Zr4MnO9 crystallizes in the triclinic P1 space group. There are four inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), one O(6), and one O(7) atom. In the second Zr site, Zr(2) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(4), one O(5), one O(7), one O(8), and one O(9) atom. In the third Zr site, Zr(3) is bonded in a 7-coordinate geometry to one O(2), one O(3), one O(5), one O(6), one O(7), one O(8), and one O(9) atom. In the fourth Zr site, Zr(4) is bonded in a distorted pentagonal bipyramidal geometry to one O(1), one O(2), one O(3), one O(6), one O(7), one O(8), and one O(9) atom. Mn(1) is bonded in a 7-coordinate geometry to one O(1), one O(3), one O(4), one O(5), one O(6), one O(8), and one O(9) atom. There are nine inequivalent O sites. In the first O site, O(1) is bonded to one Zr(1), one Zr(2), one Zr(4), and one Mn(1) atom to form distorted OZr3Mn tetrahedra that share  a cornercorner with one O(3)Zr3Mn tetrahedra,  a cornercorner with one O(5)Zr3Mn tetrahedra,  a cornercorner with one O(8)Zr3Mn tetrahedra,  a cornercorner with one O(2)Zr4 tetrahedra, corners with three equivalent O(6)Zr3Mn tetrahedra, corners with three equivalent O(9)Zr3Mn tetrahedra, corners with three equivalent O(7)Zr4 trigonal pyramids,  an edgeedge with one O(3)Zr3Mn tetrahedra,  an edgeedge with one O(5)Zr3Mn tetrahedra,  an edgeedge with one O(8)Zr3Mn tetrahedra, and  an edgeedge with one O(2)Zr4 tetrahedra. In the second O site, O(2) is bonded to one Zr(1), one Zr(2), one Zr(3), and one Zr(4) atom to form OZr4 tetrahedra that share  a cornercorner with one O(1)Zr3Mn tetrahedra,  a cornercorner with one O(6)Zr3Mn tetrahedra,  a cornercorner with one O(9)Zr3Mn tetrahedra, corners with three equivalent O(3)Zr3Mn tetrahedra, corners with three equivalent O(5)Zr3Mn tetrahedra, corners with three equivalent O(8)Zr3Mn tetrahedra,  an edgeedge with one O(1)Zr3Mn tetrahedra,  an edgeedge with one O(6)Zr3Mn tetrahedra,  an edgeedge with one O(9)Zr3Mn tetrahedra, and edges with two equivalent O(7)Zr4 trigonal pyramids. In the third O site, O(3) is bonded to one Zr(1), one Zr(3), one Zr(4), and one Mn(1) atom to form OZr3Mn tetrahedra that share  a cornercorner with one O(1)Zr3Mn tetrahedra,  a cornercorner with one O(9)Zr3Mn tetrahedra, corners with three equivalent O(5)Zr3Mn tetrahedra, corners with three equivalent O(8)Zr3Mn tetrahedra, corners with three equivalent O(2)Zr4 tetrahedra,  a cornercorner with one O(7)Zr4 trigonal pyramid,  an edgeedge with one O(1)Zr3Mn tetrahedra,  an edgeedge with one O(9)Zr3Mn tetrahedra, edges with two equivalent O(6)Zr3Mn tetrahedra, and  an edgeedge with one O(7)Zr4 trigonal pyramid. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Zr(1), one Zr(2), and one Mn(1) atom. In the fifth O site, O(5) is bonded to one Zr(1), one Zr(2), one Zr(3), and one Mn(1) atom to form distorted OZr3Mn tetrahedra that share  a cornercorner with one O(1)Zr3Mn tetrahedra,  a cornercorner with one O(6)Zr3Mn tetrahedra,  a cornercorner with one O(9)Zr3Mn tetrahedra, corners with three equivalent O(3)Zr3Mn tetrahedra, corners with three equivalent O(8)Zr3Mn tetrahedra, corners with three equivalent O(2)Zr4 tetrahedra,  a cornercorner with one O(7)Zr4 trigonal pyramid,  an edgeedge with one O(1)Zr3Mn tetrahedra,  an edgeedge with one O(6)Zr3Mn tetrahedra,  an edgeedge with one O(9)Zr3Mn tetrahedra, and  an edgeedge with one O(7)Zr4 trigonal pyramid. In the sixth O site, O(6) is bonded to one Zr(1), one Zr(3), one Zr(4), and one Mn(1) atom to form OZr3Mn tetrahedra that share  a cornercorner with one O(5)Zr3Mn tetrahedra,  a cornercorner with one O(8)Zr3Mn tetrahedra,  a cornercorner with one O(2)Zr4 tetrahedra, corners with three equivalent O(1)Zr3Mn tetrahedra, corners with three equivalent O(9)Zr3Mn tetrahedra, corners with three equivalent O(7)Zr4 trigonal pyramids,  an edgeedge with one O(5)Zr3Mn tetrahedra,  an edgeedge with one O(8)Zr3Mn tetrahedra,  an edgeedge with one O(2)Zr4 tetrahedra, and edges with two equivalent O(3)Zr3Mn tetrahedra. In the seventh O site, O(7) is bonded to one Zr(1), one Zr(2), one Zr(3), and one Zr(4) atom to form distorted OZr4 trigonal pyramids that share  a cornercorner with one O(3)Zr3Mn tetrahedra,  a cornercorner with one O(5)Zr3Mn tetrahedra,  a cornercorner with one O(8)Zr3Mn tetrahedra, corners with three equivalent O(1)Zr3Mn tetrahedra, corners with three equivalent O(6)Zr3Mn tetrahedra, corners with three equivalent O(9)Zr3Mn tetrahedra,  an edgeedge with one O(3)Zr3Mn tetrahedra,  an edgeedge with one O(5)Zr3Mn tetrahedra,  an edgeedge with one O(8)Zr3Mn tetrahedra, and edges with two equivalent O(2)Zr4 tetrahedra. In the eighth O site, O(8) is bonded to one Zr(2), one Zr(3), one Zr(4), and one Mn(1) atom to form OZr3Mn tetrahedra that share  a cornercorner with one O(1)Zr3Mn tetrahedra,  a cornercorner with one O(6)Zr3Mn tetrahedra, corners with three equivalent O(3)Zr3Mn tetrahedra, corners with three equivalent O(5)Zr3Mn tetrahedra, corners with three equivalent O(2)Zr4 tetrahedra,  a cornercorner with one O(7)Zr4 trigonal pyramid,  an edgeedge with one O(1)Zr3Mn tetrahedra,  an edgeedge with one O(6)Zr3Mn tetrahedra, edges with two equivalent O(9)Zr3Mn tetrahedra, and  an edgeedge with one O(7)Zr4 trigonal pyramid. In the ninth O site, O(9) is bonded to one Zr(2), one Zr(3), one Zr(4), and one Mn(1) atom to form OZr3Mn tetrahedra that share  a cornercorner with one O(3)Zr3Mn tetrahedra,  a cornercorner with one O(5)Zr3Mn tetrahedra,  a cornercorner with one O(2)Zr4 tetrahedra, corners with three equivalent O(1)Zr3Mn tetrahedra, corners with three equivalent O(6)Zr3Mn tetrahedra, corners with three equivalent O(7)Zr4 trigonal pyramids,  an edgeedge with one O(3)Zr3Mn tetrahedra,  an edgeedge with one O(5)Zr3Mn tetrahedra,  an edgeedge with one O(2)Zr4 tetrahedra, and edges with two equivalent O(8)Zr3Mn tetrahedra.
Zr4MnO9 crystallizes in the triclinic P1 space group. There are four inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), one O(6), and one O(7) atom. The Zr(1)-O(1) bond length is 2.19 Å. The Zr(1)-O(2) bond length is 2.40 Å. The Zr(1)-O(3) bond length is 2.29 Å. The Zr(1)-O(4) bond length is 2.06 Å. The Zr(1)-O(5) bond length is 2.18 Å. The Zr(1)-O(6) bond length is 2.09 Å. The Zr(1)-O(7) bond length is 2.18 Å. In the second Zr site, Zr(2) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(4), one O(5), one O(7), one O(8), and one O(9) atom. The Zr(2)-O(1) bond length is 2.19 Å. The Zr(2)-O(2) bond length is 2.21 Å. The Zr(2)-O(4) bond length is 2.07 Å. The Zr(2)-O(5) bond length is 2.17 Å. The Zr(2)-O(7) bond length is 2.35 Å. The Zr(2)-O(8) bond length is 2.18 Å. The Zr(2)-O(9) bond length is 2.20 Å. In the third Zr site, Zr(3) is bonded in a 7-coordinate geometry to one O(2), one O(3), one O(5), one O(6), one O(7), one O(8), and one O(9) atom. The Zr(3)-O(2) bond length is 2.13 Å. The Zr(3)-O(3) bond length is 2.09 Å. The Zr(3)-O(5) bond length is 2.08 Å. The Zr(3)-O(6) bond length is 2.34 Å. The Zr(3)-O(7) bond length is 2.50 Å. The Zr(3)-O(8) bond length is 2.05 Å. The Zr(3)-O(9) bond length is 2.29 Å. In the fourth Zr site, Zr(4) is bonded in a distorted pentagonal bipyramidal geometry to one O(1), one O(2), one O(3), one O(6), one O(7), one O(8), and one O(9) atom. The Zr(4)-O(1) bond length is 2.16 Å. The Zr(4)-O(2) bond length is 2.26 Å. The Zr(4)-O(3) bond length is 2.25 Å. The Zr(4)-O(6) bond length is 2.11 Å. The Zr(4)-O(7) bond length is 2.15 Å. The Zr(4)-O(8) bond length is 2.16 Å. The Zr(4)-O(9) bond length is 2.24 Å. Mn(1) is bonded in a 7-coordinate geometry to one O(1), one O(3), one O(4), one O(5), one O(6), one O(8), and one O(9) atom. The Mn(1)-O(1) bond length is 2.64 Å. The Mn(1)-O(3) bond length is 2.15 Å. The Mn(1)-O(4) bond length is 2.29 Å. The Mn(1)-O(5) bond length is 2.41 Å. The Mn(1)-O(6) bond length is 2.32 Å. The Mn(1)-O(8) bond length is 2.33 Å. The Mn(1)-O(9) bond length is 2.14 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded to one Zr(1), one Zr(2), one Zr(4), and one Mn(1) atom to form distorted OZr3Mn tetrahedra that share  a cornercorner with one O(3)Zr3Mn tetrahedra,  a cornercorner with one O(5)Zr3Mn tetrahedra,  a cornercorner with one O(8)Zr3Mn tetrahedra,  a cornercorner with one O(2)Zr4 tetrahedra, corners with three equivalent O(6)Zr3Mn tetrahedra, corners with three equivalent O(9)Zr3Mn tetrahedra, corners with three equivalent O(7)Zr4 trigonal pyramids,  an edgeedge with one O(3)Zr3Mn tetrahedra,  an edgeedge with one O(5)Zr3Mn tetrahedra,  an edgeedge with one O(8)Zr3Mn tetrahedra, and  an edgeedge with one O(2)Zr4 tetrahedra. In the second O site, O(2) is bonded to one Zr(1), one Zr(2), one Zr(3), and one Zr(4) atom to form OZr4 tetrahedra that share  a cornercorner with one O(1)Zr3Mn tetrahedra,  a cornercorner with one O(6)Zr3Mn tetrahedra,  a cornercorner with one O(9)Zr3Mn tetrahedra, corners with three equivalent O(3)Zr3Mn tetrahedra, corners with three equivalent O(5)Zr3Mn tetrahedra, corners with three equivalent O(8)Zr3Mn tetrahedra,  an edgeedge with one O(1)Zr3Mn tetrahedra,  an edgeedge with one O(6)Zr3Mn tetrahedra,  an edgeedge with one O(9)Zr3Mn tetrahedra, and edges with two equivalent O(7)Zr4 trigonal pyramids. In the third O site, O(3) is bonded to one Zr(1), one Zr(3), one Zr(4), and one Mn(1) atom to form OZr3Mn tetrahedra that share  a cornercorner with one O(1)Zr3Mn tetrahedra,  a cornercorner with one O(9)Zr3Mn tetrahedra, corners with three equivalent O(5)Zr3Mn tetrahedra, corners with three equivalent O(8)Zr3Mn tetrahedra, corners with three equivalent O(2)Zr4 tetrahedra,  a cornercorner with one O(7)Zr4 trigonal pyramid,  an edgeedge with one O(1)Zr3Mn tetrahedra,  an edgeedge with one O(9)Zr3Mn tetrahedra, edges with two equivalent O(6)Zr3Mn tetrahedra, and  an edgeedge with one O(7)Zr4 trigonal pyramid. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Zr(1), one Zr(2), and one Mn(1) atom. In the fifth O site, O(5) is bonded to one Zr(1), one Zr(2), one Zr(3), and one Mn(1) atom to form distorted OZr3Mn tetrahedra that share  a cornercorner with one O(1)Zr3Mn tetrahedra,  a cornercorner with one O(6)Zr3Mn tetrahedra,  a cornercorner with one O(9)Zr3Mn tetrahedra, corners with three equivalent O(3)Zr3Mn tetrahedra, corners with three equivalent O(8)Zr3Mn tetrahedra, corners with three equivalent O(2)Zr4 tetrahedra,  a cornercorner with one O(7)Zr4 trigonal pyramid,  an edgeedge with one O(1)Zr3Mn tetrahedra,  an edgeedge with one O(6)Zr3Mn tetrahedra,  an edgeedge with one O(9)Zr3Mn tetrahedra, and  an edgeedge with one O(7)Zr4 trigonal pyramid. In the sixth O site, O(6) is bonded to one Zr(1), one Zr(3), one Zr(4), and one Mn(1) atom to form OZr3Mn tetrahedra that share  a cornercorner with one O(5)Zr3Mn tetrahedra,  a cornercorner with one O(8)Zr3Mn tetrahedra,  a cornercorner with one O(2)Zr4 tetrahedra, corners with three equivalent O(1)Zr3Mn tetrahedra, corners with three equivalent O(9)Zr3Mn tetrahedra, corners with three equivalent O(7)Zr4 trigonal pyramids,  an edgeedge with one O(5)Zr3Mn tetrahedra,  an edgeedge with one O(8)Zr3Mn tetrahedra,  an edgeedge with one O(2)Zr4 tetrahedra, and edges with two equivalent O(3)Zr3Mn tetrahedra. In the seventh O site, O(7) is bonded to one Zr(1), one Zr(2), one Zr(3), and one Zr(4) atom to form distorted OZr4 trigonal pyramids that share  a cornercorner with one O(3)Zr3Mn tetrahedra,  a cornercorner with one O(5)Zr3Mn tetrahedra,  a cornercorner with one O(8)Zr3Mn tetrahedra, corners with three equivalent O(1)Zr3Mn tetrahedra, corners with three equivalent O(6)Zr3Mn tetrahedra, corners with three equivalent O(9)Zr3Mn tetrahedra,  an edgeedge with one O(3)Zr3Mn tetrahedra,  an edgeedge with one O(5)Zr3Mn tetrahedra,  an edgeedge with one O(8)Zr3Mn tetrahedra, and edges with two equivalent O(2)Zr4 tetrahedra. In the eighth O site, O(8) is bonded to one Zr(2), one Zr(3), one Zr(4), and one Mn(1) atom to form OZr3Mn tetrahedra that share  a cornercorner with one O(1)Zr3Mn tetrahedra,  a cornercorner with one O(6)Zr3Mn tetrahedra, corners with three equivalent O(3)Zr3Mn tetrahedra, corners with three equivalent O(5)Zr3Mn tetrahedra, corners with three equivalent O(2)Zr4 tetrahedra,  a cornercorner with one O(7)Zr4 trigonal pyramid,  an edgeedge with one O(1)Zr3Mn tetrahedra,  an edgeedge with one O(6)Zr3Mn tetrahedra, edges with two equivalent O(9)Zr3Mn tetrahedra, and  an edgeedge with one O(7)Zr4 trigonal pyramid. In the ninth O site, O(9) is bonded to one Zr(2), one Zr(3), one Zr(4), and one Mn(1) atom to form OZr3Mn tetrahedra that share  a cornercorner with one O(3)Zr3Mn tetrahedra,  a cornercorner with one O(5)Zr3Mn tetrahedra,  a cornercorner with one O(2)Zr4 tetrahedra, corners with three equivalent O(1)Zr3Mn tetrahedra, corners with three equivalent O(6)Zr3Mn tetrahedra, corners with three equivalent O(7)Zr4 trigonal pyramids,  an edgeedge with one O(3)Zr3Mn tetrahedra,  an edgeedge with one O(5)Zr3Mn tetrahedra,  an edgeedge with one O(2)Zr4 tetrahedra, and edges with two equivalent O(8)Zr3Mn tetrahedra.