MgMn4(ZnS4)2 is Aluminum carbonitride-derived structured and crystallizes in the monoclinic Cm space group. Mg(1) is bonded to one S(1), one S(3), and two equivalent S(5) atoms to form distorted MgS4 tetrahedra that share corners with three equivalent Mn(1)S6 octahedra, corners with three equivalent Mn(3)S6 octahedra, corners with two equivalent Zn(1)S4 tetrahedra, and  an edgeedge with one Zn(2)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 38-66°. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one S(3), one S(6), two equivalent S(2), and two equivalent S(5) atoms to form distorted MnS6 octahedra that share corners with three equivalent Mg(1)S4 tetrahedra, corners with three equivalent Zn(1)S4 tetrahedra, corners with three equivalent Zn(2)S4 tetrahedra, and edges with two equivalent Mn(3)S6 octahedra. In the second Mn site, Mn(2) is bonded in a 5-coordinate geometry to one S(1), one S(2), one S(3), one S(4), and one S(6) atom. In the third Mn site, Mn(3) is bonded to one S(1), one S(4), two equivalent S(2), and two equivalent S(5) atoms to form distorted MnS6 octahedra that share corners with three equivalent Mg(1)S4 tetrahedra, corners with three equivalent Zn(1)S4 tetrahedra, corners with three equivalent Zn(2)S4 tetrahedra, and edges with two equivalent Mn(1)S6 octahedra. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form ZnS4 tetrahedra that share corners with three equivalent Mn(1)S6 octahedra, corners with three equivalent Mn(3)S6 octahedra, and corners with two equivalent Mg(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 58-61°. In the second Zn site, Zn(2) is bonded to one S(4), one S(6), and two equivalent S(5) atoms to form ZnS4 tetrahedra that share corners with three equivalent Mn(1)S6 octahedra, corners with three equivalent Mn(3)S6 octahedra, and  an edgeedge with one Mg(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-60°. There are six inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to one Mg(1), one Mn(3), two equivalent Mn(2), and one Zn(1) atom. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Mn(1), one Mn(2), one Mn(3), and one Zn(1) atom. In the third S site, S(3) is bonded in a 5-coordinate geometry to one Mg(1), one Mn(1), two equivalent Mn(2), and one Zn(1) atom. In the fourth S site, S(4) is bonded to one Mn(3), two equivalent Mn(2), and one Zn(2) atom to form SMn3Zn tetrahedra that share  a cornercorner with one S(6)Mn3Zn tetrahedra, corners with four equivalent S(5)MgMn2Zn tetrahedra, and  an edgeedge with one S(6)Mn3Zn tetrahedra. In the fifth S site, S(5) is bonded to one Mg(1), one Mn(1), one Mn(3), and one Zn(2) atom to form distorted SMgMn2Zn tetrahedra that share corners with two equivalent S(4)Mn3Zn tetrahedra, corners with two equivalent S(6)Mn3Zn tetrahedra, and edges with two equivalent S(5)MgMn2Zn tetrahedra. In the sixth S site, S(6) is bonded to one Mn(1), two equivalent Mn(2), and one Zn(2) atom to form SMn3Zn tetrahedra that share  a cornercorner with one S(4)Mn3Zn tetrahedra, corners with four equivalent S(5)MgMn2Zn tetrahedra, and  an edgeedge with one S(4)Mn3Zn tetrahedra.
MgMn4(ZnS4)2 is Aluminum carbonitride-derived structured and crystallizes in the monoclinic Cm space group. Mg(1) is bonded to one S(1), one S(3), and two equivalent S(5) atoms to form distorted MgS4 tetrahedra that share corners with three equivalent Mn(1)S6 octahedra, corners with three equivalent Mn(3)S6 octahedra, corners with two equivalent Zn(1)S4 tetrahedra, and  an edgeedge with one Zn(2)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 38-66°. The Mg(1)-S(1) bond length is 2.44 Å. The Mg(1)-S(3) bond length is 2.45 Å. Both Mg(1)-S(5) bond lengths are 2.39 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one S(3), one S(6), two equivalent S(2), and two equivalent S(5) atoms to form distorted MnS6 octahedra that share corners with three equivalent Mg(1)S4 tetrahedra, corners with three equivalent Zn(1)S4 tetrahedra, corners with three equivalent Zn(2)S4 tetrahedra, and edges with two equivalent Mn(3)S6 octahedra. The Mn(1)-S(3) bond length is 3.05 Å. The Mn(1)-S(6) bond length is 2.60 Å. Both Mn(1)-S(2) bond lengths are 2.45 Å. Both Mn(1)-S(5) bond lengths are 2.45 Å. In the second Mn site, Mn(2) is bonded in a 5-coordinate geometry to one S(1), one S(2), one S(3), one S(4), and one S(6) atom. The Mn(2)-S(1) bond length is 2.51 Å. The Mn(2)-S(2) bond length is 2.47 Å. The Mn(2)-S(3) bond length is 2.50 Å. The Mn(2)-S(4) bond length is 2.41 Å. The Mn(2)-S(6) bond length is 2.41 Å. In the third Mn site, Mn(3) is bonded to one S(1), one S(4), two equivalent S(2), and two equivalent S(5) atoms to form distorted MnS6 octahedra that share corners with three equivalent Mg(1)S4 tetrahedra, corners with three equivalent Zn(1)S4 tetrahedra, corners with three equivalent Zn(2)S4 tetrahedra, and edges with two equivalent Mn(1)S6 octahedra. The Mn(3)-S(1) bond length is 3.06 Å. The Mn(3)-S(4) bond length is 2.58 Å. Both Mn(3)-S(2) bond lengths are 2.45 Å. Both Mn(3)-S(5) bond lengths are 2.45 Å. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form ZnS4 tetrahedra that share corners with three equivalent Mn(1)S6 octahedra, corners with three equivalent Mn(3)S6 octahedra, and corners with two equivalent Mg(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 58-61°. The Zn(1)-S(1) bond length is 2.39 Å. The Zn(1)-S(3) bond length is 2.40 Å. Both Zn(1)-S(2) bond lengths are 2.41 Å. In the second Zn site, Zn(2) is bonded to one S(4), one S(6), and two equivalent S(5) atoms to form ZnS4 tetrahedra that share corners with three equivalent Mn(1)S6 octahedra, corners with three equivalent Mn(3)S6 octahedra, and  an edgeedge with one Mg(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-60°. The Zn(2)-S(4) bond length is 2.33 Å. The Zn(2)-S(6) bond length is 2.32 Å. Both Zn(2)-S(5) bond lengths are 2.44 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to one Mg(1), one Mn(3), two equivalent Mn(2), and one Zn(1) atom. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Mn(1), one Mn(2), one Mn(3), and one Zn(1) atom. In the third S site, S(3) is bonded in a 5-coordinate geometry to one Mg(1), one Mn(1), two equivalent Mn(2), and one Zn(1) atom. In the fourth S site, S(4) is bonded to one Mn(3), two equivalent Mn(2), and one Zn(2) atom to form SMn3Zn tetrahedra that share  a cornercorner with one S(6)Mn3Zn tetrahedra, corners with four equivalent S(5)MgMn2Zn tetrahedra, and  an edgeedge with one S(6)Mn3Zn tetrahedra. In the fifth S site, S(5) is bonded to one Mg(1), one Mn(1), one Mn(3), and one Zn(2) atom to form distorted SMgMn2Zn tetrahedra that share corners with two equivalent S(4)Mn3Zn tetrahedra, corners with two equivalent S(6)Mn3Zn tetrahedra, and edges with two equivalent S(5)MgMn2Zn tetrahedra. In the sixth S site, S(6) is bonded to one Mn(1), two equivalent Mn(2), and one Zn(2) atom to form SMn3Zn tetrahedra that share  a cornercorner with one S(4)Mn3Zn tetrahedra, corners with four equivalent S(5)MgMn2Zn tetrahedra, and  an edgeedge with one S(4)Mn3Zn tetrahedra.