MgZn2(Ni2S5)2 crystallizes in the monoclinic Pm space group. Mg(1) is bonded in a 6-coordinate geometry to one S(3), one S(9), two equivalent S(10), and two equivalent S(4) atoms. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one S(10), one S(2), one S(4), and two equivalent S(3) atoms to form NiS5 trigonal bipyramids that share  a cornercorner with one Ni(4)S5 trigonal bipyramid, corners with two equivalent Ni(1)S5 trigonal bipyramids, corners with two equivalent Zn(1)S5 trigonal bipyramids, and edges with two equivalent Ni(2)S5 trigonal bipyramids. In the second Ni site, Ni(2) is bonded to one S(1), one S(3), one S(9), and two equivalent S(4) atoms to form NiS5 trigonal bipyramids that share  a cornercorner with one Ni(3)S5 trigonal bipyramid, corners with two equivalent Ni(2)S5 trigonal bipyramids, corners with two equivalent Zn(2)S5 trigonal bipyramids, and edges with two equivalent Ni(1)S5 trigonal bipyramids. In the third Ni site, Ni(3) is bonded to one S(1), one S(5), one S(8), and two equivalent S(6) atoms to form NiS5 trigonal bipyramids that share  a cornercorner with one Ni(2)S5 trigonal bipyramid,  a cornercorner with one Zn(1)S5 trigonal bipyramid, corners with two equivalent Ni(3)S5 trigonal bipyramids, corners with two equivalent Zn(2)S5 trigonal bipyramids, edges with two equivalent Ni(4)S5 trigonal bipyramids, and edges with two equivalent Zn(2)S5 trigonal bipyramids. In the fourth Ni site, Ni(4) is bonded to one S(2), one S(6), one S(7), and two equivalent S(5) atoms to form NiS5 trigonal bipyramids that share  a cornercorner with one Ni(1)S5 trigonal bipyramid,  a cornercorner with one Zn(2)S5 trigonal bipyramid, corners with two equivalent Ni(4)S5 trigonal bipyramids, corners with two equivalent Zn(1)S5 trigonal bipyramids, edges with two equivalent Ni(3)S5 trigonal bipyramids, and edges with two equivalent Zn(1)S5 trigonal bipyramids. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one S(5), two equivalent S(2), and two equivalent S(7) atoms to form distorted ZnS5 trigonal bipyramids that share  a cornercorner with one Ni(3)S5 trigonal bipyramid, corners with two equivalent Ni(1)S5 trigonal bipyramids, corners with two equivalent Ni(4)S5 trigonal bipyramids, edges with two equivalent Ni(4)S5 trigonal bipyramids, and edges with two equivalent Zn(1)S5 trigonal bipyramids. In the second Zn site, Zn(2) is bonded to one S(6), two equivalent S(1), and two equivalent S(8) atoms to form distorted ZnS5 trigonal bipyramids that share  a cornercorner with one Ni(4)S5 trigonal bipyramid, corners with two equivalent Ni(2)S5 trigonal bipyramids, corners with two equivalent Ni(3)S5 trigonal bipyramids, edges with two equivalent Ni(3)S5 trigonal bipyramids, and edges with two equivalent Zn(2)S5 trigonal bipyramids. There are ten inequivalent S sites. In the first S site, S(1) is bonded to one Ni(2), one Ni(3), and two equivalent Zn(2) atoms to form distorted SZn2Ni2 trigonal pyramids that share corners with two equivalent S(4)Mg2Ni3 square pyramids,  a cornercorner with one S(3)MgNi3 trigonal pyramid, and corners with two equivalent S(1)Zn2Ni2 trigonal pyramids. In the second S site, S(2) is bonded to one Ni(1), one Ni(4), and two equivalent Zn(1) atoms to form distorted SZn2Ni2 trigonal pyramids that share  a cornercorner with one S(4)Mg2Ni3 square pyramid, corners with two equivalent S(3)MgNi3 trigonal pyramids, and corners with two equivalent S(2)Zn2Ni2 trigonal pyramids. In the third S site, S(3) is bonded to one Mg(1), one Ni(2), and two equivalent Ni(1) atoms to form SMgNi3 trigonal pyramids that share corners with two equivalent S(4)Mg2Ni3 square pyramids,  a cornercorner with one S(1)Zn2Ni2 trigonal pyramid, corners with two equivalent S(3)MgNi3 trigonal pyramids, corners with two equivalent S(2)Zn2Ni2 trigonal pyramids, and edges with two equivalent S(4)Mg2Ni3 square pyramids. In the fourth S site, S(4) is bonded to two equivalent Mg(1), one Ni(1), and two equivalent Ni(2) atoms to form SMg2Ni3 square pyramids that share  a cornercorner with one S(2)Zn2Ni2 trigonal pyramid, corners with two equivalent S(3)MgNi3 trigonal pyramids, corners with two equivalent S(1)Zn2Ni2 trigonal pyramids, edges with two equivalent S(4)Mg2Ni3 square pyramids, and edges with two equivalent S(3)MgNi3 trigonal pyramids. In the fifth S site, S(5) is bonded in a distorted see-saw-like geometry to one Ni(3), two equivalent Ni(4), and one Zn(1) atom. In the sixth S site, S(6) is bonded in a distorted see-saw-like geometry to one Ni(4), two equivalent Ni(3), and one Zn(2) atom. In the seventh S site, S(7) is bonded in a distorted rectangular see-saw-like geometry to one Ni(4), two equivalent Zn(1), and one S(10) atom. In the eighth S site, S(8) is bonded in a distorted rectangular see-saw-like geometry to one Ni(3), two equivalent Zn(2), and one S(9) atom. In the ninth S site, S(9) is bonded in a 3-coordinate geometry to one Mg(1), one Ni(2), and one S(8) atom. In the tenth S site, S(10) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Mg(1), one Ni(1), and one S(7) atom.
MgZn2(Ni2S5)2 crystallizes in the monoclinic Pm space group. Mg(1) is bonded in a 6-coordinate geometry to one S(3), one S(9), two equivalent S(10), and two equivalent S(4) atoms. The Mg(1)-S(3) bond length is 2.57 Å. The Mg(1)-S(9) bond length is 2.69 Å. Both Mg(1)-S(10) bond lengths are 2.62 Å. Both Mg(1)-S(4) bond lengths are 2.67 Å. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one S(10), one S(2), one S(4), and two equivalent S(3) atoms to form NiS5 trigonal bipyramids that share  a cornercorner with one Ni(4)S5 trigonal bipyramid, corners with two equivalent Ni(1)S5 trigonal bipyramids, corners with two equivalent Zn(1)S5 trigonal bipyramids, and edges with two equivalent Ni(2)S5 trigonal bipyramids. The Ni(1)-S(10) bond length is 2.20 Å. The Ni(1)-S(2) bond length is 2.19 Å. The Ni(1)-S(4) bond length is 2.27 Å. Both Ni(1)-S(3) bond lengths are 2.27 Å. In the second Ni site, Ni(2) is bonded to one S(1), one S(3), one S(9), and two equivalent S(4) atoms to form NiS5 trigonal bipyramids that share  a cornercorner with one Ni(3)S5 trigonal bipyramid, corners with two equivalent Ni(2)S5 trigonal bipyramids, corners with two equivalent Zn(2)S5 trigonal bipyramids, and edges with two equivalent Ni(1)S5 trigonal bipyramids. The Ni(2)-S(1) bond length is 2.20 Å. The Ni(2)-S(3) bond length is 2.24 Å. The Ni(2)-S(9) bond length is 2.15 Å. Both Ni(2)-S(4) bond lengths are 2.34 Å. In the third Ni site, Ni(3) is bonded to one S(1), one S(5), one S(8), and two equivalent S(6) atoms to form NiS5 trigonal bipyramids that share  a cornercorner with one Ni(2)S5 trigonal bipyramid,  a cornercorner with one Zn(1)S5 trigonal bipyramid, corners with two equivalent Ni(3)S5 trigonal bipyramids, corners with two equivalent Zn(2)S5 trigonal bipyramids, edges with two equivalent Ni(4)S5 trigonal bipyramids, and edges with two equivalent Zn(2)S5 trigonal bipyramids. The Ni(3)-S(1) bond length is 2.24 Å. The Ni(3)-S(5) bond length is 2.26 Å. The Ni(3)-S(8) bond length is 2.22 Å. Both Ni(3)-S(6) bond lengths are 2.24 Å. In the fourth Ni site, Ni(4) is bonded to one S(2), one S(6), one S(7), and two equivalent S(5) atoms to form NiS5 trigonal bipyramids that share  a cornercorner with one Ni(1)S5 trigonal bipyramid,  a cornercorner with one Zn(2)S5 trigonal bipyramid, corners with two equivalent Ni(4)S5 trigonal bipyramids, corners with two equivalent Zn(1)S5 trigonal bipyramids, edges with two equivalent Ni(3)S5 trigonal bipyramids, and edges with two equivalent Zn(1)S5 trigonal bipyramids. The Ni(4)-S(2) bond length is 2.24 Å. The Ni(4)-S(6) bond length is 2.27 Å. The Ni(4)-S(7) bond length is 2.22 Å. Both Ni(4)-S(5) bond lengths are 2.24 Å. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one S(5), two equivalent S(2), and two equivalent S(7) atoms to form distorted ZnS5 trigonal bipyramids that share  a cornercorner with one Ni(3)S5 trigonal bipyramid, corners with two equivalent Ni(1)S5 trigonal bipyramids, corners with two equivalent Ni(4)S5 trigonal bipyramids, edges with two equivalent Ni(4)S5 trigonal bipyramids, and edges with two equivalent Zn(1)S5 trigonal bipyramids. The Zn(1)-S(5) bond length is 2.47 Å. Both Zn(1)-S(2) bond lengths are 2.48 Å. Both Zn(1)-S(7) bond lengths are 2.49 Å. In the second Zn site, Zn(2) is bonded to one S(6), two equivalent S(1), and two equivalent S(8) atoms to form distorted ZnS5 trigonal bipyramids that share  a cornercorner with one Ni(4)S5 trigonal bipyramid, corners with two equivalent Ni(2)S5 trigonal bipyramids, corners with two equivalent Ni(3)S5 trigonal bipyramids, edges with two equivalent Ni(3)S5 trigonal bipyramids, and edges with two equivalent Zn(2)S5 trigonal bipyramids. The Zn(2)-S(6) bond length is 2.49 Å. Both Zn(2)-S(1) bond lengths are 2.47 Å. Both Zn(2)-S(8) bond lengths are 2.50 Å. There are ten inequivalent S sites. In the first S site, S(1) is bonded to one Ni(2), one Ni(3), and two equivalent Zn(2) atoms to form distorted SZn2Ni2 trigonal pyramids that share corners with two equivalent S(4)Mg2Ni3 square pyramids,  a cornercorner with one S(3)MgNi3 trigonal pyramid, and corners with two equivalent S(1)Zn2Ni2 trigonal pyramids. In the second S site, S(2) is bonded to one Ni(1), one Ni(4), and two equivalent Zn(1) atoms to form distorted SZn2Ni2 trigonal pyramids that share  a cornercorner with one S(4)Mg2Ni3 square pyramid, corners with two equivalent S(3)MgNi3 trigonal pyramids, and corners with two equivalent S(2)Zn2Ni2 trigonal pyramids. In the third S site, S(3) is bonded to one Mg(1), one Ni(2), and two equivalent Ni(1) atoms to form SMgNi3 trigonal pyramids that share corners with two equivalent S(4)Mg2Ni3 square pyramids,  a cornercorner with one S(1)Zn2Ni2 trigonal pyramid, corners with two equivalent S(3)MgNi3 trigonal pyramids, corners with two equivalent S(2)Zn2Ni2 trigonal pyramids, and edges with two equivalent S(4)Mg2Ni3 square pyramids. In the fourth S site, S(4) is bonded to two equivalent Mg(1), one Ni(1), and two equivalent Ni(2) atoms to form SMg2Ni3 square pyramids that share  a cornercorner with one S(2)Zn2Ni2 trigonal pyramid, corners with two equivalent S(3)MgNi3 trigonal pyramids, corners with two equivalent S(1)Zn2Ni2 trigonal pyramids, edges with two equivalent S(4)Mg2Ni3 square pyramids, and edges with two equivalent S(3)MgNi3 trigonal pyramids. In the fifth S site, S(5) is bonded in a distorted see-saw-like geometry to one Ni(3), two equivalent Ni(4), and one Zn(1) atom. In the sixth S site, S(6) is bonded in a distorted see-saw-like geometry to one Ni(4), two equivalent Ni(3), and one Zn(2) atom. In the seventh S site, S(7) is bonded in a distorted rectangular see-saw-like geometry to one Ni(4), two equivalent Zn(1), and one S(10) atom. The S(7)-S(10) bond length is 2.20 Å. In the eighth S site, S(8) is bonded in a distorted rectangular see-saw-like geometry to one Ni(3), two equivalent Zn(2), and one S(9) atom. The S(8)-S(9) bond length is 2.14 Å. In the ninth S site, S(9) is bonded in a 3-coordinate geometry to one Mg(1), one Ni(2), and one S(8) atom. In the tenth S site, S(10) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Mg(1), one Ni(1), and one S(7) atom.