.30 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded to one Fe(1), two equivalent Cu(1), and one Ge(1) atom to form SFeCu2Ge tetrahedra that share corners with two equivalent S(1)FeCu2Ge tetrahedra, corners with two equivalent S(2)ZnCu2Ge tetrahedra, corners with four equivalent S(3)FeCu2Ge tetrahedra, and corners with four equivalent S(4)ZnCu2Ge tetrahedra. In the second S site, S(2) is bonded to two equivalent Cu(1), one Zn(1), and one Ge(2) atom to form SZnCu2Ge tetrahedra that share corners with two equivalent S(1)FeCu2Ge tetrahedra, corners with two equivalent S(2)ZnCu2Ge tetrahedra, corners with four equivalent S(3)FeCu2Ge tetrahedra, and corners with four equivalent S(4)ZnCu2Ge tetrahedra. In the third S site, S(3) is bonded to one Fe(1), two equivalent Cu(1), and one Ge(2) atom to form SFeCu2Ge tetrahedra that share corners with two equivalent S(3)FeCu2Ge tetrahedra, corners with two equivalent S(4)ZnCu2Ge tetrahedra, corners with four equivalent S(1)FeCu2Ge tetrahedra, and corners with four equivalent S(2)ZnCu2Ge tetrahedra. In the fourth S site, S(4) is bonded to two equivalent Cu(1), one Zn(1), and one Ge(1) atom to form SZnCu2Ge tetrahedra that share corners with two equivalent S(3)FeCu2Ge tetrahedra, corners with two equivalent S(4)ZnCu2Ge tetrahedra, corners with four equivalent S(1)FeCu2Ge tetrahedra, and corners with four equivalent S(2)ZnCu2Ge tetrahedra.