Ca3TiFe2O8 crystallizes in the monoclinic P2_1 space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 6-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 Ca site, Ca(2) is bonded in a 6-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 third Ca site, Ca(3) is bonded in a 9-coordinate geometry to one O(3), one O(4), two equivalent O(1), two equivalent O(2), and three equivalent O(8) atoms. Ti(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(7), and one O(8) atom to form TiO6 octahedra that share corners with five equivalent Fe(2)O6 octahedra and  a cornercorner with one Fe(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 16-26°. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(6), one O(7), and two equivalent O(5) atoms to form FeO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra, and corners with two equivalent Fe(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 42-43°. In the second Fe site, Fe(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(8) atom to form FeO6 octahedra that share corners with five equivalent Ti(1)O6 octahedra and  a cornercorner with one Fe(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 16-26°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Ca(1), one Ca(2), two equivalent Ca(3), one Ti(1), and one Fe(2) atom. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Ca(1), one Ca(2), two equivalent Ca(3), one Ti(1), and one Fe(2) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(2), one Ca(3), one Ti(1), and one Fe(2) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Ca(1), one Ca(2), one Ca(3), one Ti(1), and one Fe(2) atom. In the fifth O site, O(5) is bonded to one Ca(1), one Ca(2), and two equivalent Fe(1) atoms to form distorted corner-sharing OCa2Fe2 tetrahedra. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(2), one Fe(1), and one Fe(2) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(2), one Ti(1), and one Fe(1) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to three equivalent Ca(3), one Ti(1), and one Fe(2) atom.
Ca3TiFe2O8 crystallizes in the monoclinic P2_1 space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 6-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 Ca(1)-O(1) bond length is 2.87 Å. The Ca(1)-O(2) bond length is 2.46 Å. The Ca(1)-O(3) bond length is 2.36 Å. The Ca(1)-O(4) bond length is 2.48 Å. The Ca(1)-O(5) bond length is 2.36 Å. The Ca(1)-O(6) bond length is 2.47 Å. The Ca(1)-O(7) bond length is 2.30 Å. In the second Ca site, Ca(2) is bonded in a 6-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 Ca(2)-O(1) bond length is 2.46 Å. The Ca(2)-O(2) bond length is 2.88 Å. The Ca(2)-O(3) bond length is 2.45 Å. The Ca(2)-O(4) bond length is 2.35 Å. The Ca(2)-O(5) bond length is 2.36 Å. The Ca(2)-O(6) bond length is 2.31 Å. The Ca(2)-O(7) bond length is 2.48 Å. In the third Ca site, Ca(3) is bonded in a 9-coordinate geometry to one O(3), one O(4), two equivalent O(1), two equivalent O(2), and three equivalent O(8) atoms. The Ca(3)-O(3) bond length is 2.92 Å. The Ca(3)-O(4) bond length is 2.90 Å. There is one shorter (2.44 Å) and one longer (2.58 Å) Ca(3)-O(1) bond length. There is one shorter (2.44 Å) and one longer (2.58 Å) Ca(3)-O(2) bond length. There are a spread of Ca(3)-O(8) bond distances ranging from 2.41-2.99 Å. Ti(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(7), and one O(8) atom to form TiO6 octahedra that share corners with five equivalent Fe(2)O6 octahedra and  a cornercorner with one Fe(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 16-26°. The Ti(1)-O(1) bond length is 2.02 Å. The Ti(1)-O(2) bond length is 2.00 Å. The Ti(1)-O(3) bond length is 1.94 Å. The Ti(1)-O(4) bond length is 1.91 Å. The Ti(1)-O(7) bond length is 2.24 Å. The Ti(1)-O(8) bond length is 1.87 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(6), one O(7), and two equivalent O(5) atoms to form FeO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Fe(2)O6 octahedra, and corners with two equivalent Fe(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 42-43°. The Fe(1)-O(6) bond length is 1.88 Å. The Fe(1)-O(7) bond length is 1.87 Å. There is one shorter (1.95 Å) and one longer (1.96 Å) Fe(1)-O(5) bond length. In the second Fe site, Fe(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(8) atom to form FeO6 octahedra that share corners with five equivalent Ti(1)O6 octahedra and  a cornercorner with one Fe(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 16-26°. The Fe(2)-O(1) bond length is 2.02 Å. The Fe(2)-O(2) bond length is 2.05 Å. The Fe(2)-O(3) bond length is 1.99 Å. The Fe(2)-O(4) bond length is 2.02 Å. The Fe(2)-O(6) bond length is 2.15 Å. The Fe(2)-O(8) bond length is 2.02 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Ca(1), one Ca(2), two equivalent Ca(3), one Ti(1), and one Fe(2) atom. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Ca(1), one Ca(2), two equivalent Ca(3), one Ti(1), and one Fe(2) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(2), one Ca(3), one Ti(1), and one Fe(2) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Ca(1), one Ca(2), one Ca(3), one Ti(1), and one Fe(2) atom. In the fifth O site, O(5) is bonded to one Ca(1), one Ca(2), and two equivalent Fe(1) atoms to form distorted corner-sharing OCa2Fe2 tetrahedra. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(2), one Fe(1), and one Fe(2) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Ca(1), one Ca(2), one Ti(1), and one Fe(1) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to three equivalent Ca(3), one Ti(1), and one Fe(2) atom.