V4MnFe(Pb2O9)2 crystallizes in the triclinic P-1 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form VO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra and  a cornercorner with one Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-58°. In the second V site, V(2) is bonded to one O(1), one O(7), one O(8), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra and  a cornercorner with one Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-50°. Mn(1) is bonded to two equivalent O(3), two equivalent O(6), and two equivalent O(7) atoms to form MnO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, and edges with two equivalent Fe(1)O6 octahedra. Fe(1) is bonded to two equivalent O(4), two equivalent O(6), and two equivalent O(7) atoms to form FeO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, and edges with two equivalent Mn(1)O6 octahedra. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 4-coordinate geometry to one O(5), one O(6), one O(8), and one O(9) atom. In the second Pb site, Pb(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(8), and one O(9) atom. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one V(2) and one Pb(2) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one V(1) and one Pb(2) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one V(1), one Mn(1), and one Pb(2) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one V(1), one Fe(1), and one Pb(2) atom. In the fifth O site, O(5) is bonded in a single-bond geometry to one V(1) and one Pb(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1), one Fe(1), and one Pb(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(2), one Mn(1), and one Fe(1) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one V(2), one Pb(1), and one Pb(2) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one V(2), one Pb(1), and one Pb(2) atom.
V4MnFe(Pb2O9)2 crystallizes in the triclinic P-1 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form VO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra and  a cornercorner with one Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-58°. The V(1)-O(2) bond length is 1.72 Å. The V(1)-O(3) bond length is 1.79 Å. The V(1)-O(4) bond length is 1.79 Å. The V(1)-O(5) bond length is 1.69 Å. In the second V site, V(2) is bonded to one O(1), one O(7), one O(8), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra and  a cornercorner with one Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-50°. The V(2)-O(1) bond length is 1.67 Å. The V(2)-O(7) bond length is 1.83 Å. The V(2)-O(8) bond length is 1.75 Å. The V(2)-O(9) bond length is 1.75 Å. Mn(1) is bonded to two equivalent O(3), two equivalent O(6), and two equivalent O(7) atoms to form MnO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, and edges with two equivalent Fe(1)O6 octahedra. Both Mn(1)-O(3) bond lengths are 1.93 Å. Both Mn(1)-O(6) bond lengths are 1.93 Å. Both Mn(1)-O(7) bond lengths are 1.96 Å. Fe(1) is bonded to two equivalent O(4), two equivalent O(6), and two equivalent O(7) atoms to form FeO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, and edges with two equivalent Mn(1)O6 octahedra. Both Fe(1)-O(4) bond lengths are 1.96 Å. Both Fe(1)-O(6) bond lengths are 1.90 Å. Both Fe(1)-O(7) bond lengths are 2.13 Å. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 4-coordinate geometry to one O(5), one O(6), one O(8), and one O(9) atom. The Pb(1)-O(5) bond length is 2.74 Å. The Pb(1)-O(6) bond length is 2.60 Å. The Pb(1)-O(8) bond length is 2.56 Å. The Pb(1)-O(9) bond length is 2.54 Å. In the second Pb site, Pb(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(8), and one O(9) atom. The Pb(2)-O(1) bond length is 2.58 Å. The Pb(2)-O(2) bond length is 2.56 Å. The Pb(2)-O(3) bond length is 2.77 Å. The Pb(2)-O(4) bond length is 2.81 Å. The Pb(2)-O(8) bond length is 2.46 Å. The Pb(2)-O(9) bond length is 2.47 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one V(2) and one Pb(2) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one V(1) and one Pb(2) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one V(1), one Mn(1), and one Pb(2) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one V(1), one Fe(1), and one Pb(2) atom. In the fifth O site, O(5) is bonded in a single-bond geometry to one V(1) and one Pb(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Mn(1), one Fe(1), and one Pb(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(2), one Mn(1), and one Fe(1) atom. In the eighth O site, O(8) is bonded in a distorted single-bond geometry to one V(2), one Pb(1), and one Pb(2) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one V(2), one Pb(1), and one Pb(2) atom.