Fe4Zn3(BiO4)6 crystallizes in the triclinic P-1 space group. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(3), one O(6), one O(7), one O(9), and two equivalent O(4) atoms to form FeO6 octahedra that share  a cornercorner with one Bi(3)O6 octahedra, corners with two equivalent Bi(1)O6 octahedra, corners with two equivalent Bi(2)O6 pentagonal pyramids,  an edgeedge with one Fe(1)O6 octahedra, and  an edgeedge with one Bi(2)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 38-55°. In the second Fe site, Fe(2) is bonded to one O(10), one O(11), one O(12), one O(5), and two equivalent O(8) atoms to form distorted FeO6 octahedra that share  a cornercorner with one Bi(3)O6 octahedra, corners with two equivalent Bi(1)O6 octahedra,  a cornercorner with one Bi(2)O6 pentagonal pyramid,  an edgeedge with one Fe(2)O6 octahedra, edges with two equivalent Bi(3)O6 octahedra, and  an edgeedge with one Bi(2)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 36-55°. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(3) atoms. In the second Zn site, Zn(2) is bonded in a distorted pentagonal planar geometry to one O(11), one O(2), one O(5), one O(6), and one O(7) atom. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(1), one O(10), one O(11), one O(2), one O(3), and one O(6) atom to form BiO6 octahedra that share  a cornercorner with one Bi(3)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, and corners with two equivalent Bi(2)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 40-55°. In the second Bi site, Bi(2) is bonded to one O(1), one O(11), one O(4), one O(7), one O(8), and one O(9) atom to form distorted BiO6 pentagonal pyramids that share  a cornercorner with one Fe(2)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent Bi(1)O6 octahedra,  an edgeedge with one Fe(1)O6 octahedra,  an edgeedge with one Fe(2)O6 octahedra, and  an edgeedge with one Bi(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 35-54°. In the third Bi site, Bi(3) is bonded to one O(2), one O(5), one O(8), one O(9), and two equivalent O(12) atoms to form distorted BiO6 octahedra that share  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Bi(1)O6 octahedra,  an edgeedge with one Bi(3)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and  an edgeedge with one Bi(2)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 36-52°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Zn(1), one Bi(1), and one Bi(2) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Zn(2), one Bi(1), and one Bi(3) atom. In the third O site, O(3) is bonded in a trigonal non-coplanar geometry to one Fe(1), one Zn(1), and one Bi(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Fe(1) and one Bi(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Fe(2), one Zn(2), and one Bi(3) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Fe(1), one Zn(2), and one Bi(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one Fe(1), one Zn(2), and one Bi(2) atom. In the eighth O site, O(8) is bonded to two equivalent Fe(2), one Bi(2), and one Bi(3) atom to form distorted OFe2Bi2 tetrahedra that share  a cornercorner with one O(11)ZnFeBi2 trigonal pyramid,  an edgeedge with one O(8)Fe2Bi2 tetrahedra, and  an edgeedge with one O(11)ZnFeBi2 trigonal pyramid. In the ninth O site, O(9) is bonded in a distorted trigonal non-coplanar geometry to one Fe(1), one Bi(2), and one Bi(3) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Fe(2) and one Bi(1) atom. In the eleventh O site, O(11) is bonded to one Fe(2), one Zn(2), one Bi(1), and one Bi(2) atom to form a mixture of distorted corner and edge-sharing OZnFeBi2 trigonal pyramids. In the twelfth O site, O(12) is bonded in a distorted trigonal non-coplanar geometry to one Fe(2) and two equivalent Bi(3) atoms.
Fe4Zn3(BiO4)6 crystallizes in the triclinic P-1 space group. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(3), one O(6), one O(7), one O(9), and two equivalent O(4) atoms to form FeO6 octahedra that share  a cornercorner with one Bi(3)O6 octahedra, corners with two equivalent Bi(1)O6 octahedra, corners with two equivalent Bi(2)O6 pentagonal pyramids,  an edgeedge with one Fe(1)O6 octahedra, and  an edgeedge with one Bi(2)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 38-55°. The Fe(1)-O(3) bond length is 2.04 Å. The Fe(1)-O(6) bond length is 2.01 Å. The Fe(1)-O(7) bond length is 1.94 Å. The Fe(1)-O(9) bond length is 2.13 Å. There is one shorter (2.03 Å) and one longer (2.04 Å) Fe(1)-O(4) bond length. In the second Fe site, Fe(2) is bonded to one O(10), one O(11), one O(12), one O(5), and two equivalent O(8) atoms to form distorted FeO6 octahedra that share  a cornercorner with one Bi(3)O6 octahedra, corners with two equivalent Bi(1)O6 octahedra,  a cornercorner with one Bi(2)O6 pentagonal pyramid,  an edgeedge with one Fe(2)O6 octahedra, edges with two equivalent Bi(3)O6 octahedra, and  an edgeedge with one Bi(2)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 36-55°. The Fe(2)-O(10) bond length is 1.87 Å. The Fe(2)-O(11) bond length is 2.03 Å. The Fe(2)-O(12) bond length is 2.01 Å. The Fe(2)-O(5) bond length is 2.04 Å. There is one shorter (2.07 Å) and one longer (2.17 Å) Fe(2)-O(8) bond length. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(3) atoms. Both Zn(1)-O(1) bond lengths are 2.19 Å. Both Zn(1)-O(3) bond lengths are 1.92 Å. In the second Zn site, Zn(2) is bonded in a distorted pentagonal planar geometry to one O(11), one O(2), one O(5), one O(6), and one O(7) atom. The Zn(2)-O(11) bond length is 2.39 Å. The Zn(2)-O(2) bond length is 2.02 Å. The Zn(2)-O(5) bond length is 1.99 Å. The Zn(2)-O(6) bond length is 1.98 Å. The Zn(2)-O(7) bond length is 2.09 Å. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(1), one O(10), one O(11), one O(2), one O(3), and one O(6) atom to form BiO6 octahedra that share  a cornercorner with one Bi(3)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, and corners with two equivalent Bi(2)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 40-55°. The Bi(1)-O(1) bond length is 2.25 Å. The Bi(1)-O(10) bond length is 2.04 Å. The Bi(1)-O(11) bond length is 2.19 Å. The Bi(1)-O(2) bond length is 2.30 Å. The Bi(1)-O(3) bond length is 2.17 Å. The Bi(1)-O(6) bond length is 2.12 Å. In the second Bi site, Bi(2) is bonded to one O(1), one O(11), one O(4), one O(7), one O(8), and one O(9) atom to form distorted BiO6 pentagonal pyramids that share  a cornercorner with one Fe(2)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent Bi(1)O6 octahedra,  an edgeedge with one Fe(1)O6 octahedra,  an edgeedge with one Fe(2)O6 octahedra, and  an edgeedge with one Bi(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 35-54°. The Bi(2)-O(1) bond length is 2.17 Å. The Bi(2)-O(11) bond length is 2.25 Å. The Bi(2)-O(4) bond length is 2.11 Å. The Bi(2)-O(7) bond length is 2.10 Å. The Bi(2)-O(8) bond length is 2.18 Å. The Bi(2)-O(9) bond length is 2.30 Å. In the third Bi site, Bi(3) is bonded to one O(2), one O(5), one O(8), one O(9), and two equivalent O(12) atoms to form distorted BiO6 octahedra that share  a cornercorner with one Fe(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra,  a cornercorner with one Bi(1)O6 octahedra,  an edgeedge with one Bi(3)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and  an edgeedge with one Bi(2)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 36-52°. The Bi(3)-O(2) bond length is 2.16 Å. The Bi(3)-O(5) bond length is 2.08 Å. The Bi(3)-O(8) bond length is 2.33 Å. The Bi(3)-O(9) bond length is 2.16 Å. There is one shorter (2.14 Å) and one longer (2.24 Å) Bi(3)-O(12) bond length. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Zn(1), one Bi(1), and one Bi(2) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Zn(2), one Bi(1), and one Bi(3) atom. In the third O site, O(3) is bonded in a trigonal non-coplanar geometry to one Fe(1), one Zn(1), and one Bi(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Fe(1) and one Bi(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Fe(2), one Zn(2), and one Bi(3) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Fe(1), one Zn(2), and one Bi(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one Fe(1), one Zn(2), and one Bi(2) atom. In the eighth O site, O(8) is bonded to two equivalent Fe(2), one Bi(2), and one Bi(3) atom to form distorted OFe2Bi2 tetrahedra that share  a cornercorner with one O(11)ZnFeBi2 trigonal pyramid,  an edgeedge with one O(8)Fe2Bi2 tetrahedra, and  an edgeedge with one O(11)ZnFeBi2 trigonal pyramid. In the ninth O site, O(9) is bonded in a distorted trigonal non-coplanar geometry to one Fe(1), one Bi(2), and one Bi(3) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Fe(2) and one Bi(1) atom. In the eleventh O site, O(11) is bonded to one Fe(2), one Zn(2), one Bi(1), and one Bi(2) atom to form a mixture of distorted corner and edge-sharing OZnFeBi2 trigonal pyramids. In the twelfth O site, O(12) is bonded in a distorted trigonal non-coplanar geometry to one Fe(2) and two equivalent Bi(3) atoms.