Mn4ZnO6 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), two equivalent O(1), and three equivalent O(3) atoms to form a mixture of corner and edge-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles range from 0-18°. In the second Mn site, Mn(2) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form a mixture of distorted corner and edge-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles range from 0-68°. Zn(1) is bonded in a 6-coordinate geometry to two equivalent O(4) and four equivalent O(2) atoms. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Mn(2) and four equivalent Mn(1) atoms to form OMn6 octahedra that share corners with four equivalent O(3)Mn5 square pyramids, corners with two equivalent O(4)Mn2Zn2 tetrahedra, edges with two equivalent O(1)Mn6 octahedra, edges with six equivalent O(3)Mn5 square pyramids, and edges with four equivalent O(2)Mn3Zn2 trigonal bipyramids. In the second O site, O(2) is bonded to one Mn(1), two equivalent Mn(2), and two equivalent Zn(1) atoms to form distorted OMn3Zn2 trigonal bipyramids that share corners with five equivalent O(3)Mn5 square pyramids, corners with four equivalent O(4)Mn2Zn2 tetrahedra, corners with two equivalent O(2)Mn3Zn2 trigonal bipyramids, edges with two equivalent O(1)Mn6 octahedra,  an edgeedge with one O(3)Mn5 square pyramid,  an edgeedge with one O(4)Mn2Zn2 tetrahedra, and edges with three equivalent O(2)Mn3Zn2 trigonal bipyramids. In the third O site, O(3) is bonded to two equivalent Mn(2) and three equivalent Mn(1) atoms to form OMn5 square pyramids that share corners with two equivalent O(1)Mn6 octahedra, corners with two equivalent O(4)Mn2Zn2 tetrahedra, corners with five equivalent O(2)Mn3Zn2 trigonal bipyramids, edges with three equivalent O(1)Mn6 octahedra, edges with four equivalent O(3)Mn5 square pyramids, and  an edgeedge with one O(2)Mn3Zn2 trigonal bipyramid. The corner-sharing octahedral tilt angles are 8°. In the fourth O site, O(4) is bonded to two equivalent Mn(2) and two equivalent Zn(1) atoms to form OMn2Zn2 tetrahedra that share corners with two equivalent O(1)Mn6 octahedra, corners with four equivalent O(3)Mn5 square pyramids, corners with two equivalent O(4)Mn2Zn2 tetrahedra, corners with eight equivalent O(2)Mn3Zn2 trigonal bipyramids, and edges with two equivalent O(2)Mn3Zn2 trigonal bipyramids. The corner-sharing octahedral tilt angles are 9°.
Mn4ZnO6 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), two equivalent O(1), and three equivalent O(3) atoms to form a mixture of corner and edge-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles range from 0-18°. The Mn(1)-O(2) bond length is 1.95 Å. Both Mn(1)-O(1) bond lengths are 2.18 Å. There is one shorter (2.01 Å) and two longer (2.16 Å) Mn(1)-O(3) bond lengths. In the second Mn site, Mn(2) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form a mixture of distorted corner and edge-sharing MnO6 octahedra. The corner-sharing octahedral tilt angles range from 0-68°. The Mn(2)-O(1) bond length is 2.40 Å. The Mn(2)-O(4) bond length is 2.05 Å. Both Mn(2)-O(2) bond lengths are 2.16 Å. Both Mn(2)-O(3) bond lengths are 2.25 Å. Zn(1) is bonded in a 6-coordinate geometry to two equivalent O(4) and four equivalent O(2) atoms. Both Zn(1)-O(4) bond lengths are 2.04 Å. All Zn(1)-O(2) bond lengths are 2.38 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Mn(2) and four equivalent Mn(1) atoms to form OMn6 octahedra that share corners with four equivalent O(3)Mn5 square pyramids, corners with two equivalent O(4)Mn2Zn2 tetrahedra, edges with two equivalent O(1)Mn6 octahedra, edges with six equivalent O(3)Mn5 square pyramids, and edges with four equivalent O(2)Mn3Zn2 trigonal bipyramids. In the second O site, O(2) is bonded to one Mn(1), two equivalent Mn(2), and two equivalent Zn(1) atoms to form distorted OMn3Zn2 trigonal bipyramids that share corners with five equivalent O(3)Mn5 square pyramids, corners with four equivalent O(4)Mn2Zn2 tetrahedra, corners with two equivalent O(2)Mn3Zn2 trigonal bipyramids, edges with two equivalent O(1)Mn6 octahedra,  an edgeedge with one O(3)Mn5 square pyramid,  an edgeedge with one O(4)Mn2Zn2 tetrahedra, and edges with three equivalent O(2)Mn3Zn2 trigonal bipyramids. In the third O site, O(3) is bonded to two equivalent Mn(2) and three equivalent Mn(1) atoms to form OMn5 square pyramids that share corners with two equivalent O(1)Mn6 octahedra, corners with two equivalent O(4)Mn2Zn2 tetrahedra, corners with five equivalent O(2)Mn3Zn2 trigonal bipyramids, edges with three equivalent O(1)Mn6 octahedra, edges with four equivalent O(3)Mn5 square pyramids, and  an edgeedge with one O(2)Mn3Zn2 trigonal bipyramid. The corner-sharing octahedral tilt angles are 8°. In the fourth O site, O(4) is bonded to two equivalent Mn(2) and two equivalent Zn(1) atoms to form OMn2Zn2 tetrahedra that share corners with two equivalent O(1)Mn6 octahedra, corners with four equivalent O(3)Mn5 square pyramids, corners with two equivalent O(4)Mn2Zn2 tetrahedra, corners with eight equivalent O(2)Mn3Zn2 trigonal bipyramids, and edges with two equivalent O(2)Mn3Zn2 trigonal bipyramids. The corner-sharing octahedral tilt angles are 9°.