Ca2WFeO6 crystallizes in the orthorhombic Pmm2 space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to two equivalent O(1), two equivalent O(2), two equivalent O(3), two equivalent O(4), two equivalent O(5), and two equivalent O(6) atoms to form CaO12 cuboctahedra that share corners with four equivalent Ca(1)O12 cuboctahedra, corners with eight equivalent Ca(2)O12 cuboctahedra, faces with two equivalent Ca(1)O12 cuboctahedra, faces with four equivalent Ca(2)O12 cuboctahedra, faces with two equivalent W(1)O6 octahedra, faces with two equivalent W(2)O6 octahedra, faces with two equivalent Fe(1)O6 octahedra, and faces with two equivalent Fe(2)O6 octahedra. In the second Ca site, Ca(2) is bonded to two equivalent O(1), two equivalent O(2), two equivalent O(3), two equivalent O(4), two equivalent O(5), and two equivalent O(6) atoms to form distorted CaO12 cuboctahedra that share corners with four equivalent Ca(2)O12 cuboctahedra, corners with eight equivalent Ca(1)O12 cuboctahedra, faces with two equivalent Ca(2)O12 cuboctahedra, faces with four equivalent Ca(1)O12 cuboctahedra, faces with two equivalent W(1)O6 octahedra, faces with two equivalent W(2)O6 octahedra, faces with two equivalent Fe(1)O6 octahedra, and faces with two equivalent Fe(2)O6 octahedra. There are two inequivalent W sites. In the first W site, W(1) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms to form WO6 octahedra that share corners with two equivalent Fe(2)O6 octahedra, corners with four equivalent Fe(1)O6 octahedra, faces with four equivalent Ca(1)O12 cuboctahedra, and faces with four equivalent Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 3-6°. In the second W site, W(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(6) atoms to form WO6 octahedra that share corners with two equivalent Fe(1)O6 octahedra, corners with four equivalent Fe(2)O6 octahedra, faces with four equivalent Ca(1)O12 cuboctahedra, and faces with four equivalent Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-4°. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form FeO6 octahedra that share corners with two equivalent W(2)O6 octahedra, corners with four equivalent W(1)O6 octahedra, faces with four equivalent Ca(1)O12 cuboctahedra, and faces with four equivalent Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 3-6°. In the second Fe site, Fe(2) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(6) atoms to form FeO6 octahedra that share corners with two equivalent W(1)O6 octahedra, corners with four equivalent W(2)O6 octahedra, faces with four equivalent Ca(1)O12 cuboctahedra, and faces with four equivalent Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-3°. There are six inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ca(1), two equivalent Ca(2), one W(2), and one Fe(2) atom to form a mixture of distorted face, edge, and corner-sharing OCa4FeW octahedra. The corner-sharing octahedral tilt angles are 1°. In the second O site, O(2) is bonded in a 2-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), one W(2), and one Fe(1) atom. In the third O site, O(3) is bonded in a 6-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), one W(1), and one Fe(1) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), one W(1), and one Fe(1) atom. In the fifth O site, O(5) is bonded in a 2-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), one W(1), and one Fe(2) atom. In the sixth O site, O(6) is bonded to two equivalent Ca(1), two equivalent Ca(2), one W(2), and one Fe(2) atom to form a mixture of distorted face, edge, and corner-sharing OCa4FeW octahedra. The corner-sharing octahedral tilt angles are 1°.
Ca2WFeO6 crystallizes in the orthorhombic Pmm2 space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to two equivalent O(1), two equivalent O(2), two equivalent O(3), two equivalent O(4), two equivalent O(5), and two equivalent O(6) atoms to form CaO12 cuboctahedra that share corners with four equivalent Ca(1)O12 cuboctahedra, corners with eight equivalent Ca(2)O12 cuboctahedra, faces with two equivalent Ca(1)O12 cuboctahedra, faces with four equivalent Ca(2)O12 cuboctahedra, faces with two equivalent W(1)O6 octahedra, faces with two equivalent W(2)O6 octahedra, faces with two equivalent Fe(1)O6 octahedra, and faces with two equivalent Fe(2)O6 octahedra. Both Ca(1)-O(1) bond lengths are 2.77 Å. Both Ca(1)-O(2) bond lengths are 2.80 Å. Both Ca(1)-O(3) bond lengths are 2.98 Å. Both Ca(1)-O(4) bond lengths are 2.74 Å. There is one shorter (2.68 Å) and one longer (2.99 Å) Ca(1)-O(5) bond length. Both Ca(1)-O(6) bond lengths are 2.69 Å. In the second Ca site, Ca(2) is bonded to two equivalent O(1), two equivalent O(2), two equivalent O(3), two equivalent O(4), two equivalent O(5), and two equivalent O(6) atoms to form distorted CaO12 cuboctahedra that share corners with four equivalent Ca(2)O12 cuboctahedra, corners with eight equivalent Ca(1)O12 cuboctahedra, faces with two equivalent Ca(2)O12 cuboctahedra, faces with four equivalent Ca(1)O12 cuboctahedra, faces with two equivalent W(1)O6 octahedra, faces with two equivalent W(2)O6 octahedra, faces with two equivalent Fe(1)O6 octahedra, and faces with two equivalent Fe(2)O6 octahedra. Both Ca(2)-O(1) bond lengths are 2.70 Å. There is one shorter (2.63 Å) and one longer (3.05 Å) Ca(2)-O(2) bond length. Both Ca(2)-O(3) bond lengths are 2.72 Å. Both Ca(2)-O(4) bond lengths are 3.02 Å. Both Ca(2)-O(5) bond lengths are 2.80 Å. Both Ca(2)-O(6) bond lengths are 2.83 Å. There are two inequivalent W sites. In the first W site, W(1) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms to form WO6 octahedra that share corners with two equivalent Fe(2)O6 octahedra, corners with four equivalent Fe(1)O6 octahedra, faces with four equivalent Ca(1)O12 cuboctahedra, and faces with four equivalent Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 3-6°. Both W(1)-O(3) bond lengths are 1.97 Å. Both W(1)-O(4) bond lengths are 1.99 Å. Both W(1)-O(5) bond lengths are 1.98 Å. In the second W site, W(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(6) atoms to form WO6 octahedra that share corners with two equivalent Fe(1)O6 octahedra, corners with four equivalent Fe(2)O6 octahedra, faces with four equivalent Ca(1)O12 cuboctahedra, and faces with four equivalent Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-4°. Both W(2)-O(1) bond lengths are 2.01 Å. Both W(2)-O(2) bond lengths are 1.94 Å. Both W(2)-O(6) bond lengths are 1.99 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form FeO6 octahedra that share corners with two equivalent W(2)O6 octahedra, corners with four equivalent W(1)O6 octahedra, faces with four equivalent Ca(1)O12 cuboctahedra, and faces with four equivalent Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 3-6°. Both Fe(1)-O(2) bond lengths are 2.00 Å. Both Fe(1)-O(3) bond lengths are 2.03 Å. Both Fe(1)-O(4) bond lengths are 1.98 Å. In the second Fe site, Fe(2) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(6) atoms to form FeO6 octahedra that share corners with two equivalent W(1)O6 octahedra, corners with four equivalent W(2)O6 octahedra, faces with four equivalent Ca(1)O12 cuboctahedra, and faces with four equivalent Ca(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-3°. Both Fe(2)-O(1) bond lengths are 1.97 Å. Both Fe(2)-O(5) bond lengths are 1.96 Å. Both Fe(2)-O(6) bond lengths are 2.00 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ca(1), two equivalent Ca(2), one W(2), and one Fe(2) atom to form a mixture of distorted face, edge, and corner-sharing OCa4FeW octahedra. The corner-sharing octahedral tilt angles are 1°. In the second O site, O(2) is bonded in a 2-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), one W(2), and one Fe(1) atom. In the third O site, O(3) is bonded in a 6-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), one W(1), and one Fe(1) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), one W(1), and one Fe(1) atom. In the fifth O site, O(5) is bonded in a 2-coordinate geometry to two equivalent Ca(1), two equivalent Ca(2), one W(1), and one Fe(2) atom. In the sixth O site, O(6) is bonded to two equivalent Ca(1), two equivalent Ca(2), one W(2), and one Fe(2) atom to form a mixture of distorted face, edge, and corner-sharing OCa4FeW octahedra. The corner-sharing octahedral tilt angles are 1°.