Ca3Fe4(WO4)6 crystallizes in the triclinic P-1 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), and two equivalent O(3) atoms to form CaO6 octahedra that share corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent W(1)O4 tetrahedra, corners with two equivalent W(2)O4 tetrahedra, corners with two equivalent W(3)O4 tetrahedra, and corners with two equivalent Ca(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 55°. In the second Ca site, Ca(2) is bonded to one O(11), one O(2), one O(5), one O(6), and one O(7) atom to form distorted CaO5 trigonal bipyramids that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one W(2)O4 tetrahedra, corners with two equivalent W(1)O4 tetrahedra, corners with two equivalent W(3)O4 tetrahedra,  an edgeedge with one Fe(1)O6 octahedra, and  an edgeedge with one Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles are 58°. There are three inequivalent W sites. In the first W site, W(1) is bonded to one O(10), one O(11), one O(3), and one O(6) atom to form WO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, and corners with two equivalent Ca(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 16-63°. In the second W site, W(2) is bonded to one O(1), one O(4), one O(7), and one O(8) atom to form WO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra, and  a cornercorner with one Ca(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 33-61°. In the third W site, W(3) is bonded to one O(12), one O(2), one O(5), and one O(9) atom to form WO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, and corners with two equivalent Ca(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 26-60°. 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 Ca(1)O6 octahedra,  a cornercorner with one W(3)O4 tetrahedra, corners with two equivalent W(1)O4 tetrahedra, corners with three equivalent W(2)O4 tetrahedra,  an edgeedge with one Fe(1)O6 octahedra, and  an edgeedge with one Ca(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 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 FeO6 octahedra that share corners with two equivalent W(1)O4 tetrahedra, corners with two equivalent W(2)O4 tetrahedra, corners with two equivalent W(3)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra, and  an edgeedge with one Ca(2)O5 trigonal bipyramid. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Ca(1) and one W(2) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Ca(1), one Ca(2), and one W(3) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Ca(1), one W(1), and one Fe(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one W(2) and two equivalent Fe(1) atoms. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Ca(2), one W(3), and one Fe(2) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Ca(2), one W(1), and one Fe(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Ca(2), one W(2), and one Fe(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one W(2) and two equivalent Fe(2) atoms. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one W(3) and one Fe(1) atom. In the tenth O site, O(10) is bonded in a linear geometry to one W(1) and one Fe(2) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Ca(2), one W(1), and one Fe(2) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one W(3) and one Fe(2) atom.
Ca3Fe4(WO4)6 crystallizes in the triclinic P-1 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), and two equivalent O(3) atoms to form CaO6 octahedra that share corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent W(1)O4 tetrahedra, corners with two equivalent W(2)O4 tetrahedra, corners with two equivalent W(3)O4 tetrahedra, and corners with two equivalent Ca(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 55°. Both Ca(1)-O(1) bond lengths are 2.34 Å. Both Ca(1)-O(2) bond lengths are 2.54 Å. Both Ca(1)-O(3) bond lengths are 2.40 Å. In the second Ca site, Ca(2) is bonded to one O(11), one O(2), one O(5), one O(6), and one O(7) atom to form distorted CaO5 trigonal bipyramids that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one W(2)O4 tetrahedra, corners with two equivalent W(1)O4 tetrahedra, corners with two equivalent W(3)O4 tetrahedra,  an edgeedge with one Fe(1)O6 octahedra, and  an edgeedge with one Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles are 58°. The Ca(2)-O(11) bond length is 2.29 Å. The Ca(2)-O(2) bond length is 2.33 Å. The Ca(2)-O(5) bond length is 2.34 Å. The Ca(2)-O(6) bond length is 2.24 Å. The Ca(2)-O(7) bond length is 2.29 Å. There are three inequivalent W sites. In the first W site, W(1) is bonded to one O(10), one O(11), one O(3), and one O(6) atom to form WO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, and corners with two equivalent Ca(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 16-63°. The W(1)-O(10) bond length is 1.85 Å. The W(1)-O(11) bond length is 1.91 Å. The W(1)-O(3) bond length is 1.91 Å. The W(1)-O(6) bond length is 1.90 Å. In the second W site, W(2) is bonded to one O(1), one O(4), one O(7), and one O(8) atom to form WO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra, and  a cornercorner with one Ca(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 33-61°. The W(2)-O(1) bond length is 1.79 Å. The W(2)-O(4) bond length is 1.84 Å. The W(2)-O(7) bond length is 1.83 Å. The W(2)-O(8) bond length is 1.83 Å. In the third W site, W(3) is bonded to one O(12), one O(2), one O(5), and one O(9) atom to form WO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, and corners with two equivalent Ca(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 26-60°. The W(3)-O(12) bond length is 1.79 Å. The W(3)-O(2) bond length is 1.84 Å. The W(3)-O(5) bond length is 1.85 Å. The W(3)-O(9) bond length is 1.79 Å. 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 Ca(1)O6 octahedra,  a cornercorner with one W(3)O4 tetrahedra, corners with two equivalent W(1)O4 tetrahedra, corners with three equivalent W(2)O4 tetrahedra,  an edgeedge with one Fe(1)O6 octahedra, and  an edgeedge with one Ca(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 55°. The Fe(1)-O(3) bond length is 2.10 Å. The Fe(1)-O(6) bond length is 2.10 Å. The Fe(1)-O(7) bond length is 2.24 Å. The Fe(1)-O(9) bond length is 2.09 Å. There is one shorter (2.21 Å) and one longer (2.24 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 FeO6 octahedra that share corners with two equivalent W(1)O4 tetrahedra, corners with two equivalent W(2)O4 tetrahedra, corners with two equivalent W(3)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra, and  an edgeedge with one Ca(2)O5 trigonal bipyramid. The Fe(2)-O(10) bond length is 2.01 Å. The Fe(2)-O(11) bond length is 2.12 Å. The Fe(2)-O(12) bond length is 2.14 Å. The Fe(2)-O(5) bond length is 2.41 Å. There is one shorter (2.16 Å) and one longer (2.33 Å) Fe(2)-O(8) bond length. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Ca(1) and one W(2) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Ca(1), one Ca(2), and one W(3) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Ca(1), one W(1), and one Fe(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one W(2) and two equivalent Fe(1) atoms. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Ca(2), one W(3), and one Fe(2) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Ca(2), one W(1), and one Fe(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Ca(2), one W(2), and one Fe(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one W(2) and two equivalent Fe(2) atoms. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one W(3) and one Fe(1) atom. In the tenth O site, O(10) is bonded in a linear geometry to one W(1) and one Fe(2) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Ca(2), one W(1), and one Fe(2) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one W(3) and one Fe(2) atom.