Mn3Zn2O8 crystallizes in the hexagonal P6_3mc space group. Mn(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form MnO6 octahedra that share corners with two equivalent Zn(1)O6 octahedra, corners with three equivalent Zn(2)O4 tetrahedra,  an edgeedge with one Zn(1)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form ZnO6 octahedra that share corners with six equivalent Mn(1)O6 octahedra, corners with three equivalent Zn(2)O4 tetrahedra, and edges with three equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. In the second Zn site, Zn(2) is bonded to one O(4) and three equivalent O(2) atoms to form ZnO4 tetrahedra that share corners with three equivalent Zn(1)O6 octahedra and corners with nine equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 59-63°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to two equivalent Mn(1) and one Zn(1) atom. In the second O site, O(2) is bonded to two equivalent Mn(1), one Zn(1), and one Zn(2) atom to form distorted OMn2Zn2 tetrahedra that share corners with two equivalent O(2)Mn2Zn2 tetrahedra,  a cornercorner with one O(4)Mn3Zn trigonal pyramid, edges with two equivalent O(2)Mn2Zn2 tetrahedra, and  an edgeedge with one O(4)Mn3Zn trigonal pyramid. In the third O site, O(3) is bonded in a distorted T-shaped geometry to three equivalent Mn(1) atoms. In the fourth O site, O(4) is bonded to three equivalent Mn(1) and one Zn(2) atom to form a mixture of distorted edge and corner-sharing OMn3Zn trigonal pyramids.
Mn3Zn2O8 crystallizes in the hexagonal P6_3mc space group. Mn(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form MnO6 octahedra that share corners with two equivalent Zn(1)O6 octahedra, corners with three equivalent Zn(2)O4 tetrahedra,  an edgeedge with one Zn(1)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. The Mn(1)-O(3) bond length is 1.90 Å. The Mn(1)-O(4) bond length is 1.96 Å. Both Mn(1)-O(1) bond lengths are 1.86 Å. Both Mn(1)-O(2) bond lengths are 1.93 Å. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form ZnO6 octahedra that share corners with six equivalent Mn(1)O6 octahedra, corners with three equivalent Zn(2)O4 tetrahedra, and edges with three equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. All Zn(1)-O(1) bond lengths are 2.02 Å. All Zn(1)-O(2) bond lengths are 2.16 Å. In the second Zn site, Zn(2) is bonded to one O(4) and three equivalent O(2) atoms to form ZnO4 tetrahedra that share corners with three equivalent Zn(1)O6 octahedra and corners with nine equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 59-63°. The Zn(2)-O(4) bond length is 2.01 Å. All Zn(2)-O(2) bond lengths are 1.91 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to two equivalent Mn(1) and one Zn(1) atom. In the second O site, O(2) is bonded to two equivalent Mn(1), one Zn(1), and one Zn(2) atom to form distorted OMn2Zn2 tetrahedra that share corners with two equivalent O(2)Mn2Zn2 tetrahedra,  a cornercorner with one O(4)Mn3Zn trigonal pyramid, edges with two equivalent O(2)Mn2Zn2 tetrahedra, and  an edgeedge with one O(4)Mn3Zn trigonal pyramid. In the third O site, O(3) is bonded in a distorted T-shaped geometry to three equivalent Mn(1) atoms. In the fourth O site, O(4) is bonded to three equivalent Mn(1) and one Zn(2) atom to form a mixture of distorted edge and corner-sharing OMn3Zn trigonal pyramids.