ZnMn2O4 crystallizes in the monoclinic P2_1 space group. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 6-coordinate geometry to one O(1), one O(3), two equivalent O(5), and two equivalent O(7) atoms. In the second Mn site, Mn(2) is bonded to one O(2), one O(4), two equivalent O(6), and two equivalent O(8) atoms to form distorted edge-sharing MnO6 octahedra. In the third Mn site, Mn(3) is bonded to one O(5), one O(7), two equivalent O(1), and two equivalent O(3) atoms to form edge-sharing MnO6 octahedra. In the fourth Mn site, Mn(4) is bonded to one O(6), one O(8), two equivalent O(2), and two equivalent O(4) atoms to form edge-sharing MnO6 octahedra. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(5), one O(6), one O(7), and one O(8) atom. In the second Zn site, Zn(2) is bonded in a 6-coordinate geometry to one O(3), one O(4), one O(5), one O(6), one O(7), and one O(8) atom. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Mn(1), two equivalent Mn(3), and one Zn(1) atom to form OMn3Zn trigonal pyramids that share  a cornercorner with one O(5)Mn3Zn2 square pyramid,  a cornercorner with one O(6)Mn3Zn2 square pyramid,  a cornercorner with one O(8)Mn3Zn2 trigonal bipyramid,  a cornercorner with one O(2)Mn3Zn trigonal pyramid, corners with two equivalent O(1)Mn3Zn trigonal pyramids, corners with three equivalent O(3)Mn3Zn trigonal pyramids, edges with two equivalent O(5)Mn3Zn2 square pyramids, and  an edgeedge with one O(3)Mn3Zn trigonal pyramid. In the second O site, O(2) is bonded to one Mn(2), two equivalent Mn(4), and one Zn(1) atom to form distorted OMn3Zn trigonal pyramids that share  a cornercorner with one O(5)Mn3Zn2 square pyramid,  a cornercorner with one O(6)Mn3Zn2 square pyramid,  a cornercorner with one O(8)Mn3Zn2 trigonal bipyramid,  a cornercorner with one O(1)Mn3Zn trigonal pyramid, corners with two equivalent O(2)Mn3Zn trigonal pyramids, corners with three equivalent O(4)Mn3Zn trigonal pyramids, edges with two equivalent O(6)Mn3Zn2 square pyramids, edges with two equivalent O(8)Mn3Zn2 trigonal bipyramids, and  an edgeedge with one O(4)Mn3Zn trigonal pyramid. In the third O site, O(3) is bonded to one Mn(1), two equivalent Mn(3), and one Zn(2) atom to form OMn3Zn trigonal pyramids that share  a cornercorner with one O(5)Mn3Zn2 square pyramid,  a cornercorner with one O(6)Mn3Zn2 square pyramid,  a cornercorner with one O(8)Mn3Zn2 trigonal bipyramid,  a cornercorner with one O(4)Mn3Zn trigonal pyramid, corners with two equivalent O(3)Mn3Zn trigonal pyramids, corners with three equivalent O(1)Mn3Zn trigonal pyramids, edges with two equivalent O(5)Mn3Zn2 square pyramids, and  an edgeedge with one O(1)Mn3Zn trigonal pyramid. In the fourth O site, O(4) is bonded to one Mn(2), two equivalent Mn(4), and one Zn(2) atom to form OMn3Zn trigonal pyramids that share  a cornercorner with one O(5)Mn3Zn2 square pyramid,  a cornercorner with one O(6)Mn3Zn2 square pyramid,  a cornercorner with one O(8)Mn3Zn2 trigonal bipyramid,  a cornercorner with one O(3)Mn3Zn trigonal pyramid, corners with two equivalent O(4)Mn3Zn trigonal pyramids, corners with three equivalent O(2)Mn3Zn trigonal pyramids, edges with two equivalent O(6)Mn3Zn2 square pyramids, edges with two equivalent O(8)Mn3Zn2 trigonal bipyramids, and  an edgeedge with one O(2)Mn3Zn trigonal pyramid. In the fifth O site, O(5) is bonded to one Mn(3), two equivalent Mn(1), one Zn(1), and one Zn(2) atom to form distorted OMn3Zn2 square pyramids that share corners with two equivalent O(5)Mn3Zn2 square pyramids, corners with two equivalent O(6)Mn3Zn2 square pyramids,  a cornercorner with one O(1)Mn3Zn trigonal pyramid,  a cornercorner with one O(2)Mn3Zn trigonal pyramid,  a cornercorner with one O(3)Mn3Zn trigonal pyramid,  a cornercorner with one O(4)Mn3Zn trigonal pyramid,  an edgeedge with one O(8)Mn3Zn2 trigonal bipyramid, edges with two equivalent O(1)Mn3Zn trigonal pyramids, and edges with two equivalent O(3)Mn3Zn trigonal pyramids. In the sixth O site, O(6) is bonded to one Mn(4), two equivalent Mn(2), one Zn(1), and one Zn(2) atom to form distorted OMn3Zn2 square pyramids that share corners with two equivalent O(5)Mn3Zn2 square pyramids, corners with two equivalent O(6)Mn3Zn2 square pyramids,  a cornercorner with one O(8)Mn3Zn2 trigonal bipyramid,  a cornercorner with one O(1)Mn3Zn trigonal pyramid,  a cornercorner with one O(2)Mn3Zn trigonal pyramid,  a cornercorner with one O(3)Mn3Zn trigonal pyramid,  a cornercorner with one O(4)Mn3Zn trigonal pyramid, edges with three equivalent O(8)Mn3Zn2 trigonal bipyramids, edges with two equivalent O(2)Mn3Zn trigonal pyramids, and edges with two equivalent O(4)Mn3Zn trigonal pyramids. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Mn(3), two equivalent Mn(1), one Zn(1), and one Zn(2) atom. In the eighth O site, O(8) is bonded to one Mn(4), two equivalent Mn(2), one Zn(1), and one Zn(2) atom to form distorted OMn3Zn2 trigonal bipyramids that share  a cornercorner with one O(6)Mn3Zn2 square pyramid, corners with two equivalent O(8)Mn3Zn2 trigonal bipyramids,  a cornercorner with one O(1)Mn3Zn trigonal pyramid,  a cornercorner with one O(2)Mn3Zn trigonal pyramid,  a cornercorner with one O(3)Mn3Zn trigonal pyramid,  a cornercorner with one O(4)Mn3Zn trigonal pyramid,  an edgeedge with one O(5)Mn3Zn2 square pyramid, edges with three equivalent O(6)Mn3Zn2 square pyramids, edges with two equivalent O(2)Mn3Zn trigonal pyramids, and edges with two equivalent O(4)Mn3Zn trigonal pyramids.
ZnMn2O4 crystallizes in the monoclinic P2_1 space group. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 6-coordinate geometry to one O(1), one O(3), two equivalent O(5), and two equivalent O(7) atoms. The Mn(1)-O(1) bond length is 1.99 Å. The Mn(1)-O(3) bond length is 1.89 Å. There is one shorter (2.19 Å) and one longer (2.52 Å) Mn(1)-O(5) bond length. There is one shorter (1.99 Å) and one longer (2.02 Å) Mn(1)-O(7) bond length. In the second Mn site, Mn(2) is bonded to one O(2), one O(4), two equivalent O(6), and two equivalent O(8) atoms to form distorted edge-sharing MnO6 octahedra. The Mn(2)-O(2) bond length is 2.01 Å. The Mn(2)-O(4) bond length is 1.90 Å. There is one shorter (2.19 Å) and one longer (2.46 Å) Mn(2)-O(6) bond length. There is one shorter (1.99 Å) and one longer (2.01 Å) Mn(2)-O(8) bond length. In the third Mn site, Mn(3) is bonded to one O(5), one O(7), two equivalent O(1), and two equivalent O(3) atoms to form edge-sharing MnO6 octahedra. The Mn(3)-O(5) bond length is 1.98 Å. The Mn(3)-O(7) bond length is 2.00 Å. There is one shorter (1.98 Å) and one longer (2.00 Å) Mn(3)-O(1) bond length. There is one shorter (2.19 Å) and one longer (2.24 Å) Mn(3)-O(3) bond length. In the fourth Mn site, Mn(4) is bonded to one O(6), one O(8), two equivalent O(2), and two equivalent O(4) atoms to form edge-sharing MnO6 octahedra. The Mn(4)-O(6) bond length is 1.99 Å. The Mn(4)-O(8) bond length is 2.01 Å. There is one shorter (1.97 Å) and one longer (1.99 Å) Mn(4)-O(2) bond length. There is one shorter (2.20 Å) and one longer (2.27 Å) Mn(4)-O(4) bond length. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(5), one O(6), one O(7), and one O(8) atom. The Zn(1)-O(1) bond length is 2.11 Å. The Zn(1)-O(2) bond length is 2.14 Å. The Zn(1)-O(5) bond length is 2.07 Å. The Zn(1)-O(6) bond length is 2.04 Å. The Zn(1)-O(7) bond length is 2.59 Å. The Zn(1)-O(8) bond length is 2.44 Å. In the second Zn site, Zn(2) is bonded in a 6-coordinate geometry to one O(3), one O(4), one O(5), one O(6), one O(7), and one O(8) atom. The Zn(2)-O(3) bond length is 2.06 Å. The Zn(2)-O(4) bond length is 2.01 Å. The Zn(2)-O(5) bond length is 2.23 Å. The Zn(2)-O(6) bond length is 2.35 Å. The Zn(2)-O(7) bond length is 2.33 Å. The Zn(2)-O(8) bond length is 2.45 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Mn(1), two equivalent Mn(3), and one Zn(1) atom to form OMn3Zn trigonal pyramids that share  a cornercorner with one O(5)Mn3Zn2 square pyramid,  a cornercorner with one O(6)Mn3Zn2 square pyramid,  a cornercorner with one O(8)Mn3Zn2 trigonal bipyramid,  a cornercorner with one O(2)Mn3Zn trigonal pyramid, corners with two equivalent O(1)Mn3Zn trigonal pyramids, corners with three equivalent O(3)Mn3Zn trigonal pyramids, edges with two equivalent O(5)Mn3Zn2 square pyramids, and  an edgeedge with one O(3)Mn3Zn trigonal pyramid. In the second O site, O(2) is bonded to one Mn(2), two equivalent Mn(4), and one Zn(1) atom to form distorted OMn3Zn trigonal pyramids that share  a cornercorner with one O(5)Mn3Zn2 square pyramid,  a cornercorner with one O(6)Mn3Zn2 square pyramid,  a cornercorner with one O(8)Mn3Zn2 trigonal bipyramid,  a cornercorner with one O(1)Mn3Zn trigonal pyramid, corners with two equivalent O(2)Mn3Zn trigonal pyramids, corners with three equivalent O(4)Mn3Zn trigonal pyramids, edges with two equivalent O(6)Mn3Zn2 square pyramids, edges with two equivalent O(8)Mn3Zn2 trigonal bipyramids, and  an edgeedge with one O(4)Mn3Zn trigonal pyramid. In the third O site, O(3) is bonded to one Mn(1), two equivalent Mn(3), and one Zn(2) atom to form OMn3Zn trigonal pyramids that share  a cornercorner with one O(5)Mn3Zn2 square pyramid,  a cornercorner with one O(6)Mn3Zn2 square pyramid,  a cornercorner with one O(8)Mn3Zn2 trigonal bipyramid,  a cornercorner with one O(4)Mn3Zn trigonal pyramid, corners with two equivalent O(3)Mn3Zn trigonal pyramids, corners with three equivalent O(1)Mn3Zn trigonal pyramids, edges with two equivalent O(5)Mn3Zn2 square pyramids, and  an edgeedge with one O(1)Mn3Zn trigonal pyramid. In the fourth O site, O(4) is bonded to one Mn(2), two equivalent Mn(4), and one Zn(2) atom to form OMn3Zn trigonal pyramids that share  a cornercorner with one O(5)Mn3Zn2 square pyramid,  a cornercorner with one O(6)Mn3Zn2 square pyramid,  a cornercorner with one O(8)Mn3Zn2 trigonal bipyramid,  a cornercorner with one O(3)Mn3Zn trigonal pyramid, corners with two equivalent O(4)Mn3Zn trigonal pyramids, corners with three equivalent O(2)Mn3Zn trigonal pyramids, edges with two equivalent O(6)Mn3Zn2 square pyramids, edges with two equivalent O(8)Mn3Zn2 trigonal bipyramids, and  an edgeedge with one O(2)Mn3Zn trigonal pyramid. In the fifth O site, O(5) is bonded to one Mn(3), two equivalent Mn(1), one Zn(1), and one Zn(2) atom to form distorted OMn3Zn2 square pyramids that share corners with two equivalent O(5)Mn3Zn2 square pyramids, corners with two equivalent O(6)Mn3Zn2 square pyramids,  a cornercorner with one O(1)Mn3Zn trigonal pyramid,  a cornercorner with one O(2)Mn3Zn trigonal pyramid,  a cornercorner with one O(3)Mn3Zn trigonal pyramid,  a cornercorner with one O(4)Mn3Zn trigonal pyramid,  an edgeedge with one O(8)Mn3Zn2 trigonal bipyramid, edges with two equivalent O(1)Mn3Zn trigonal pyramids, and edges with two equivalent O(3)Mn3Zn trigonal pyramids. In the sixth O site, O(6) is bonded to one Mn(4), two equivalent Mn(2), one Zn(1), and one Zn(2) atom to form distorted OMn3Zn2 square pyramids that share corners with two equivalent O(5)Mn3Zn2 square pyramids, corners with two equivalent O(6)Mn3Zn2 square pyramids,  a cornercorner with one O(8)Mn3Zn2 trigonal bipyramid,  a cornercorner with one O(1)Mn3Zn trigonal pyramid,  a cornercorner with one O(2)Mn3Zn trigonal pyramid,  a cornercorner with one O(3)Mn3Zn trigonal pyramid,  a cornercorner with one O(4)Mn3Zn trigonal pyramid, edges with three equivalent O(8)Mn3Zn2 trigonal bipyramids, edges with two equivalent O(2)Mn3Zn trigonal pyramids, and edges with two equivalent O(4)Mn3Zn trigonal pyramids. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Mn(3), two equivalent Mn(1), one Zn(1), and one Zn(2) atom. In the eighth O site, O(8) is bonded to one Mn(4), two equivalent Mn(2), one Zn(1), and one Zn(2) atom to form distorted OMn3Zn2 trigonal bipyramids that share  a cornercorner with one O(6)Mn3Zn2 square pyramid, corners with two equivalent O(8)Mn3Zn2 trigonal bipyramids,  a cornercorner with one O(1)Mn3Zn trigonal pyramid,  a cornercorner with one O(2)Mn3Zn trigonal pyramid,  a cornercorner with one O(3)Mn3Zn trigonal pyramid,  a cornercorner with one O(4)Mn3Zn trigonal pyramid,  an edgeedge with one O(5)Mn3Zn2 square pyramid, edges with three equivalent O(6)Mn3Zn2 square pyramids, edges with two equivalent O(2)Mn3Zn trigonal pyramids, and edges with two equivalent O(4)Mn3Zn trigonal pyramids.