MnZnO2 crystallizes in the monoclinic C2/m space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 5-coordinate geometry to one O(2), two equivalent O(1), and two equivalent O(3) atoms. In the second Mn site, Mn(2) is bonded to one O(1), two equivalent O(2), and three equivalent O(4) atoms to form MnO6 octahedra that share corners with four equivalent Zn(1)O5 square pyramids, edges with four equivalent Mn(2)O6 octahedra, and  a faceface with one Zn(1)O5 square pyramid. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(1), two equivalent O(3), and two equivalent O(4) atoms to form ZnO5 square pyramids that share corners with four equivalent Mn(2)O6 octahedra, edges with two equivalent Zn(1)O5 square pyramids, and  a faceface with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. In the second Zn site, Zn(2) is bonded in a 3-coordinate geometry to one O(3), one O(4), and two equivalent O(2) atoms. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Mn(2), two equivalent Mn(1), and one Zn(1) atom to form distorted OMn3Zn trigonal pyramids that share corners with four equivalent O(3)Mn2Zn3 square pyramids, corners with four equivalent O(2)Mn3Zn2 trigonal bipyramids, corners with two equivalent O(1)Mn3Zn trigonal pyramids, and  an edgeedge with one O(3)Mn2Zn3 square pyramid. In the second O site, O(2) is bonded to one Mn(1), two equivalent Mn(2), and two equivalent Zn(2) atoms to form distorted OMn3Zn2 trigonal bipyramids that share corners with four equivalent O(1)Mn3Zn trigonal pyramids, edges with two equivalent O(3)Mn2Zn3 square pyramids, and edges with two equivalent O(2)Mn3Zn2 trigonal bipyramids. In the third O site, O(3) is bonded to two equivalent Mn(1), one Zn(2), and two equivalent Zn(1) atoms to form distorted OMn2Zn3 square pyramids that share corners with four equivalent O(1)Mn3Zn trigonal pyramids, edges with two equivalent O(3)Mn2Zn3 square pyramids, edges with two equivalent O(2)Mn3Zn2 trigonal bipyramids, and  an edgeedge with one O(1)Mn3Zn trigonal pyramid. In the fourth O site, O(4) is bonded in a 6-coordinate geometry to three equivalent Mn(2), one Zn(2), and two equivalent Zn(1) atoms.
MnZnO2 crystallizes in the monoclinic C2/m space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 5-coordinate geometry to one O(2), two equivalent O(1), and two equivalent O(3) atoms. The Mn(1)-O(2) bond length is 2.22 Å. Both Mn(1)-O(1) bond lengths are 2.00 Å. Both Mn(1)-O(3) bond lengths are 2.11 Å. In the second Mn site, Mn(2) is bonded to one O(1), two equivalent O(2), and three equivalent O(4) atoms to form MnO6 octahedra that share corners with four equivalent Zn(1)O5 square pyramids, edges with four equivalent Mn(2)O6 octahedra, and  a faceface with one Zn(1)O5 square pyramid. The Mn(2)-O(1) bond length is 2.09 Å. Both Mn(2)-O(2) bond lengths are 2.25 Å. There is one shorter (2.21 Å) and two longer (2.31 Å) Mn(2)-O(4) bond lengths. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(1), two equivalent O(3), and two equivalent O(4) atoms to form ZnO5 square pyramids that share corners with four equivalent Mn(2)O6 octahedra, edges with two equivalent Zn(1)O5 square pyramids, and  a faceface with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. The Zn(1)-O(1) bond length is 2.18 Å. Both Zn(1)-O(3) bond lengths are 2.13 Å. Both Zn(1)-O(4) bond lengths are 2.08 Å. In the second Zn site, Zn(2) is bonded in a 3-coordinate geometry to one O(3), one O(4), and two equivalent O(2) atoms. The Zn(2)-O(3) bond length is 2.20 Å. The Zn(2)-O(4) bond length is 2.52 Å. Both Zn(2)-O(2) bond lengths are 2.04 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Mn(2), two equivalent Mn(1), and one Zn(1) atom to form distorted OMn3Zn trigonal pyramids that share corners with four equivalent O(3)Mn2Zn3 square pyramids, corners with four equivalent O(2)Mn3Zn2 trigonal bipyramids, corners with two equivalent O(1)Mn3Zn trigonal pyramids, and  an edgeedge with one O(3)Mn2Zn3 square pyramid. In the second O site, O(2) is bonded to one Mn(1), two equivalent Mn(2), and two equivalent Zn(2) atoms to form distorted OMn3Zn2 trigonal bipyramids that share corners with four equivalent O(1)Mn3Zn trigonal pyramids, edges with two equivalent O(3)Mn2Zn3 square pyramids, and edges with two equivalent O(2)Mn3Zn2 trigonal bipyramids. In the third O site, O(3) is bonded to two equivalent Mn(1), one Zn(2), and two equivalent Zn(1) atoms to form distorted OMn2Zn3 square pyramids that share corners with four equivalent O(1)Mn3Zn trigonal pyramids, edges with two equivalent O(3)Mn2Zn3 square pyramids, edges with two equivalent O(2)Mn3Zn2 trigonal bipyramids, and  an edgeedge with one O(1)Mn3Zn trigonal pyramid. In the fourth O site, O(4) is bonded in a 6-coordinate geometry to three equivalent Mn(2), one Zn(2), and two equivalent Zn(1) atoms.